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Analysis Methods of Chloride Ions with Industrial Applications

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 BULETINUL
INSTITUTULUI
POLITEHNIC
DIN IAŞI

Tomul LX (LXIV)
Fasc. 2

CHIMIE şi INGINERIE CHIMICĂ

2014 Editura POLITEHNIUM

 BULETINUL INSTITUTULUI POLITEHNIC DIN IAŞI
PUBLISHED BY
“GHEORGHE ASACHI” TECHNICAL UNIVERSITY OF IAŞI
Editorial Office: Bd. D. Mangeron 63, 700050, Iaşi, ROMÂNIA
Tel. 40-232-278683; Fax: 40-232-237666; e-mail: polytech@mail.tuiasi.ro

Editorial Board
President: Prof. dr. eng. Ion Giurma, Member of the Academy of Agricultural
Sciences and Forest, Rector of the “Gheorghe Asachi” Technical University of Iaşi
Editor-in-Chief: Prof. dr. eng. Carmen Teodosiu, Vice-Rector of the
“Gheorghe Asachi” Technical University of Iaşi
Honorary Editors of the Bulletin: Prof. dr. eng. Alfred Braier,
Prof. dr. eng. Hugo Rosman,
Prof. dr. eng. Mihail Voicu, Corresponding Member of the Romanian Academy

Editor in Chief of the CHEMISTRY and CHEMICAL ENGINEERING

Section
Prof. dr. eng. Teodor MăluŃan
Associated Editor: Lecturer dr. chem. Gabriela Apostolescu

Editorial Advisory Board

Prof.dr.eng. Dan Caşcaval, “Gheorghe Asachi”
Technical University of Iaşi
Prof.dr.eng. Gabriela Cârjă, “Gheorghe Asachi”
Technical University of Iaşi
Prof.dr.eng. Silvia Curteanu, “Gheorghe Asachi”
Technical University of Iaşi
Prof.dr. Jurek Duszczyk, Delft University of
Technology, Netherlands
Prof.dr.eng. Anca Galaction, University
“Gr.T.Popa”, Iaşi
Prof.dr.eng. Maria Gavrilescu, “Gheorghe Asachi”
Technical University of Iaşi
Prof.dr.eng. Dan Gavrilescu, “Gheorghe Asachi”
Technical University of Iaşi
Assoc.prof.dr.eng. Doina Horoba, “Gheorghe
Asachi” Technical University of Iaşi
Assoc.prof.dr.eng. Eugen Horoba, “Gheorghe
Asachi” Technical University of Iaşi
Prof.dr. eng. Vasile Hulea, Institut Charles Gerhardt,
FranŃa
Prof.dr.eng. Nicolae Hurduc, “Gheorghe Asachi”
Technical University of Iaşi
Prof.dr.eng. Florin Dan Irimie, University Babeş-
Bolyai, Cluj- Napoca
Assoc.prof.dr.eng. Gabriela Lisă, “Gheorghe
Asachi” Technical University of Iaşi
Prof.dr.eng. Matei Macoveanu, “Gheorghe Asachi”
Technical University of Iaşi
Prof.dr.eng. Ion Mangalagiu, “Al.I.Cuza” University,
Iaşi
Prof.dr.eng. Ioan Mămăligă, “Gheorghe Asachi”
Technical University of Iaşi
Prof.dr. Shin’ichi Nakatsuji, University of Hyogo,
Japonia
Prof.dr.eng. Ionel Marcel Popa, “Gheorghe Asachi”
Technical University of Iaşi
Prof.dr.eng. Marcel Popa, “Gheorghe Asachi”
Technical University of Iaşi
Prof.dr.eng. Valentin I. Popa, “Gheorghe Asachi”
Technical University of Iaşi
Prof.dr.eng. Aurel Pui, “Al.I.Cuza” University,
Iaşi
Prof.dr. Nicolas Sbirrazzuoli, Université de Nice
Sophia Antipolis, FranŃa
Prof.dr.eng. Dan Scutaru, “Gheorghe Asachi”
Technical University of Iaşi
Academician prof.dr.eng. Bogdan Simionescu,
“Gheorghe Asachi” Technical University of Iaşi
Prof.dr.eng. Dan Sutiman, “Gheorghe Asachi”
Technical University of Iaşi
Assoc.prof.dr.eng. Dana Şuteu, “Gheorghe Asachi”
Technical University of Iaşi
Prof.dr.eng. Mihai VâŃă, “Gheorghe Asachi”
Technical University of Iaşi
ISSN 0254-7104
BULETINUL INSTITUTULUI POLITEHNIC DIN IAŞI
BULLETIN OF THE POLYTECHNIC INSTITUTE OF IAŞI
Tomul LX (LXIV), Fasc. 2 2014

