Arabian Journal of Chemistry (2019) 12, 388–397

King Saud University

Arabian Journal of Chemistry

www.ksu.edu.sa
www.sciencedirect.com

ORIGINAL ARTICLE

Lanthanum(III) potentiometric sensors based on

ethyl benzoyl acetateq
Eman Y.Z. Frag a,*, Refat F. Aglan b, Hala A. Mohamed a

a
Chemistry Department, Faculty of Science, Cairo University, Gamaa Str., 12613 Giza, Egypt
b
Hot Laboratory Center, Atomic Energy Authority, Cairo, Egypt

Received 25 July 2016; accepted 26 November 2016

Available online 5 December 2016

KEYWORDS Abstract Modified carbon paste electrode (CPE) and screen printed electrode (SPE) based on
SPE; ethyl benzoyl acetate (EBA) were prepared and investigated as lanthanum ion selective electrodes.
CPE; Effect of various plasticizers (o-NPOE, TCP, DBP, DOS, and DOP) and ionophore content was
Lanthanum(III); studied. The reaction mechanism between La(III) and b-diketone ionophore at the electrode surface
b-diketone; was studied through scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX)
SEM; and IR spectra measurement. The best performance was obtained using modified SPE and CPE
EDX electrodes with o-NPOE and TCP plasticizers. These electrodes showed potentiometric response
with a Nernstian slope of 21.0, 19.5 and 20.5 mV decade
1 over a concentration range from
1.0  10
6 to 1.0  10
2 mol L
1 with a fast response time of 9, 10 and 13 s over the linear concen-
tration range for modified SPE (electrode I; TCP plasticizer) and two modified CPE plasticized with
o-NPOE (electrode II) and TCP (electrode III), respectively. The electrodes exhibited constant
potentiometric response in pH range 4–8, 5–8 and 4–7 for electrodes I, II and III, respectively. They
showed satisfactory good sensitivity toward lanthanum ions with regard to most common transition
metal ions. The sensors were applied for determination of La(III) ion in different water samples (tap
water and wastewater) with satisfactory and good reproducibility results.
Ó 2016 The Authors. Production and hosting by Elsevier B.V. on behalf of King Saud University. This is
an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

1. Introduction

q The reaction mechanism between La(III) and ethyl benzoyl

acetate ionophore at the electrode surface was studied through
scanning electron microscopy (SEM) energy dispersive X ray (EDX)
and IR spectra measurement.
* Corresponding author.
E-mail address: e_uossry@yahoo.com (E.Y.Z. Frag).
Peer review under responsibility of King Saud University.
Production and hosting by Elsevier
Lanthanides were considered due to the unique physical and chemical
properties of the rare earth elements (REEs). Lanthanides were used
widely in metallurgy, medicine, chemical engineering, electronics and
electrooptics, biomedicine, for manufacturing of magnetostriction
materials, lasers, storage batteries with long service life for electric
vehicles, etc. (Tadjarodi et al., 2015). Lanthanum was one of lan-
thanide elements found in rare earth minerals such as cerite, monazite,
allanite and bastnasite (Khan et al., 2014). Lanthanum(III) was consid-
ered as fission products. It may be leaked to the environment and cause
risks. So they were considered as hazardous materials (Besharati-
Seidani and Shamsipur, 2015). The lanthanum alloy LaCo5 was used

