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Article BULLETIN OF THE

DOI: 10.1002/bkcs.10554 H.-S. Bae et al. KOREAN CHEMICAL SOCIETY

Argentometric Titration Apparatus with a Light Emitting Diode-based


Nephelometric Detection System
Hyun-Soo Bae,† Hoon Hwang,‡ and In-Yong Eom†,*

Department of Life Chemistry & Natural Science Research Institute, Catholic University of Daegu,
Gyeongsan 712-702, Republic of Korea. *E-mail: einyong@cu.ac.kr

Department of Chemistry, Kangwon National University, Chuncheon 192-1, Republic of Korea
Received July 17, 2015, Accepted July 29, 2015, Published online October 1, 2015

A newly revised apparatus for argentometric precipitate titrations was fabricated and evaluated. A light emit-
ting diode was adapted as a solid-state light source and a syringe pump was used for manipulating titrant both
in stopped flow mode and continuous mode. The performance of the two modes was compared in terms of
accuracy and precision. The continuous flow mode is much faster and shows generally higher accuracy under
given experimental conditions. The patterns of precipitate titration curves were changed with different coag-
ulant concentrations and addition flow rates of titrant. However, end point volumes were not affected by these
experimental factors tested here.
Keywords: Nephelometry, Argentometric titrimetry, Titration curve, Coagulant, Syringe pump

Introduction optical detection system with a minimized noise level. In this


system, the standard solution of sliver ions (i.e., titrant) was
Precipitation titration is one of the classical volumetric analy- gravimetrically added to an aqueous solution of halide ions
sis techniques that measure the volume of titrant to determine under a stopped flow mode. AgCl precipitate was formed by
the concentration of an ionic analyte which forms insoluble adding a drop of titrant (one step) and light intensity reflected
precipitates. This method is often used to determine halide from the precipitates was monitored simultaneously. The
ions by precipitating them with aqueous silver (I) solution. intensity of reflected light increased as the Ag(I) ion added
This technique is called argentometric titration which has been to the aqueous solution of halide ions but it did not increase
widely used for halide ion quantification because of its sim- after an end point because the precipitate did not form any
plicity and accuracy. more. Therefore, the end point volume was determined by
The end point of this titration process can be determined by counting the steps of titrant added just before the end point.
monitoring color change of indicator right after an equivalent This system was simple but could determine the millimolar
point passed. Mohr, Volhard, and Fajans methods are three concentrations of chloride ions accurately.9,10 The similar sys-
types of the argentometric titration based on the formation tem was used to determine the binary mixture of I− and Br−,
of red substances at the end points.1 Potentiometry2,3 (i.e., simultaneously.10
adapting a silver ion selective electrode) is also widely used We revisit this technique after revising the system by means
to find an end point so as to determine an equivalent point. of a flow manipulation. The originally developed system was
Optical technique4 is another alternative to determine an operated gravimetrically only under stopped flow mode. So,
end point by measuring fluorescence, absorbance, or reflect- the accuracy for the system was truly depending on a volume
ance from the precipitates. Measuring the reflected and/or of a drop of a titrant. However, unfortunately the volume of a
scattered light from precipitate forming during a titration proc- drop could be varied (could be getting smaller) as the titration
ess is called nephelometry,5,6 which is known to be more pre- process goes on due to the fact that the height of titrant inside a
cise for determining an end point for lower concentration of burette is lowered so the pressure on the bottom of the burette
halide ions because the reflected light change is very sensitive is decreased. This possible limitation was clearly solved by
to the very low level of reflective particle’s concentration. replacing the burette with a step motored syringe pump. Using
Recently, pseudo nephelometry using light emitting diodes the syringe pump enables the system operating under contin-
(LEDs) was reported and used to determine halide ion uous mode, which is eventually more convenient and makes a
concentration.7 – 12 This LED-based nephelometric detection titration process faster. Also, the volume of a drop, unlike the
system takes advantages from the nephelometry and LEDs initially reported system,9,10,12 does not vary under the
as a solid-state light source: nephelometry has a potential to stopped flow mode because the flow is regulated not gravime-
find an end point more clearly for the lower concentration trically but stepped-motor driven for the currently revised
of analytes and LEDs are very stable in intensity fluctuation apparatus. Reportedly, in nephelometry the reflectance
so as to be suitable for developing an accurate and robust increased linearly and reached the maximum at the end point