CHIMIE şi INGINERIE CHIMICĂ

SUMAR
Pag.
ADRIANA MARINOIU, CONSTANTIN TEODORESCU, DANIELA
MARINESCU, MIHAI VARLAM, CLAUDIA COBZARU,
AMALIA SOARE şi CRISTINA IONESCU, Grafene pentru pile de
combustie (engl., rez. rom.) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
ETELKA DAVID şi IOAN MĂMĂLIGĂ, Materiale pe bază de carbon
nanostructurate pentru adsorbŃia compuşilor organici volatili (engl.,
rez. rom.) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
LOREDANA FLUERARU, GABRIELA RĂUL, MĂDĂLINA TĂTARU şi
LAURA BULGARIU, Metode de analiză a ionilor clorură cu aplicaŃii
industriale (engl., rez. rom.) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
CORINA CERNĂTESCU, CLAUDIA COBZARU, ROXANA CANTA şi
ADRIANA MARINOIU, Sinteza a patru noi hidroxiazometine (engl.,
rez. rom.) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
SUSANA SOLANO ARANA şi GABRIELA CIOBANU, Sinteza şi
caracterizarea zeolitului H-ZSM-5 (engl., rez. rom.) . . . . . . . . . . . . . . . 67
IRINA DĂBULEANU, MIHAELA GABRIELA DUMITRU şi AURORA
REISS, ObŃinerea unui biofertilizant pe bază de acizi humici şi
galactomanani extraşi din seminŃele de Gleditsia triacanthos folosit în
fertilizarea extraradiculară a plantelor (engl., rez. rom.) . . . . . . . . . . . . . 75
BULETINUL INSTITUTULUI POLITEHNIC DIN IAŞI
BULLETIN OF THE POLYTECHNIC INSTITUTE OF IAŞI
Tomul LX (LXIV), Fasc. 2 2014

CHEMISTRY and CHEMICAL ENGINEERING

CONTENTS Pp.

ADRIANA MARINOIU, CONSTANTIN TEODORESCU, DANIELA

MARINESCU, MIHAI VARLAM, CLAUDIA COBZARU,
AMALIA SOARE and CRISTINA IONESCU, Graphene-Based
Materials for Fuel Cell Applications (English, Romanian summary) . . . 9
ETELKA DAVID and IOAN MĂMĂLIGĂ, Modified Nanotextured Carbon
Materials for Volatile Organic Compounds Adsorption (English,
Romanian summary) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
LOREDANA FLUERARU, GABRIELA RĂUL, MĂDĂLINA TĂTARU and
LAURA BULGARIU, Analysis Methods of Chloride Ions with
Industrial Applications (English, Romanian summary) . . . . . . . . . . . . . 45
CORINA CERNĂTESCU, CLAUDIA COBZARU, ROXANA CANTA and
ADRIANA MARINOIU, Synthesis of Four New Hydroxyl
Azomethines (English, Romanian summary) . . . . . . . . . . . . . . . . . . . . . 57
SUSANA SOLANO ARANA and GABRIELA CIOBANU, Synthesis and
Characterization of H-ZSM-5 Zeolite (English, Romanian
summary) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
IRINA DĂBULEANU, MIHAELA GABRIELA DUMITRU and AURORA REISS,
The Effect of the Biofertilizer Based on Potassium Humates and
Galactomannans Extracted from Seeds of Gleditsia Triacanthos Used
in Extraroot Plant Fertilization (English, Romanian summary) . . . . . . . 75
 BULETINUL INSTITUTULUI POLITEHNIC DIN IAŞI
Publicat de
Universitatea Tehnică „Gheorghe Asachi” din Iaşi
Tomul LX (LXIV), Fasc. 2, 2014
SecŃia
CHIMIE şi INGINERIE CHIMICĂ