http://dx.doi.org/10.1016/j.arabjc.2016.11.015
1878-5352 Ó 2016 The Authors. Production and hosting by Elsevier B.V. on behalf of King Saud University.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
Lanthanum(III) potentiometric sensors
as a permanent magnet and LaNi5 for hydrogen storage. Its high index
of refraction made very pure La2O3 a useful additive to optical glass
for camera lenses (Singh et al., 2012).
Because of the discharge of lanthanum ions in the environment and
its useful and harmful biological activity, the La(III) ion determination
was carried out using different analytical methods. These methods
included flame photometry, atomic absorption spectrometry, induc-
tively coupled plasma-mass spectrometry (ICP-MS) Islamnezhad
et al. (2011), ion chromatography (Al-Shawi and Dahl, 1996), atomic
emission spectrometry (Jia et al., 2008), inductively coupled plasma-
optical emission spectrometry (ICP-OES) Waqar et al. (2009), sector
field inductively coupled plasma mass spectrometry (Chung, 2009)
and electrothermal vaporization inductively coupled plasma mass
spectrometry (Zhang et al., 2007), etc.
During last two decades, a general interest in metal b-diketonates
(Mehrotra et al., 1978) was reflected in the chemistry of lanthanides.
This resulted in detailed investigation unfolding some lesser known
facts of general lanthanide coordination chemistry. Early methods
used for preparation of lanthanide tris-b-diketonates were examined
previously (Moeller et al., 1961). It was established that the products
from aqueous solutions were invariably hydrates while sometimes
hydroxy derivatives were also formed. A large number of
b-diketonates of lanthanides were prepared (Dutt et al., 1971; Dutt
and Rahut, 1971; Dutt and Samyal, 1971; Stites et al., 1948).
One of the most important analytical techniques capable of deter-
mining both organic and inorganic materials in medico-biological
practice (Mohamed et al., 2013) was ion selective electrodes (ISE).
There was a constant progress in the number of electrodes capable
of selectively determining large numbers of metal ions such as carbon
paste electrodes (CPEs). Although the CPEs had an important role in
the electrochemical analysis, the prepared pastes were soft, non-
compactable and had to be packed into a special piston shaped holder.
However, in the case of determinations in flowing streams or field
monitoring with portable analyzers, the shapes and designs of such
sensors were not suitable for every purpose as where the respective
detection units need sensors of special characters (Svancara et al.,
2005).
While screen printing electrodes were reproducible, inexpensive
and sensitive disposable electrochemical electrodes were used for the
determination of trace levels of substances in environmental, pharma-
ceutical and biomedical samples (Fanjul-Bolado et al., 2008).
The use of modified chemical sensors in determination of metal
ions was developed in recent years as they provide fast, accurate, sen-
sitive, reliable and low cost method rather than the methods mentioned
before. So the aim of the present paper was to fabricate modified
screen printed electrode (electrode I) and carbon paste electrodes
(II and III) with ethyl benzoyl acetate (EBA) as electroactive material
for selective determination of lanthanum (III) ion in different water
samples.
The type and content of ionophore, suitable pH, plasticizer type,
effect of interfering ions and temperature effect on the performance
of the electrodes were also studied. The reaction mechanism at the elec-
trode surface was studied using IR spectra. The change in the electrode
surface as the results of complex formation between EBA ionophore