Bull. Korean Chem. Soc. 2015, Vol. 36, 2725–2729 © 2015 Korean Chemical Society, Seoul & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Wiley Online Library 2725
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and then decreased after the end point passed due to the dilu- polytetrafluoroethylene (PTFE) tubing (PT, 0.76 mm
tion effect.13 However, the titration curve was not like that i.d. Upchurch, Oak Harbor, WA, USA) of which end-tip
with our system. The reflected light intensity was not increased (stainless steel tubing, approximately 100 μm i.d.) was
linearly as the precipitates were formed before the end point. immersed in the titrand in order to prevent a drop formation
The reflectance increment was exponentially increased nearly on the end-tip. The syringe pump controls the flow rates very
just before the end point. precisely. A light source (LS) is a blue LED powered by 5 dc
With a revised argentometric titration apparatus here, we volt with a current limiting resistance (VR, 1 KΩ potentiom-
compared the stopped flow mode and continuous flow mode eter). The source light traverses a light guide (LG, 4.5 mm
in accuracy and precision. Using coagulant and different flow i.d. glass tube wrapped with a PTFE tape which taped again
rates of titrant affected the patterns of titration curves dramat- with a black electric tape, see more details described in Ref.
ically but the end point volumes were not affected by the use of 12) and illuminates a spot (ca. 10 mm diameter) on the
coagulant (see Results and Discussion). QV’s outer wall. A small silicone photodiode (PD; Goldmine,
Scottsdale, AZ, USA) converts the source light reflected from
Experimental the quartz’s outer surface into a voltage (conversion rate 1 volt/
μA), which further amplified (circuit shown in Figure 2)
Silver nitrate (AgNO3; Junsei Chemical Co., Tokyo, Japan), through an operational amplifier (OA, TL082-cp; Texas
sodium chloride (NaCl; Duksan Pharmaceutical Co., Seoul, Instrument, Dallas, TX, USA). The reflected light intensity
South Korea), and sodium nitrate (NaNO3; Duksan Pharma- was finally recorded (Ch1 signal in Figure 1) on a desktop
ceutical Co.) were all reagent grade and used without any fur- computer (PC) through a digital input and output card (DA,
ther purification. LED-based reflectance measurement system 12; Measurement Computing, Norton, MA, USA) for further
was fabricated newly (see below for details) for this study. A data processing. The black PVC pipe (PP, 50 mm i.d. and 60
blue LED (nominal λmax = 455 nm) was purchased from mm o.d.) and the black lid enclosed the QV and other optical
Nichia Co. (Tokushima, Japan). components to accomplish light proof system.
The argentometric titration system (shown in Figure 1) was Titrant (AgNO3) was added into titrand (aqueous NaCl
modified from the previously reported system12 by replacing solution) in two ways; a stopped flow mode and a continuous
the burette (containing titrant) with a step motored (48 000 flow mode. Note that only the stopped flow mode was used in
steps) syringe pump (Versa 6; Kloehn, Las Vegas, NV, the previously reported titration system12 because of difficulty
USA). The pump aspirates the AgNO3 solution (ca. 0.1 M) of getting precise flow controls under such a gravimetric flow
from the reservoir (SN) and then dispenses the titrant into force. The use of syringe pump here made it possible to per-
the halide solution (HS) in a quartz vessel (QV). The QV form a titration under the continuous flow mode. Due to the
was placed on a magnetic stirrer (MS) and the white stir bar two different addition modes of titrant, end points could be
(SB, 1.5 mm long) agitates HS continuously to suspend AgCl determined in two ways. For the stopped flow mode, a pre-
precipitates during the whole titration process. Aspiration and cisely allocated volume (i.e., one step volume) of titrant added
dispense modes were controlled by the distribution valve once and then waited for 2 min to monitor the reflectance
(DV) and KCOMM™ software provided from the manufac- change before the next addition of the equally allocated vol-
turer (Kloehn). The titrant was delivering through a ume of titrant. In this case, end point volumes were determined
by counting the number of additions of titrant (i.e., number of
steps of titrant addition). To count the number of additions, an

Figure 1. Schematic diagram of argentometric titration system


equipped with a LED reflectance detector: PP, PVC pipe; QV, quartz
vessel containing halide solution (HS); SB, stir bar; MS, magnetic
stirrer; LS, light source (i.e., blue LED powered by 5 V with a current
limiting resistance); LG, light guide; PD, photodiode; VR, variable
resistance (1 KΩ); OA, operational amplifier; DA, data acquisition Figure 2. Circuitry of current-to-voltage converter and voltage
card; PC, desktop computer; SN, silver nitrate standard solution; amplifier using an operational amplifier. PD: photodiode. See text
SP, syringe pump; DV, distribution valve, see text for details. for details.