ANALYSIS METHODS OF CHLORIDE IONS WITH

INDUSTRIAL APPLICATIONS
BY

LOREDANA FLUERARU, GABRIELA RĂUL,

MĂDĂLINA TĂTARU and LAURA BULGARIU∗

“Gheorghe Asachi” Technical University of Iaşi,

Faculty of Chemical Engineering and Environmental Protection

Received: October 10, 2014

Accepted for publication: November 5, 2014

Abstract. Chloride ions concentration is an important parameter in many

industrial processes and from this reason it must be determined with high
accuracy. The Romanian standard recommends the analysis of chloride ions
from various industrial samples by Mohr method. Unfortunately, the Mohr
method cannot be always utilized for this purpose. In this study we have
comparatively examined three different methods that can be used for chloride
ions determination from industrial aqueous samples, in order to establish the
applicability limits in each case. All these methods, namely: Mohr method,
conductometric titration and turbidimetric method, are based on the reaction
between chloride ions and AgNO3 standardized solution. The analytical
parameters (such as: utilizable concentration range, detection limit, precision,
etc.) were calculated from experimental results. The interferences caused by
several common ions and heavy metals, that can be present in industrial
samples were identified. The experimental results show that these three
methods complement each other and allow the analysis of chloride ions from a
much wider range samples.
Key words: chloride ions; analysis methods; industrial applications.

∗
Corresponding author; e-mail: lbulg@ch.tuiasi.ro
46 Loredana Flueraru et al.

1. Introduction

Chloride ions are involved in many industrial processes both as

feedstock (in chloro-compounds or pesticide manufacturing) but also as
auxiliary material (in electroplating industry where HCl is used as pickling
agent, catalyst production, etc.). Therefore, in many cases the chloride ions
concentration is an important parameter of industrial processes that must be
rigorously determined with high accuracy.
From analytical point of view, various analytical methods, such as ion-
chromatography (Chassanial & Thomas, 2006; Biesaga et al., 2004), FIA-
spectrometry (Li & Dong, 2004), colorimetry (Skowronski & Wedl, 1982),
spectrophotometry (Yokoi, 2002; Mesquito et al., 2002) or potentiometry
(Sanderson, 1957; Tang-Fei & Gordon, 1980) can be used for chloride ions
analysis, mainly due to their excellent performances, like low detection limit or
high sensitivity and selectivity, and allows the determination of very low
chloride ions concentration (only few ppm) in very complex samples.
Unfortunately, most of these methods are not easy to use because required
expensive instruments and reagents, laborious work methodology, long time of
analysis and high energy consumption. Mainly because of laborious work
methodology, the applicability of these methods in chloride ions analysis at
industrial level is very reduced, and Romanian standard recommend that the
determination of chloride ions concentration from industrial samples to be done
by Morh method (STAS 8663-70).
Mohr method is a simple and inexpensive classical titration method,
based on the reaction between chloride ions and standardized AgNO3 solution,
in presence of K2CrO4 as indicator (Fresenius et al., 1998; Bejan et al., 2006).
This method can be easy utilized in chloride ions analysis from various
industrial samples, but high accuracy of experimental result is obtained only
when the analyzed samples are clear, the chloride ions concentration is higher
than 50 mg·L-1, the samples pH is higher than 4.0, and the content of heavy
metals is relatively low (Bulgariu et al., 2007). These limitations make that
Mohr method to can’t be always applicable in the determination of chloride ions
concentration from industrial samples, and in consequence other methods must
be developed. In order to maintain the advantages of Mohr method (simple
work methodology, cheap reagents, etc.), two different methods based on the
same reaction between chloride ions and AgNO3 (conductometric titration and
turbidimetric method) have been tested.
In this study, we have comparatively examined three different methods,
namely Mohr method, conductometric titration and turbidimetric method, that
can be easy applicable for the chloride ions analysis in industrial samples. All
these methods are based on the reaction between chloride ions and AgNO3
solution, which make that their work methodologies to be comparable. In order
to establish the limits and performances of each method, the most important
 Bul. Inst. Polit. Iaşi, t. LX (LXIV), f. 2, 2014 47

analytical parameters (such as: utilizable concentration range, detection limit,

precision, interferences caused by other ions that can be also present in industrial
samples, etc.) have been evaluated from experimental results.