and La(III) ion was studied using SEM, EDX and IR spectra. The
method was successfully applied for determination of lanthanum(III)
ion in different real water samples using spiking technique. Method
validation parameters were optimized according to ICH guidelines
and the proposed potentiometric method can be applied successfully
for the determination of La(III) ions in routine samples.
2. Experimental
2.1. Materials
Reagent grade acetyl acetone (AA), b-diketone 1-benzoyl-2-
nonanone (Lix 54), ethylacetoacetate (EAA), and ethyl
389
benzoyl acetate (EBA) were supplied from Aldrich as elec-
troactive materials. Lanthanum chloride was supplied from
Aldrich. Graphite fine powder (extra pure) was of analytical
grade and purchased from Merck. High molecular weight
polyvinyl chloride (PVC) powder was supplied from Aldrich,
while o-nitrophenyl octyl ether (o-NPOE) was supplied from
Fluka. Dioctylphthalate (DOP), tricresyl phosphate (TCP),
dibutyl phthalate (DBP) and dioctylsebacate (DOS) were sup-
plied from BDH. Acetone and cyclohexanone were supplied
from Fluka (Switzerland).
2.2. Apparatus and emf measurements
Digital Hanna pH/mV meter (model 8417) was used for all
potentiometric measurements at 25 °C. Spectrophotometer
(U-2001, model 121-0032 Hitachi, Tokyo, Japan) and scanning
electron microscope (National Research Center Quanta
FEG250) were used and microanalysis was completed using
the energy dispersive X-ray analyzer (EDX) (National research
center, Egypt). FT-IR spectra were recorded on a Perkin-
Elmer 1650 spectrometer (4000–400 cm
1) in KBr pellets at
the Microanalytical Center, Cairo University, Egypt. Ag/AgCl
reference electrode contains 10% (w/v) potassium chloride.
2.3. Sensors preparation (screen printed and carbon paste)
CPEs were prepared using Teflon holder for carbon paste
filling as the electrode body, and the carbon paste was formed
by mixing graphite powder (250 mg), a suitable liquid
binder (DOP, TCP, DBP, DOS or o-NPOE) (100 lL) and
2.5–12.5 mg of ionophore. This matrix was thoroughly mixed
in the mortar and the resulted paste was used to fill the
electrode body. A new carbon-paste surface was obtained by
pushing gently the stainless-steel screw forward.
SPEs were printed in arrays of six couples consisting of the
working electrodes (each 5  35 mm) following the procedures
previously described (Nour El-Dien et al., 2012; Frag et al.,
2011a–c, 2012; Akl et al., 2013; Mohamed et al., 2010). A poly-
vinyl chloride flexible sheet (0.2 mm) was used as a substrate
which was not affected by the curing temperature or the ink
solvent and easily cut by scissors. The working electrodes were
printed using homemade carbon ink (prepared by mixing
1–15 mg of EBA electroactive material, 450 mg TCP, 1.25 g
of polyvinyl chloride (8% wnv) and 0.75 g carbon powder).
They were printed and cured at 50 °C for 2 h. A layer of an
insulator was then placed onto the printed electrodes, leaving
a defined rectangular shaped (5  5 mm) working area and a
similar area (for the electrical contact) on the other side. Fabri-
cated electrodes were stored at 4 °C and used directly in the
potentiometric measurements without any preconditioning.
2.4. EMF measurements
The emf measurement with the plasticized SPE and CPEs was
carried out with the following cell assemblies:
AgjAgCljsatd: KClksample solutionjsensor ðCPE and SPEÞ:
The detection limit was taken at the point of intersection of
the extrapolated linear segments of the calibration curve which
was plotted with emf as a function of the negative logarithm of
lanthanum ion concentration, and the selectivity of the
390
electrodes is obtained by measuring the selectivity coefficient

