Simultaneous Determination of the Halides (F-, Cl-, Br- and I-) in Combination of their Corresponding Ion-Selective Electrodes in a Parallel Arrangement in a FIA System

Fadhil M Najib & Tara F. Tahir
Chemistry Dept. Sulaimani University, Kurdistan Region- Iraq

Abstract
The determinations of four halides were achieved simultaneously using flow- through ion selective electrodes, specially home - designed manifold to suit parallel arrangement. The flow through electrodes except fluoride, were home- made from compressed pellets of mixtures of Ag2S/ AgX (X= Cl-, Br- or I-) drilled longitudinally (1mm diameter). Suppressor columns of AgCl and amalgamated lead were used to eliminate interferences of Cl-, Br-, I- and S2-. Interferences from trace metals espcially Fe(III) and Al(III) on F-electrode were also eliminated by pumping TISAB solution, through the F- line. A syringe pump was used to force the carrier stream of 0.1M sodium perchlorate (pH 4) at a flow rate of 0.7ml/ min instead of a peristaltic pump. The sample loop was 128 µ l. Calibration plots were linear, with almost theoretical slopes, down to 1x10-6M I-, 5x10-5M Br-, 1x10-4M Cl- and 2x10-5M F-, with precision between (1-2%) below 1x10-3M and less than 1% at higher concentrations and accuracy was between (3 – 8%) . Sampling frequency was 60 samples/hr and used for the determination of these ions in water and toothpaste samples.

Keywords: -Simultaneous determination,of halides, FIA- ISE, Parallel design, A syring pump.
(ISEs) as detectors in the same manifold, than other methods. This is due to the small size of such systems and the fast response of the electrodes [2]. Few such applications have been reported [29] in the literature especially for the halides [5]. In the present work, home–made AgCl/Ag2S, AgBr/Ag2S and AgI/Ag2S
.Part of her M.SC.Thesis *

Introduction
Castro and Valcarcel [1] defined the simultaneous analysis as the determination of several analytes from a single sample injection. This means two or more signals could be obtained from a single injection. Such analysis is, perhaps more easily performed by combining a number of ion – selective electrodes

membranes were prepared and used together with a commercial fluoride–

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Reagents
All chemicals were of analytical grade unless otherwise reported. Ordinary distilled water was used for all preparations. Silver sulfide was prepared [10] by adding a 130ml portion of 0.5M silver nitrate solution dropwise to a 100ml of 0.5M sodium sulfide solution. The precipitate was collected, washed first with 0.1M nitric acid, then with distilled water and dried at 110 C0 for 12 hours. TISAB solution was prepared [11] by adding 57ml glacial acetic acid, 58g NaCl, 0.3g potassium citrate and 4g EDTA to 500ml distilled water. The pH of the solution was adjusted between (5 – 5.5) by adding 5M NaOH solution, using combined glass electrode and the solution was then completed to 1L with distilled water.

selective electrode as a modification of the work reported earlier [5]. The ISEs were combined in parallel in a specially designed manifold instead of a combination between parallel and series arrangement. Such a manifold has not been found reported earlier. Mutual interferences between the halides were also eliminated automatically in the manifold using minicolumns.

Experimental Apparatus
The propelling system was: a syringe pump model Perfusor VI, a small peristaltic pump, used in conjunction with SVP rotary injection valve with a sample loop of 128µl. All connecting tubes used in the manifold were 0.8mm i.d. The commercial electrodes used for batch analysis were, an Orion 94-09 for fluoride, a 39604 Cl- (B-8) for chloride, an Orion 94-53 for iodide and a single and a double–junction Hg/Hg2Cl2 as a reference electrode. Potentials were measured with an Orion 601 Ionalyzer, a Philips PW 9420 and a Metrohm 632, and recorded with a Saffron Walden WPA CQ 75, a Linear Instrument Corp. 261/E2, X–Y chart recorder type 733 and a Philips PM 8120 X–Y recorder with a home–made automatic potential scanning to drive the t– axis of the recorder at a desired speed. An AC. automatic voltage regulator SVC –350 was also used.

Preparation of Flow – Through Pellets
A 6.5g of a 3:1 molar ratio mixture of AgCl, AgBr and AgI with Ag2S separately, was crushed to pass 200 mesh sieve. The fine dry powder was pressed between two 11mm diameter stainlesssteel pellets in a KBr-disk maker under 10 tons pressure with continuos withdrawal of air before pressing and until one hour after that then left under pressure for 12 hours. The pellet thus obtained was about 8-10mm thick and 11mm Ø. It was drilled longitudinally to make a channel of 1mm Ø and electrical connection was made, as

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(b) flow-through cell for Felectrode. 1= electrical conducting wire; 2= PVC tape; 3=solder ; 4= inlet/ outlet; 5= commercial F- electrode; 6= Perspex.