2. Experimental
2.1. Materials

All reagents were analytical reagents degree and were used without
further purifications. Sodium chloride (purchased from Fluka) was used as
chloride ions source. The stock solution of 0.1 mol·L-1 sodium chloride was
prepared by salt dissolving in doubly distilled water and dilution to 500 mL.
Working solutions of chloride ions were prepared by dilution of a given volume of
stock solution with doubly distilled water. The silver nitrate solution (0.1 mol·L-1)
was obtained by AgNO3 salt (from Reactivul Bucharest) dissolving in doubly
distilled water, following by solution standardization (Bejan et al., 2006).

2.2. Methods

In case of Mohr method, an exact measured volume of chloride ions

solution (6.0 mL) was titrated in a 250 mL conical flask with standardized
solution of AgNO3. A solution of 5% K2CrO4 was used as indicator, and the
titration was performed until at color change (from yellow to light brick-red)
was observed.
For conductometric titration measurements, 5.0 mL of chloride ions
solution was measured and directly diluted to 100 mL in conductometric cell.
Portions of 0.5 mL AgNO3 solution was added from 10-mL burette. After each
addition of AgNO3, the solution was homogenized and the electrical
conductibility was measured with a Radelkis OK-109 conductometer, equipped
with a glass conductometric cell (cell constant is 1.47 cm-1). The
conductometric titration was stopped only after at least five measured values
after equivalence point was made. The exact equivalence volume was obtained
from titration curve.
The chloride analysis by turbidimetric method was done using a
prepared calibration curve. The calibration curve was obtained as follow:
volumes containing 2-10 mg·L-1 chloride was transferred in 50 mL volumetric
flasks, and diluted with doubly distilled water until a 40 mL. 1.0 mL of 25%
HNO3 and 0.5 mL of 0.1 mol·L-1 AgNO3 solution were added. The solutions
were diluted to the mark with doubly distilled water and mix. After 20 min of
stand-by (time required for the formation of disperse system), the turbidity was
measured using a FeK-M fotometer (blue filter, 1 cm glass cell) against a blank
solution, which has the same composition but without chloride. The chloride
48 Loredana Flueraru et al.

concentration from unknown samples was determined by calculation from

regression equation of calibration curve.
The selectivity coefficients (aCl, j) were calculated as the ration between
chloride ions concentration and interfering ions concentration which gives a 5%
property change (equivalence volume or turbidity) in a reference solution that
contains 5 mg Cl-·L-1 in case of turbidimetric method and 50 mg Cl-·L-1 in case
of Mohr method and conductometric titration. The interferences caused by
different foreign ions were noted with “+” if the interfering ion give a property
change higher than 5%, and with “-”, if the property change caused by these is
lower than 5%.
The validation of considered methods was done by recovery test, using
tap water from “Gheorghe Asachi” Technical University of Iaşi laboratories and
a wastewater resulted from a galvanization process, without any preliminary
treatment. The main characteristics of tap water and wastewater samples are
summarized in Table 1.

Table 1
Several Characteristics of Tap Water and Wastewater
Samples Used for Recovery Test
Parameter Tap Water Wastewater
Suspension, [mg·L-1] Clear solution 1715.52
pH 6.57 4.32
Chloride, [mg·L-1] 62.53 3748
Fe total, [mg·L-1] 3.23 2204
Zn, [mg·L-1] 1.02 2.43
Pb, [mg·L-1] − 3.11

3. Results and Discussions

All the methods considered for chloride analysis in this study are based
on the well known reaction between chloride ions and AgNO3, when a white
precipitate of AgCl is formed, according with the following equation:

Cl- + AgNO3
AgCl + NO3- (1)

The obtained precipitate has a low solubility in water (Ps = 1.7 10-10)
(Dean, 1995) and acid media, and it is soluble only in concentrated ammonia
solution (Bejan et al., 2006). These characteristics makes that the methods
based on this reaction to have a good sensibility and accuracy. In addition,
because only halide and sulfide ions precipitate in presence of AgNO3, such
methods have a good selectivity in quantitative analysis of chloride ions. All
these advantages have been checked in case of examined methods (Mohr
 Bul. Inst. Polit. Iaşi, t. LX (LXIV), f. 2, 2014 49

method, conductometric titration and turbidimetric method), in order to

establish their applicability in chloride ions analysis from industrial samples.