1
(Kpot
La,J) using the separate solution method using 0.001 mol L
La(III) and interfering ions.
2.5. Determination of La(III) ion in different water samples
Tap water and wastewater samples were collected from differ-
ent environment filtered and analyzed for La(III) ion by the
proposed method. Tap water (sample 1) and wastewater (sam-
ple 2) samples were supplied from Sandoub, Mansoura,
Dakahliya, Egypt.
The water samples were spiked with known amounts of lan-
thanum(III) ion, the pH was adjusted with acetate buffer
(pH = 4) and they were analyzed by the proposed general
procedure.
For spectrophotometric measurements at 430 nm a given
amount of alizarin Red S was added to 5 beakers containing
10 ml spiked water samples with acetate buffer solution and
the pH of the solution was adjusted to 4.60 with hydrochloric
acid or sodium hydroxide and then diluted to 50 ml. This was
followed by absorbance measurements. The molecular ratio of
lanthanum:alizarin Red S is 1:2 (Kawashima et al., 1961).
2.6. Surface analysis
Scanning electron microscope (SEM) and energy dispersive
X-ray (EDX) analyzer were used for morphological analysis
of the sensors surface at 4000 magnifications for electrodes
I and III before and after the interaction with lanthanum
(III) ion.
3. Result and discussion
3.1. Electrode composition
3.1.1. Type of ionophore
An important requirement for the preparation of an ion selec-
tive sensor was the electroactive material (ionophore), which
was used in the paste. It should exhibit high lipophilicity and
strong affinity for a particular ion to be determined and poor
affinity for others. They should have rapid exchange kinetics
and adequate complex formation constants in the paste and
should be well soluble in the paste matrix. It should have a suf-
ficient lipophilicity to prevent leaching from the paste into the
sample solution.
The lanthanum ion showed high affinity toward b-diketone
compounds due to the higher oxidation-reduction potential,
higher bond energy with oxygen and larger atomic radius
(Bian et al., 2006). Different b-diketone compounds namely
acetyl acetone (AA), Lix 54, ethyl acetoacetate (EAA), and
ethyl benzoyl acetate (EBA) were used to study the selectivity
toward lanthanum(III) ion showing potentiometric response
with slope values of 23.0, 18.0, 12.5 and 19.9 mV decade
1,
respectively. It was obvious that the EBA ionophore was the
best electroactive material toward lanthanum(III) ion since it
gave the best slope within the studied concentration range.
3.1.2. Ionophore content
Different amounts of EBA ionophore as electroactive material
were used to prepare the modified SPE and CPEs for La(III)
E.Y.Z. Frag et al.
ion determination. The potential response is shown in Figs. 1
and 2 for modified SPE and CPEs electrodes, respectively.
It was found from the figures that the sensors modified with
2.5 mg and 10 mg of EBA ionophore which was the most effec-
tive amount gave the best sensitivity with the best Nernstian
slope of 21.0, 19.9 and 20.5 mV decade
1, over a wide concen-
tration range from 1.0  10
6 to 1.0  10
2 mol L
1 with a
good correlation coefficient and very low detection limit for
electrodes I, II and III, respectively. The limits of detection
were determined from the intersection of the two extrapolated
segments of the calibration plots and were found to be
1.0  10
6 mol L
1.
3.1.3. Effect of plasticizers type in CPE
The nature of plasticizer was expected to play a key role in
determining the ion-selective characteristics as it influences
the dielectric constant of the paste of the electrode, the mobil-
ity of the ionophore molecule and state of ligand (Gupta et al.,
2003). It also caused selective extraction of the target ion which
created the electrochemical phase boundary potential due to
thermodynamic equilibria at the interface. So, various plasti-
cizers were used namely DBP, DOP, o-NPOE, DOS and
TCP in order to study their influence on the performance of
the sensors.
Among these plasticizers, o-NPOE and TCP provided fas-
ter, more stable and sensitive response in the concentration
range from 1.0  10
6 to 1.0  10
2 mol L
1 as shown from
the graph. The slope was 19.9 and 20.5 mV per decade for
CPE electrodes II and III, respectively. This can be explained
due to its high dielectric constant and relatively high molecular
weight.
According to the Lubricating Theory of plasticization
(Wilkes et al., 2005), the plasticizer molecules diffuse into the
polymer and act as shields to reduce polymer–polymer interac-
tive forces (van der Waals forces) and hence prevent the forma-
tion of a rigid network. This lowers the PVC Tg and allows the
polymer chains to move rapidly each other, resulting in
Fig. 1 Effect of ionophore content on potential response
of SPE (electrode I) for determination of La(III) in acetate buffer
(pH = 4).
Lanthanum(III) potentiometric sensors
Fig. 2 Effect of ionophore content on potential response of CPE
(electrode III) for determination of La(III) in acetate buffer
(pH = 4).
increased flexibility, softness, and elongation. Different plasti-
cizers yield different plasticization effects because of the differ-