Preparation of Interference Suppressor Columns

AgCl column. A 55mm long glass tube of 2mm bore was filled with the salt of (36 mesh) closed at both ends with glass wool connected to two PTFE tubes and finally wrapped with black PVC tape to protect it from light. The column was placed in the manifold between the splitter and the chloride electrode. This column was regenerated by passing 10ml of 0.2M silver nitrate through it at a rate of 0.5ml /min, followed by distilled water until the washing solutions became free from Ag+ ions [5]. Amalgamated lead column. This is prepared in a similar way of preparing Zn–amalgam for jones–Reductor [12]with slight modifications. Granulated lead (16 mesh) was treated with 1M hydrochloric acid in a small beaker for 1min, then a poured off, and washed several times with (a) flow-through pressed pellets distilled water.The cleaned Pb was stirredof I-, Br-, Clelectrodes, with 30ml of 0.2 M mercuric nitrate for 3 b min and the amalgamated lead was washed well with distilled water, dried between two filter papers, packed in a

shown in Fig.1a, by making another two holes of the same diameter and about 2mm deep on the opposite sides of the pellet. Two copper wires, 100mm long and 0.8mm diameter, were fixed in each hole by molten lead. One of the wires was then bent round the pellet and soldered to the other to become a single wire which was insulated with PVC tape, properly screened together with the electrode with a thin aluminium foil and earthed. The wire lead was connected to the pH-meter. Two PTFE tubes of 0.8mm i.d. and 25mm long were fixed in the two ends of the channel with molten silicon. The flow-through cell for the fluoride electrode was made of two flat pieces of Perspex (40х30x6mm), one of them was drilled at the center to fix the end of the electrode firmly with a thin O-ring around it. The other piece was drilled only slightly to 1mm depth, eye- shaped, at the same position with two diagonally channels, as shown in Fig. 1b. The two pieces were attached to each other using chloroform under some pressure and left for 12 hours. Two PTFE tubes, 30mm long were fixed at the ends of the two channels. Fig. ( 1 ) Schematic diagrams for

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valve is closed, while the other arm is free to empty air from the main tube. The key is then reversed allowing the carrier stream to flow through the manifold.

glass tube (25mm long, 2mm bore), and placed in the manifold before bromide electrode. Regeneration must be acheived every day before using it by passing 1% Hg(NO3)2 solution through it until a shiny amalgam is restored [5].

The Manifold
Figure 2 shows a propelling system consisted of a piston- driven syringe pump, instead of the multichannel peristaltic pump, with a 60ml capacity plastic syringe. Its outlet was connected to a polyethylene tube of 3mm i.d. and 120mm long then to a “T” shape divider, where one of its arms was joined to the injection valve and the other arm led to waste. This divider has a key to open and stop the flow. When the pump is started to work, the channel leading to the injection

Fig (2): Piston-driven syringe pump with “T” divider and the rotary injection valve. 1= syringe pump; 2= syringe; 3= flexible silicone tube; 4= “T” divider; 5= injection valve.

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‫دياريكردنى ثيَكرِايي ضوار هاليد لة هاوبةندى جةمسةرة‬ ‫هةلَبذاردةكانى هاوضةشن لة ثيَرِؤى ‪ FIA‬بة تةريبى‬
‫بةشى كيميا/ كؤليجى زانست/ زانكؤى سليَمانى - هةريَمى كوردستانى عيَراق‬