3.1. Analytical Characterization of Considered Methods

As was already mentioned, Mohr method is a classical titration method

that uses K2CrO4 as color indicator. Over a exactly measured of chloride ions
solutions that contains a exactly calculated volume of 5% K2CrO4 solution as
indicator, is added AgNO3 standardized solution from burette, until at
equivalence point. The equivalence point is observed by the color change of
solution from yellow to light brick-red, due to the formation of Ag2CrO4. The
volume of AgNO3 used until at equivalence, determined experimental, will be
then used for the calculation of chloride ions concentration from analyzed
sample, based on equivalence law (Bejan et al., 2006).
The detection limit calculated as three times of standard deviation (σ)
of 10 replicate measurements, the precision (RSD %) as well as other analytical
characteristics of this method (Christian, 1994; Radojevic & Bashkin, 1999),
determined from obtained experimental results, are summarized in Table 2.

Table 2
Analytical Characteristics of Mohr Method
Analytical Parameter Determined Value
Studied concentration range 177.5 – 35500 [mg Cl-·L-1]
Limit of detection (3σ) 13.62 [mg Cl-·L-1]
Limit of quantification (10σ) 45.40 [mg Cl-·L-1]
Variation coefficient 0.34
Precision (RDS %) 3.15

The values of analytical parameters presented in Table 2 indicate that

Mohr method is simple, rapid, sensitive and precise, has reasonable
concentration range, and can be easy to use for chloride ions analysis from
clear aqueous samples, with weak acid – neutral pH (pH = 4.0-7.0). In strong
acid media (pH < 4.0), K2CrO4 no longer function as indicator, due to the
change of chrome speciation (the dimerization of CrO42- occurs) and
equivalence point cannot be observed any more. Also, the presence of solid
particles in analyzed samples disturbs the visualization of equivalence point,
and from this reason prior determination the samples should be filtered.
The second method that can be used for chloride analysis, examined
in this study is conductometric titration. Even if the titration reaction is the
same as in case of Mohr method, in case of conductometric titration is not
used any indicator, the AgNO3 solution is added both before and after
equivalence point and the volume of AgNO3 solution consumed up to
50 Loredana Flueraru et al.

equivalence is determined graphically from titration curve. The

conductometric titration curve is obtained by plotting the electrical
conductibility of analyzed solution (that contains chloride ions) as a function
of added volume of AgNO3 solution, when two linear portions with different
slopes are observed (Fig. 1).

1.1
Electrical conductibility, [mS]

0.9
(2)
0.8

0.7

0.6 (1)

0.5

0.4
ve
0 2 4 6 8
volume of AgNO3, [mL]

Fig. 1 − General shape of conductometric titration curve obtained in case

of chloride ions titration with AgNO3.

The first portion (portion 1) describes the behavior of titration system

under equivalence, when the electrical conductibility of solution is almost
constant due to the formation of low dissociated AgCl precipitate. The second
portion (portion 2) indicates the behavior of titration system after equivalence,
when the electrical conductibility of solution increase proportional with AgNO3
solution added in excess. The AgNO3 volume at equivalence point is obtained
from the intersection of the two linear portions, and this value is used for the
determination of chloride concentration, according with the usual analytical
calculation procedures (Bulgariu, 2010).
For the evaluation of analytical characteristics of this method, 10
replicate measurements have been performed, and the obtained values of
analytical parameters are summarized in Table 3.