ences in the strengths of the plasticizer–polymer and
plasticizer–plasticizer interactions. At low plasticizer levels,
the plasticizer–PVC interactions were the dominant interac-
tions, while plasticizer–plasticizer interactions can become
more significant at high plasticizer concentrations. The polar
portion of the molecule must be able to bind reversibly with
the PVC polymer, thus softening the PVC, while the non-
polar portion of the molecule allows the PVC interaction to
be controlled so it is not so powerful a solvator as to destroy
the PVC crystallinity.
3.1.4. Surface characterization
In order to characterize the morphology of the CPE and SPE,
scanning electron microscopy (SEM) and energy dispersive
X-ray (EDX) analyzer were used as shown in Figs. 3–6. All
electrodes surfaces showed a similar configuration with ran-
domly directed graphite particles ensemble into an insulator
matrix (PVC or plasticizer for SPE and CPE, respectively)
where the graphite particle size is longer for CPE than for
SPE, so this distribution of the electrode material in case of
SPE (microelectrodes) could lead to a highly packed structure.
SPE showed a more uniform surface topography rather than
CPE. Incorporation of a suitable ionophore in the paste fol-
lowed by soaking of the sensors in La(III) ion solution led to
the complex formation between the La(III) ions and EBA
ionophore which was observed in filling the space between gra-
phite surface after the interaction with La(III) ion. Formation
of ionophore-La3+ complex at electrode surface which was
subsequently extracted by the plasticizer into the paste is
shown in Figs. 4 and 6. These data are supported by IR spectra
as shown in Figs. 7 and 8, where the ligand EBA exhibited
medium intensity bands at 1740 and 1685 cm
1 due to
t(C‚O) of benzoyl and ester groups for electrodes I and III,
respectively. After soaking electrodes I and III in La(III) ion
solution for 1 h and carrying out IR spectra, a difference in
391
the spectra is observed. The bands due to t(C‚O) of benzoyl
and ester groups were shifted to lower wave numbers in the
spectrum (1729 and 1644 for electrode I and 1741 and
1613 cm
1 for electrode III) suggesting complex formation
via coordination of the EBA ionophore to La(III) ion through
the C‚O of benzoyl and C‚O of ester groups .
3.2. The effect of pH
The pH dependence of the electrode potential was investigated
over the pH range of 2.0–10.0 in a 1.0  10
3 and 1.0  10
5
mol L
1 solution of La(III) ion. The pH was adjusted by using
very small volumes of HCl and NaOH solutions. The results
indicated that the potential was independent of pH in the
range of 4–8, 5–8 and 4–7 for electrodes I, II and III, respec-
tively. Outside this range, the potential changed significantly.
The increase of potential below pH 4.0 may be ascribed to
the competitive binding of protons to the ligands on the elec-
trode surface rather than La(III) ion. The decrease of potential
above pH 8.0 can be accounted for to the formation of hydro-
xyl complexes of La(III) such as La(OH)+2, La(OH)+ 2 and La
(OH)3 which monished its ability to combine with the carrier
(Yuan et al., 2013; Shamsipur et al., 2002).
3.3. Response time
The time it takes for the electrode potential of an ion selective
electrode to become stable within a range of variation of
±1 mV depends on electrode type and structure, ion type,
concentration, and ionic strength. The response time when
measuring a high ion concentration after measuring low ion
concentrations was relatively short, while a longer response
time was obtained for the reverse process. Additionally, at
around the minimum measurement limit, the response time
was generally relatively long, being of the order of several
minutes. Hence, when using the ion electrode method, it was
necessary to wait until the potentiometer indicated a stable
value before taking a reading (Eric et al., 1997).
One of the most important factors for any ion-selective
electrode is response time. The practical response time of the
sensor was recorded by observing the potential change over
a concentration range from 1.0  10
6 to 1.0  10
2 mol L
1
of La(III). The potentials versus time traces are shown in
Fig. 9.
As can be shown in Fig. 9, electrodes reached their equilib-
rium responses in a very short time of 9, 10 and 13 s over the
linear concentration range for electrodes I, II and III, respec-
tively. This may be due to the fast exchange kinetics of com
plexation–decomplexation of La(III) ion with the ionophore
at the paste of the electrodes (Ganjali et al., 2004).
3.4. Effect of temperature
One of the important parameters which has effect on the per-
formance of the sensors is the change of temperature at test
solution. The stability of the electrodes was studied within
the temperatures 10, 20, 30, 40, 50 and 60 °C. The electrode
exhibited good Nernstian behavior in the temperature range
(10–50 °C). The slope of electrode did not show a good
Nernstian behavior at higher temperature. The standard cell
potentials (E°Cell), were determined at different temperatures
392 E.Y.Z. Frag et al.