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Figure 3. End point determination method and examples of titration curve (titration of chloride ion with silver (I) ion) obtained under the stopped
flow mode (a) and the continuous flow mode (b). For the stopped flow mode (a), 21 steps can be used to determine the end point volume because
the reflected light intensity does not increase after those steps of addition. See text for details.

instant +5 volt signal was directly generated from the syringe added into the titrand increased by the factor of 0, 5, 10, 25,
pump (Ch2 in Figure 1) for each and every addition. Under the and 50 times higher compared with the moles of chloride ions
continuous flow mode, the titrant was added into the titrand (10.05 μmol) in the titrand.
continuously. The flow rate of the Ag+ solution was generally During the titration of precipitation of Cl− by Ag+, AgCl
0.075 mL/min otherwise it was specified. At this case, the +5 nuclei are first formed and then each AgCl nucleus grows
volt signal (Ch2) was generated once at the initial moment of by adding more Ag+ into the Cl− solution. Therefore, the addi-
the titration to mark a start point. An end point, volume for the tion flow rate of titrant governs the formation rate of nucleus
continuous mode was determined by multiplying the titrant creation and the speed of particle growth throughout the whole
addition flow rate and the time at which the intensity of the process of the titration. It is well-known that the speed of pre-
reflected light did not increase any more. Figure 3 shows cipitant addition should be as slow as possible to get bigger and
examples of titration curve obtained under the stopped flow better homogenized size distribution of precipitates in gravi-
mode (a) and the continuous flow mode (b) and end point metric analysis: slower the flow rate of titrant, bigger the size
determination method from those curves. It is worth to note of AgCl precipitates, and vice versa. Different flow rates of
that end point volumes under the continuous mode could be titrant change the pattern of the reflected light, which results
determined more clearly by differentiating a titration curve in a different shape of titration curves also. Therefore, the titra-
because the intensity of reflected light increased steeply at near tion curve patterns were monitored at different flow rates
the end point but this method cannot be always applied if noise (0.075, 0.150, 0.225, 0.300, 0.375, and 0.600 mL/min) of
is too high to differentiate a titration curve. titrant (0.103 M AgNO3). The volume of titrand (2.00 mM
Because understanding a shape of titration curve is very cru- NaCl) for this study was 5.00 mL.
cial to determine the end point with higher accuracy, we were
trying to reveal what kind of factors affected the shape of titra- Results and Discussion
tion curves: the use of different concentrations of coagulant
and different flow rates of the titrant addition. Coagulant is Both modes of the stopped flow and the continuous flow were
often used to aggregate fine particles so to turn them into big- evaluated in terms of performance accuracy. Under the
ger precipitates in a gravimetric analysis. In the nephelometry, stopped flow mode, accuracy test was performed by decreas-
patterns of titration curve were greatly affected by the presence ing the allocated volume (i.e., one step volume of titrant,
of coagulant because the reflection is affected by the size of 0.100 M of AgNO3) from 2.00 μL to 0.400 μL while the vol-
particles. Here, titration curve patterns were monitored by ume of titrand (0.199 mM of NaCl) was fixed at 10.0 mL.
changing the concentration of NaNO3 (as a coagulant) while Under the continuous flow mode, the syringe pump delivered
the concentrations of chloride ions (2.01 mM) and AgNO3 the titrant (0.101 M of AgNO3) continuously to different sam-
(0.101 M) titrant were fixed. The concentration of NaNO3 ple volumes (5.0, 10.0, and 15.0 mL) of titrand (2.01 mM of

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Table 1. Comparison of two flow modes in performance accuracy and precision.