Table 3
Analytical Characteristics of Conductometric Titration Method
Analytical Parameter Determined Value
Studied concentration range 177.5 – 35500 [mg Cl-·L-1]
Limit of detection (3σ) 37.19 [mg Cl-·L-1]
Limit of quantification (10σ) 123.96 [mg Cl-·L-1]
Variation coefficient 0.47
Precision (RDS %) 2.93
 Bul. Inst. Polit. Iaşi, t. LX (LXIV), f. 2, 2014 51

It can be observed form Table 3 that the conductometric titration has

similar concentration range and precision as Mohr method, but the detection
limit and limit of quantification are higher. However, towards Mohr method, the
conductometric titration has two important advantages: (i) can be used for the
analysis of samples with various pH, without to be affected the accuracy of
experimental results, and (ii) the presence of solid particles do not influence the
conductometric titration of chloride ions, which means that is not necessary a
preliminary treatment of samples. These advantages make the conductometric
titration more suitable for the chloride ions analysis from industrial wastewater
resulted from galvanization processes.
The turbidimetric method is also based on the reaction between chloride
ions and AgNO3, which determined the formation of a disperse system that
contains AgCl. Experimental, in this method is measured the turbidity of
analyzed solutions, in well defined experimental conditions, which will be
higher as chloride ions concentration in analyzed samples is higher. The
calibration curve used in this case was obtained as described in the
Experimental section, using six standard solutions, with chloride concentration
included in the linear dynamic range (Table 4), and the linear regression
equation, obtained by using the means of 10 replicate measurements is:
y = 0.1032x + 0.0904; R2 = 0.9869 (2)
where: x is chloride ions concentration, [mg·L-1]; y is turbidity (measured
experimentally) and R2 is the correlation coefficient.
The linear dependence between turbidity and chloride ions
concentration is obeyed from 2.0 to 10.0 mg Cl-·L-1, at 490 nm (blue filter)
against a blank solution. The analytical parameters useful for the
characterization of turbidimetric method have been calculated from
experimental results, and the obtained values are presented in Table 4.

Table 4
Analytical Characteristics of Turbidimetric Method
Analytical Parameter Determined Value
Linear dynamic range 2.0 – 10.0 [mg Cl-·L-1]
Limit of detection (3σ) 0.38 [mg Cl-·L-1]
Limit of quantification (10σ) 1.26 [mg Cl-·L-1]
Variation coefficient 0.33
Precision (RDS %) 1.02

In comparison with the methods discussed previously, the turbidimetric

method has lower detection limit and limit of quantification, and a higher
precision. These better analytical characteristics together with narrow linear
dynamic range make that turbidimetric method to be more suitable for the
52 Loredana Flueraru et al.

analysis of clear samples (because the presence of solid particles reduces the
accuracy of experimental measurements) with low chloride contents (trace
concentrations).

3.2. Effect of Interfering Ions

The effect of various foreign ions that can interfere in chloride ions
determination has been quantified, for each examined method, by the selectivity
coefficients. The selectivity coefficients (aCl,j) were calculated as the ratio
between chloride concentration and interfering ions concentration which gives a
5% property change (equivalence volume or turbidity) in a reference solution
that contains 5 mg Cl-·L-1 in case of turbidimetric method and 50 mg Cl-·L-1 in
case of Mohr method and conductometric titration. The interferences cased by
various foreign ions (Table 5) were noted with “+” – which means that
interfere, if the selectivity coefficient are equal or higher than 1, and with “-” –
which means that do not interfere, if the values of selectivity coefficients are
lower than unit.

Table 5
Effect of Various Foreign Ions in Chloride Ions
Determination by Considered Methods
Foreign Mohr Conductometric Turbidimetric
Ion Method Titration Method
K+ − − −
Ca2+ +* − −
Mg2+ − − −
SO42- − − −
HCO3- − − −
CO32- − − −
Ba2+ + − −
Pb2+ + − −
Fe3+ +* − −
Zn2+ +* − −
Cd2+ − − −
*concentration higher than 250 mg·L-1.

It can be observed from Table 5 that K+, Mg2+, HCO3-, CO32-, SO42- ions
that are fairly abundant in most industrial aqueous samples do not interfere in
the chloride determination, in none of the studied methods. Also, the presence
of some heavy metals, such as: Ca2+, Ba2+, Pb2+, Fe3+ or Zn2+, do not interfere in
the chloride analysis by conductometric titration and turbidimetric method, but
have serious interferences in case of Mohr method, in special at higher
concentrations. This means that the Mohr method cannot be used for analysis of
 Bul. Inst. Polit. Iaşi, t. LX (LXIV), f. 2, 2014 53

industrial samples that contains beside chloride ions and important quantities of
such metal ions. In such conditions it is recommended that the determination of
chloride ions to be done by conductometric titration (if the chloride ions
concentration in analyzed samples is higher) or by turbidimetric method (if the
samples contains trace of chloride ions).