Fig. 3 SEM images for SPE surface, electrode I (a) before and (b) after soaking in 1  10
3 mol L
1 La(III) ion.

Fig. 4 EDX of SPE surface, electrode I (a) before and (b) after soaking in 1.0  10
3 mol L
1 La(III) ion.

Fig. 5 SEM images for CPE surface, electrode III (a) before and (b) after soaking in 1  10
3 mol L
1 La(III) ion.
Lanthanum(III) potentiometric sensors
Fig. 6 EDX of CPE surface, electrode III (a) before and (b) after soaking in 1.0  10
3 mol L
1 La(III) ion.
Fig. 7 IR spectra for electrode III (a) before and (b) after
soaking in 1.0  10
3 mol L
1 La(III) ion.
from the respective calibration plots as the intercepts of these
plots at p La(III) = 0, and were used to determine the isother-
mal temperature coefficient (dE0/dt) of the cell with the aid of
the following equation (Khalil and El-Aliem, 2002;
Electrochemistry, 1972):
E0cell þ E0reference ¼ E0electrode
Plot of E0 electrode versus (t–25) gave a straight line. The
slope of the line was taken as the isothermal temperature coef-
ficient of the La (III) electrode. It amounted to 0.121  10
2,
0.55  10
3 and 0.245  10
2 V/°C for electrodes I, II and
III, respectively. The small values of (dE0/dt)cell and
(dE0/dt)electrode revealed the high thermal stability of the
electrodes within the investigated temperature range.
393
Fig. 8 IR spectra for electrode I (a) before and (b) after soaking
in 1.0  10
3 mol L
1 La(III) ion.
3.5. Selectivity
Clearly, the selectivity was one of the most important charac-
teristics of a sensor. It often determines whether a reliable mea-
surement in the target sample was possible or not. In clinical
applications, it was critical where the allowed emf deviation
(error) may sometimes not be larger than 0.1 mV for whole
blood or serum measurements. Theoretically, selectivity
description allowed researchers to identify the key parameters
for optimizing the performance of potentiometric sensors, e.g.,
by adjusting weighing parameters (i.e., absolute membrane
concentrations) or choosing different plasticizers or matrices
(Eric et al., 1997). Ion selective electrodes have the most impor-
tant characteristic that is its relative response to other ions pre-
sent in solution, which expressed in terms of selectivity
coefficients (KPotA,B). Different methods can be used for measur-
ing the selectivity coefficients of the electrode such as separate
394
Fig. 9 Dynamic response time of (a) electrode I, (b) electrode II and (c) electrode III for La(III) in acetate buffer (pH = 4).
solution method (SSM) Bakker et al. (2000) and matched
potential method (MPM) Lindner and Umezawa (2008). In
the present study SSM was used which depends on measuring
the potential of a cell comprising an ISE and a reference elec-
trode with two separate solutions. One contains the ion of
interest A at the activity aA (but no B) and the other contains
the interfering ion B at the same activity aB = aA (but no A).
In this method, the values of the selectivity coefficient can be
derived from the following equation:
A;B ¼ ½ðEB
EA Þ=S þ ð1
ðZB =ZA ÞÞ log aA
log Kpot
EA and EB mean the potentiometric response of aA and aB,
respectively. aA is the primary ion activity and aB is the activity
of an interfering ion. The single ion activities were calculated
by the extended Debye-Hückel equation (Kamata et al., 1998).
In this work, aA (1.0  10
3 mol L
1 La(III) ion) and aB
(1.0  10
3 mol L
1 interfering ion) were used to measure
the selectivity coefficients. S, Nernstian slope, ZA and ZB are
the charge of the primary and interfering ions, respectively.
The selectivity coefficient values are listed in Table 1. The value
of selectivity coefficient reached to 1.0 indicated equal response
to both primary ion and interfering ions. If the value of
E.Y.Z. Frag et al.
selectivity coefficient was smaller than 1.0, it showed that the
sensor was selective to the primary ion over the interfering
ions. The data given in Table 1 indicate that the electrodes
(I and III) have good selectivity toward the lanthanum ion
than other metal ions. But for electrode II, it had good selec-
tivity toward primary lanthanum ion except in the presence
of Al(III), Ca(II) and Mg(II) ions, and it showed interfering
ion with those metal ions.
3.6. Life time
Electrodes (I–III) were tested at different intervals to follow up
its life time and reproducibility. It was clear from the figure
that modified SPE had the longest life time up to three weeks.
The surface of CPEs was continuously polished using a fil-
ter paper during calibration process to obtain new working
surface and rinsed carefully with double distilled water to
remove the memory effect of electrode. This indicated that
the SPE had high mechanical durability and good adherent
properties. Longer stability test was also investigated and the
electrodes were successfully used for at least 50 consecutive
measurements without any preconditioning before use.
Lanthanum(III) potentiometric sensors 395