[Cl−]experimental, mM ([Cl−]prepared)
a
Flow modes ([Ag+]prepared) End point volume, mL (%RSD) Error (%)
Stopped (0.100 M) One step volume 2.00 μL 0.0240 (0.0) 0.240 (0.199) 20.6
1.00 μL 0.0220 (0.0) 0.220 (0.199) 10.6
0.667 μL 0.0211 (1.8) 0.211 (0.199) 6.0
0.400 μL 0.0206 (4.1) 0.206 (0.199) 3.5
Continuous (0.101 Sample volume 5.00 mL 0.102 (0.6) 2.06 (2.01) 2.5
M) 10.00 mL 0.202 (0.3) 2.04 (2.01) 1.5
15.00 mL 0.296 (0.2) 2.00 (2.01) −0.5
a
Error = 100 × {([Cl−]experimental − [Cl−]prepared) / [Cl−]prepared}.

Figure 4. Changed patterns of titration curves with different molar ratio of NaNO3 to NaCl (a) different addition flow rates (mL/min) of titrant (b).
See text for details.

NaCl). These accuracy study results are summarized in in turn changed the patterns of titration curves (Figure 4).
Table 1. As expected, decreasing the allocated titrant volume To be a solid titration technique, the proposed method should
improved accuracy (lowered % error) because smaller volume find end point volumes successfully even in any case of titra-
of a drop minimizes analysis error in the stopped flow mode. tion conditions. For different molar ratio of NaNO3 to NaCl
Generally speaking, minimizing the influence of a volume of a (Figure 4(a)), end point volumes were determined and sum-
titrant is one of the main keys to improve both accuracy and marized in Table 2. For different addition flow rates (mL/min)
precision in the volumetric titration technique. Due to the same of titrant (Figure 4(b)), end point volume for each flow rate was
scope of this view, it is reasonable to show higher accuracy as determined after converted time interval to added titrant
increasing the sample volume under the continuous flow (AgNO3) volume and those volumes are also summarized in
mode. Based on these accuracy studies, we could say that Table 2. As shown in the table, even though pattern of titration
the continuous flow mode has a shorter analysis time from tens curves are affected by the different molar ratio of coagulant
of minutes to a few minutes and higher accuracy compared to and addition flow rates, end point volumes are quite similar
the stopped flow mode under these experimental conditions. for each case. Note that similar patterns were observed for
However, it should be noted here that the stopped flow mode titration of NaBr and NaI with coagulant addition (data and fig-
showed clearer end points for two components titration (i.e., I− ures not shown here). Therefore, these results prove that the
and Br− mixture10) while the continuous flow mode failed at proposed system is suitable for performing argentometric titri-
this time to differentiate each component’s concentration. metric techniques with such a low concentration of halide ion
Table 1 also proves that the proposed argentometric titration in single digit of millimolar (mM) concentration. Actually, we
apparatus shows acceptable reproducibility (less than 1% checked possibility of titration of lower concentrations (0.20
RSD) for the continuous flow mode. mM and 0.020 mM) of chloride ions with 0.100 M AgNO3 by
As stated in experimental section, the use of coagulant and monitoring whether AgCl precipitates are formed or not by
changing the addition rate of titrant (i.e., flow rate) to the raw eyes. White precipitates were clearly found by raw eyes
titrand affected the size of AgCl precipitates formed, which for 0.20 mM but not for 0.020 mM of NaCl, which means that

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Table 2. End point volumes determined at different molar ratios of continuous flow mode and about 20–30 min of titration times
NaNO3 to NaCl and different addition flow rates of titrant. for the stopped flow mode. Even though the patterns of titra-
End point tion curves were affected by the use of coagulant and different
End point Flow rate volume addition flow rates of titrant, end point volumes were not
Molar ratios volume (mL) (mL/min) (mL) affected by those factors. With such a result, the proposed
0 0.103 0.075 0.106 method can be successfully used for pedagogical purpose.
5 0.103 0.150 0.0980 A further study is in progress to use the proposed system as
10 0.101 0.225 0.102 a differential titration platform with two or three halide ion
25 0.102 0.300 0.101 mixture.
50 0.102 0.375 0.106 Acknowledgments. This work was supported by research
0.600 0.0940 grants from the Catholic University of Daegu in 2012
Average (%RSD) 0.102 (0.8) Average (% 0.101 (4.6) (20121046).
RSD)
[Cl−]experimental, 2.06 (2.7)a [Cl−]experimental, 2.08 (4.2)b
mM (error, %) mM (error, %) References
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