3.3. Recovery Test

In order to establish the applicability limits of the three examined

methods for chloride ions analysis in industrial samples, the recovery test was
done using tap water from “Gheorghe Asachi” Technical University of Iaşi
laboratories and wastewater resulted from galvanization process, without any
preliminary treatment. For recovery test, 25 mL of tap water and wastewater
was transferred to each of the three 50 mL volumetric flasks and 5.0 mL, 10.0 mL
and 15.0 mL of chloride ions standard solution (1775 mg Cl-·L-1) were added to
each flask. All samples were then analyzed by Mohr method, conductometric
titration and turbidimetric method. The average of recovery percent obtained for
the addition of chloride ions spikes to tap water and wastewater samples are
presented in Table 6.

Table 6
The Recovery Test
Tap Water Wastewater
Analysis CL-ADD
- -
Method [Mg·L-1] Cl found Recovery Cl found Recovery
[mg·L-1] [%] [mg·L-1] [%]
177.5 237.12 98.36 − −
Mohr 355.0 418.53 100.28 − −
method 532.5 596.12 100.20 − −
177.5 239.02 99.43 3925.51 100.03
Conductometric 355.0 419.34 100.51 4104.98 100.55
titration 532.5 595.92 100.16 4279.92 99.89
177.5 236.43 97.97 3922.47 98.29
Turbidimetric 355.0 415.85 99.53 4103.86 100.24
method 532.5 592.54 99.24 4279.32 99.78

The results presented in Table 6 shows that in case of tap water, a good
recovery of chloride ions was obtained for all considered methods, indicating
that the constituents of tap water sample do not interfere significantly, and each
method can be successfully used for chloride ions analysis. In case of
wastewater, where can be present important quantities of other metal ions, a
good recovery of chloride ions was obtained only in case of conductometric
54 Loredana Flueraru et al.

titration and turbidimetric method (Table 6). For chloride ions analysis in such
samples the Mohr method is inadequate due to the presence some heavy metals
(such Pb2+, Fe3+, in this case) that will precipitate with the indicator (K2CrO4),
making it impossible the visualization of equivalence point. It should also noted
that the less accurate recovery of chloride ions by turbidimetric method, both
from tap water and wastewater samples, is mainly determined by multiple
dilutions required for to obtain a chloride ions concentration that lies the linear
dynamic range. Even this method has excellent analytical characteristics and
high selectivity, it is recommended to be used for chloride ions analysis in
samples where its concentration is low (trace concentrations).

4. Conclusions

In this study we have comparatively examined three different methods

that can be used for chloride ions analysis from industrial aqueous samples, in
order to establish their applicability limits. The methods considered for
evaluation are: Mohr method (recommended by Romanian standard),
conductometric titration and turbidimetric method, and all of them are based on
the reaction between chloride ions and AgNO3 standardized solution.
The analytical characterization has shown that all methods have
excellent detection limit and precision, making them suitable for chloride ions
analysis from industrial samples. However, analyzing the utilizable
concentration range for each method it can be noted that Mohr method and
conductometric titration are suitable for analysis of samples with high chloride
ions concentration, while the turbidimetric method is more adequate for analysis
of samples that contains trace of chloride ions. On the other hand, all methods
have a good selectivity towards chloride ions at the presence of several common
ions (K+, Mg2+, HCO3-, CO32-, SO42-) that are fairly abundant in most industrial
samples. Unfortunately, the presence of some heavy metals or calcium ions in
high concentrations gives serious interferences in chloride ions determination
by Mohr method, making it unusable in such situations. All these observations
have been confirmed by the results of recovery test, for that were used two
types of water samples (tap water and wastewater).
Therefore, the method used for chloride ions analysis must be selected
as a function of type of sample. The three examined methods complement each
other, and allow the analysis of chloride ions from a much wide range samples.