1.0  10
2 mol L
1, and the minimum was 1.0  10
6
Table 1 Potentiometric selectivity coefficient values of elec-
mol L
1. The proposed Lanthanum ion-selective electrodes
trodes I, II and III using SSM.
(I-III) were used for potentiometric determination of lan-
SPE Electrode I CPE thanum(III) ion in different water samples (waste and tape
(2.5 mg EBA) water). As mentioned above in procedure (2.7) the samples
Electrode II Electrode III
Interfering Log KpotLa3+,B Log KpotLa3+,B Log KpotLa3+,B were treated and analyzed. The results obtained were also
Species compared with those from spectrophotometric analysis. The
Fe3+
11
16
21 results obtained and listed in Table 2 indicated the successful
Mn2+
9.7
10
5.7 use of the proposed electrodes (I-III) for determination of lan-
Sr2+
9.61
9
5.8 thanum ion and there was a satisfactory agreement with those
Na+
13.43 – – obtained by spectrophotometric method.
Ce3+ –
16
15
Ni2+
9.07
10.1
4.7 3.8. Method validation
Co2+
8.64
7.6
6.8
Pb2+
10.78
9.1
7.6
3.8.1. Inter- and intra-day accuracy and precision
Zn2+
8.40
2.4
5.4
Fe2+
10.07
3.2
6 Different real water samples spiked with different concentra-
K+
11.33
10
9 tions of La(III) ion were used to carry out four replicate exper-
Ba2+
8.73
3.8
7.2 iments to evaluate the validity and applicability of the
Cd2+
9.40
4.2
5.3 proposed method and reproducibility of the results obtained.
Cr3+
9.40
6.05
8.6 Tables 3 and 4 show the values of the inter- and intra-day rel-
Mg2+
7.97
2.5
5
ative standard deviations for different concentrations of the
Al3+
7.62
2.7
7.7
samples, obtained from experiments carried out over a period
Cu2+
10.07
4
10
Ca2+
7.02
2.9
4.7 of four days (inter-day) or within the same day (intra-day). It
Zr4+
10.01 – – was found that, modified SPE had reproducible response in the
V5+
5.28 – – intra-day measurements rather than modified CPE which need
to scratch the paste surface to remove the memory effect and
obtain a new surface electrode and this is considered an advan-
tage of SPE over CPE. From the data obtained, the relative
3.7. Analytical application
standard deviations were found to be small indicating reason-
able repeatability of the proposed sensors, so modified CPEs
In general, the maximum La(III) ion concentration that and SPE were successfully applied to determine La(III) in pure
ion selective electrodes can measure was found to be and wastewater samples.

Table 2 Determination of lanthanum(III) ion in water samples using proposed sensors (I–III).
Sample Taken Spectrophotometry Electrode II Electrode III Electrode I
(mg mL
1)
Found % Found % Found % Found %
(mg mL
1) Recovery (mg mL
1) Recovery (mg mL
1) Recovery (mg mL
1) Recovery
2 3.22 3.22 100.0 3.16 98.13% 3.14 97.52% 3.21 99.69%
2 1.611 1.67 103.6 1.59 98.69% 1.68 104.28% 1.611 100.0%
1 0.322 0.33 102.4 0.322 100.0% 0.322 100.0% 0.331 102.79%
1 1.611 1.66 103.0 1.58 98.08% 1.69 104.90% 1.585 98.39%