‫و تارا فوئاد تاهير‬ ‫ثوختة‬

‫فازيل محمد نجيب‬

‫دياريكردنى ضوار هاليد بة بةكارهيَنانى جةمسةرة هةلَبذاردة رِةوةنىية- تيَثةرِةكان ويةكة‬ ‫هةمةليةنةكة بةتةريبى كرا. جةمسةرى هةلَبذاردةى رِةوةنى- تيَثةر بو َ هاليدةكان جطة لة فلوَريد لة ثلى‬ ‫ثةستراو دروست دةكري َ ت هى ‪ Ag2S/ AgX (Br-,Cl-=X‬يان ‪ )-I‬بةدريَذى كونكراوة بة تير ةى 1ملم.‬ ‫دوولوولةي ثرِكراو لة ‪ AgCl‬و ‪ amalgamated lead‬بةكارهاتوة بوَ لبردنى تي َ ك هةلَضووةكانى كلؤريد,‬ ‫برِؤميد،ئايؤديدو سؤلَفيد. تيَك هةلَضووةكان لة (‪ III) Fe ، (III) Al‬دةكريَت نةهيَلَدريَن بة ثالَنانى طيراوةى‬ ‫‪ TISAB‬بؤ هيَل َ ى فلوَريد. ثالَنةريَكى سرنج بؤ ثالَنانى 1, 0 مؤلر ثيَركلؤراتى سؤديؤم لة ‪ pH‬ى (4)دا‬ ‫بةرِادةى رِةوةنى 7, 0 ميليلتر لة خولكةيةكدا بةكارهيَنراوة لة برى ثالَنةرى ‪ . peristaltic‬قةبارةى‬ ‫تيَرِذاندنةكة 821 مايكرؤليترة. هيَلَةكانى ثيَوانة بؤ تيَكةلَةى ضوار ئايؤنةكة بةكادةهيَنريَت بة رِادةكانى ثةيتى‬ ‫: (1×01-4 - 1×01-3) مؤلر كلؤريد ، (5×01-5 - 3×01-4) مؤلر برِؤميد، (1×01-6 - 3×01-5) مؤلر ئايؤديد و (‬ ‫2×01-5 - 1×01-3) مؤلر فلؤريد بة وردى نيَوان (1-2%) بؤ ثةيتى ذيَر‬ ‫1× 3-01 مؤلر و كةمترة لة 1% بؤ ثةيتى زؤرتر. رِاستى دياريكردنةكان لة نيَوان (3-8%) و خيَرايي نموونة‬ ‫06 نموونة لة ساتيَكدا بؤ دياريكردنى تاكة ئايؤني َ ك وة دةست ديَت. هةلَسةنطاندنى ئةو ئايؤنانة لة‬ ‫نموونةكانى ئاو و دةرمانى ددان كرا.‬

‫تقدير الهاليدات (‪ )-F-, Cl-, Br-, I‬سوية بالجمع بين‬ ‫اللكترودات النتقائية المعنية مع تكنيك الحقن الجرياني في نظام‬ ‫التوازي‬
‫وتارا فؤاد طاهر‬ ‫الخلصة‬
‫تم تقدير اربع هاليدات تلقائيا باستخدام اقطاب جريان انتقائية ووحدة متشعبة لتلئم‬ ‫الترتيب المتوازى. صنعت اقطاب الجريان النتقائية للهاليدات عدا الفلوريد بشكل اقراص‬ ‫مضغوطة من مزيج ‪)-Ag2S/AgX (X=Cl-, Br-, I‬مثقوبة طوليا (1 ملم قطر داخلي ). استخدم عمودين‬ ‫معباين ب ‪ AgCl‬وملغم الرصاص لزالة متداخلت الكلوريد, البروميد, اليوديد و الكبريتيد.‬ ‫المتداخلت من (‪ III) Fe‬و (‪ III)Al‬تم ازالتها بامرار تيار من محلول ‪ TISAB‬خلل قطب الفلوريد.‬ ‫استخدمت مضخة- محقنة لدفع 1 , 0مولر 4‪ NaClO‬كمحلول للتيار الحامل و مثبت الشدة اليونية‬ ‫بضبط الس الهيدروجيني له في‬ ‫(4) و بسرعة جريان 7 , 0مل/دقيقة كبديل للمضخة التمعجية. استخدم حجم المحلول المحقن‬ ‫4‬‫821 مايكرولتر. تم الحصول على منحنيات المعايرة لمزيج اليونات الربع بالتراكيز التالية: (1×01‬ ‫ 1×01-3) مولر كلوريد, (5×01-5 - 3×01-4)‬‫مولر بروميد، (1×01-6 - 3×01-5 ) مولر يوديد و(2×01-5 - 1×01-3 ) مولر فلوريد بتطابقية بين (1-‬ ‫2%) للتراكيز القل‬ ‫من 1× 01-3 مولر و اقل من 1 % للتراكيز العالية و دقة بين (3-8%). لقد كانت سرعة‬ ‫النموذجية لهذا النظام 06 أنموذج/ساعة على أساس ايون واحد. طبقت هذه الطريقة لتقدير‬ ‫اليونات الربع في انموذجات الماء و معجون السنان.‬

‫فاضل محمد نجيب‬

‫قسم الكيمياء/ كلية العلوم / جامعة السليمانية - أقليم كردستان العراق‬

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