Acknowledgements. The financial support for this paper was provided by

“Gheorghe Asachi” Technical University of Iaşi, Faculty of Chemical Engineering and
Environmental Protection, Department of Environmental Engineering and Management.
 Bul. Inst. Polit. Iaşi, t. LX (LXIV), f. 2, 2014 55

REFERENCES

*
* *Romanian Standard STAS 8663-70 (1970).
Bejan D., Bîlbă D., Tofan L., Şuteu D., Păduraru C., Bulgariu L., Chemical Methods of
Analysis (in Romanian). Iaşi, Performantica (2006).
Biesaga M., Schmidt N., Seubert A., Coupled Ion Chromatography for the
Determination of Chloride, Phosphate and Sulfate in Concentrated Nitric Acid.
J. Chromatogr. A, 1026, 195−200 (2004).
Bulgariu L., Instrumental Analysis. Iaşi, Performantica (2010).
Bulgariu L., Robu B., Bîlbă D., Macoveanu M., Analysis by Conductometric Titration
of Chlorides from Wastewaters that Contains Heavy Metals. Annals of West
Univ. of Timişoara, s. Chemistry, 16, 1, 1−8 (2007).
Chassanial K., Thomas D., Determination of Chloride and Sulfate in Ethanol Using Ion
Chromatography. Dionex Corporation, The Application Notebook,
www.dionex.com (2006).
Christian G.D., Analytical Chemistry. 5th Edition, John Wiley & Sons, Inc., New York
(1994).
Dean J.A., Analytical Chemistry Handbook. New York, McGraw-Hill Inc. (1995).
Fresenius W., Quenetin K.E., Schneider W., Water Analysis. Berlin, Springer Verlag
(1988).
Li Y.S., Dong Y.L., Determination of Anion-Exchange Resin Performance Based on
Facile Chloride-Ion Monitoring by FIA-Spectrophotometry with Applications
to Water Treatment Operation. Anal. Sci., 20, 831−836 (2004).
Mesquito R.B.R., Fernandes S.M.V., Rangel A.D.S.S., Turbidimetric Determination of
Chloride in Different Types of Water Using a Single Sequential Injection
Analysis System. J. Environm. Monit., 4, 458−461 (2002).
Radojevic M., Bashkin V., Practical Environmental Analysis. Royal Society of
Chemistry, London (1999).
Sanderson P.H., Potentiometric Determination of Chloride in Biological Fluids.
Biochem. J., 52, 502−505 (1957).
Skowronski J.S., Wedl D.J., Automated Determination of Chloride Concentration in
Wort and Beer. ASBC Journal, 40, 2, 75−77 (1982).
Tang-Fei T., Gordon G., Quantitative Determination of Chloride, Chlorite and Chlorate
Ions in a Mixture by Successive Potentiometric Titration. Anal. Chem., 52,
1430−1433 (1980).
Yokoi K., Colorimetric Determination of Chloride in Biological Sample by Using
Mercury Nitrate and Diphenylcarbazone. Biolog. Trace Elem. Research, 85, 1,
87−94 (2002).

METODE DE ANALIZĂ A IONILOR CLORURĂ

CU APLICAłII INDUSTRIALE

(Rezumat)

ConcentraŃia ionilor clorură este un parametru important în multe procese

industriale, şi din această cauză aceasta trebuie determinată cu o acurateŃe ridicată.
 56 Loredana Flueraru et al.

Standardul românesc recomandă ca analiza ionilor clorură din diferite probe industriale
să se facă utilizând metoda Mohr. Din păcate, metoda Mohr nu poate fi utilizată
întotdeauna. În acest studiu am examinat comparativ trei metode diferite care pot fi
utilizate pentru determinare ionilor clorură din probe apoase industriale, pentru a stabili
limitele de aplicabilitate pentru fiecare caz. Aceste trei metode, şi anume: metoda Mohr,
titrarea conductometrică şi metoda turbidimetrică, au la bază reacŃia dintre ionii clorură
şi o soluŃie standardizată de AgNO3. Parametrii analitici (cum sunt: domeniul de
concentraŃie utilizabil, limita de detecŃie, precizia, etc.) au fost calculaŃi din rezultatele
experimentale. InterferenŃele cauzate de unii ioni comuni şi ioni ai metalelor grele, care
pot fi prezenŃi în probele industriale, au fost identificate. Rezultatele experimentale arată
că aceste trei metode se completează una pe cealaltă şi permit analiza ionilor clorură
dintr-o gamă mult mai variată de probe.

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