Table 3 Intra and inter days precision of the determination of La (III) in pure and spiked water samples using SPE (electrode I).
Taken, mg mL
1 Found, mg mL
1 Recovery % SD RSD %
Inter day Intra day Inter day Intra day Inter day Intra day Inter day Intra day
Pure 3.249 3.235 3.216 99.57 98.90 1.270 0.577 1.29 0.542
0.325 0.318 0.322 97.80 99.00 0.350 0.955 0.359 0.793
0.033 0.033 0.032 100.0 96.90 0.411 0.478 3.87 0.367
Water sample No. 1 0.322 0.322 0.331 100.0 102.8 0.478 0.478 4.012 1.239
1.611 1.600 1.585 99.32 98.39 0.500 0.500 5.714 0.836
Water sample No. 2 3.220 3.190 3.210 99.07 99.69 0.500 0.478 6.800 0.644
1.611 1.609 1.611 99.88 100.0 0.478 0.500 6.490 1.290
396 E.Y.Z. Frag et al.

Table 4 Inter -days precision of the determination of La (III) in pure and water samples using CPE (electrodes II and III).
Taken, Found, mg mL
1 Recovery % SD RSD %
mg mL
1
Electrode Electrode Electrode Electrode Electrode Electrode Electrode Electrode
II III II III II III II III
Pure 0.325 0.321 0.316 98.70 97.23 0.500 0.157 1.526 3.125
0.033 0.032 0.032 98.00 96.97 0.478 0.479 2.139 0.450
Water sample 0.322 0.317 0.322 98.44 100.0 0.816 0.525 2.148 0.416
No. 1 1.611 1.610 1.690 99.90 104.9 0.500 0.816 6.870 0.703
Water sample 3.220 3.160 3.270 98.14 101.55 0.478 0.816 7.509 0.595
No. 2 1.611 1.611 1.680 100.0 104.28 0.577 0.645 0.289 0.431

Table 5 Response characteristics of the investigated modified electrodes.

Parameters Electrode I Electrode II Electrode III
Slope, mV decade
1 21.0 20.5 19.5
Linear range, mol L
1 1.0  10
6–1.0  10
2 1.0  10
6–1.0  10
2 1.0  10
6–1.0  10
2
Limit of detection, mol L
1 1.0  10
6 1.0  10
6 1.0  10
6
Limit of quantification, mol L
1 3.3  10
6 3.3  10
6 3.3  10
6
Working pH range, 4–8 5–8 4–7
Life time, days 25 8 8
SD 0.879 0.288 0.894
RSD 0.998 0.962 0.999
Intercept 176 199.6 204
Recovery % 101 99.0 100
Isothermal coefficient V/°C 0.121  10
2 0.55 10
3 0.2450
2

3.8.2. Limits of detection and quantification
The limit of quantification (LOQ) was determined by estab-
lishing the least concentration that can be measured according
to ICH Q2(R1) recommendations, below which the calibration
range was non linear. The results obtained are listed in Table 5.
The limit of detection (LOD) was determined by evaluating the
lowest concentration of the measuring ions analytes that can
be readily detected and were found to be 1.0  10
6 mol L
1.
The LOQ and LOD were calculated according to the following
equations (ICH 2005):
LOQ ¼ 10 Sa =b
LOD ¼ 3 Sa =b
where (Sa) is the standard deviation of the intercept of the
regression line and (b) is the slope of the calibration curve.
3.8.3. Linearity
The calibration graphs obtained by plotting the potential val-
ues versus the final concentration were found to be rectilinear
over the concentration range cited in Table 5.
4. Conclusion
In this work, modified ion selective electrodes (carbon paste
and screen printed) were fabricated based on EBA as
ionophore. The proposed electrodes possessed excellent perfor-
mance in determination of La(III) in tap water and wastewater
with high recovery in comparison with spectrophotometric
method with high sensitivity, good selectivity, fast response,
and low detection limit with Nernstian behavior over a wide
concentration range.
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