Determination of Halogens and Sulphur in Complex Matrices

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1 Determintion of Hlogens nd Sulphur in Complex Mtrices Dniel Hemmler 1, S. Kufmnn, Christin Emmenegger 3, Dirk Schmitz 3, nd Alfred Steinbch 3, 1 Alen University, Alen, Germny, Anlytik Jen AG, Jen, Germny, 3 Metrohm Interntionl Hedqurters, Herisu, Switzerlnd. This rticle presents method tht combines combustion digestion nd ion chromtogrphy into single nlysis (combustion ion chromtogrphy [CIC]) mking it possible to detect hlogens nd sulphur in complex mtrices. The method is suitble for use in wide rnge of ppliction res. Photo Credit: Mrtin Diebel/Getty Imges There re number of different methods vilble to determine fuorine, chlorine, bromine, iodine, nd sulphur in fmmble substnces. The mjority of these re bsed on independent nlysis steps, beginning with smple digestion using high-temperture combustion followed by hlogen nd sulphur nlysis. As n lterntive, combustion digestion coupled with ion chromtogrphy (CIC) combines smple digestion nd nlysis in one step. CIC cn be performed on wide rnge of smple types regrdless of whether solid, liquid, or gs. The only condition is tht the smple hs to be fmmble. In ddition to the hlogen nd sulphur nlysis processes discussed in this rticle, which re used in the plstics, power genertion, petroleum, nd fuel industries, CIC is lso suitble for smples from the phrmceuticl, environmentl, nd food sector. It is for these dvntges tht mny interntionl stndrds refer to CIC when determining the presence of hlogens nd sulphur in complex mtrices (Tble 1). CIC Method Principles Combustion: Combustion tkes plce in the presence of stem, which ensures tht the gseous hlogen nd sulphur compounds (HX, X, SO x ) re quntittively collected by the bsorption solution. Adding hydrogen peroxide to the bsorption solution (for exmple, mg/l) ensures tht ll sulphur compounds re present in the form of sulphte, which is necessry for ion chromtogrphic detection. However, when hydrogen peroxide is dded s n oxidizing gent it cn result in vrious interference peks tht overly the fuoride pek. With in-line mtrix elimintion, these interferences dispper nd the fuoride pek cn be evluted gin (Figure 1). An opticl sensor in the pyrolysis oven indictes the progression of the combustion nd regultes the feed of the smple bot. This ensures complete combustion by similrly reducing the smple s oven dwell time. 1 4

The Column Figure 1: Effect of mg/l hydrogen peroxide in the bsorption solution. Red: once with in-line mtrix elimintion; Blck: once without.

.8 This exclusive e-book ssembles the top experts in ion chromtogrphy from cross the world to provide stte-of-the-rt views nd reviews of

84» Developments in ion-exchnge columns» Advnces in detection for IC» Best prctices in.83.

interntionl stndrds Smll, the inventor of ion chromtogrphy, on the development of the technique Stndrd test method for totl fluorine,

combustion ion chromtogrphy (CIC). ASTM D 58-6 Stndrd test method for totl fluorine in col nd coke by pyrohydrolytic extrction.

2 The Column Figure 1: Effect of mg/l hydrogen peroxide in the bsorption solution. Red: once with in-line mtrix elimintion; Blck: once without. DOWNLOAD LCGC E-Book Eductionl Series: Advnces in Ion Chromtogrphy This exclusive e-book ssembles the top experts in ion chromtogrphy from cross the world to provide stte-of-the-rt views nd reviews of developments nd dvnces in this powerful seprtion technique KEY TOPICS INCLUDE:.84» Developments in ion-exchnge columns» Advnces in detection for IC» Best prctices in smple preprtion» Tools for simultion nd» High-speed nd highresolution methods» Perspectives from Hmish Combustion IC in interntionl stndrds Smll, the inventor of ion chromtogrphy, on the development of the technique Stndrd test method for totl fluorine, chlorine nd sulphur in romtic hydrocrbons nd their mixtures by oxidtive pyrohydrolytic combustion followed by ion chromtogrphy detection (combustion ion chromtogrphy-cic). A formt for everyone This e-book is vilble for the ipd or for stndrd computer web browser UOP 1-11, fluoride, nd bromide in liquid orgnics by combustion ion chromtogrphy (CIC). ASTM D 58-6 Stndrd test method for totl fluorine in col nd coke by pyrohydrolytic extrction. DIN EN Screening of totl bromine in electric nd electronic products by combustion ion chromtogrphy. DIN 51 Testing of solid fuels Determintion of chlorine content. 13 mgent cyn yellow blck SPONSORED Tody optimiztion of IC seprtions Tble 1: A selection of interntionl stndrds tht recommend combustion ion chromtogrphy s mens of determining the hlogen nd sulphur content in fmmble smples. ASTM D 35-8 PDF 1 BY 4 ES4651_LCTC14_13.pgs : ADV

The Column Figure : Determintion of hlogens nd sulphur in polymer stndrd ERM EC68k. Column: Metrosep A Supp 5-15/4., eluent: 3. mmol/l sodium crbonte, 1 mmol/l sodium hydrogen crbonte,.

3 The Column Figure : Determintion of hlogens nd sulphur in polymer stndrd ERM EC68k. Column: Metrosep A Supp 5-15/4., eluent: 3. mmol/l sodium crbonte, 1 mmol/l sodium hydrogen crbonte,. ml/min, column temperture: 3 C Tble : Certifed chlorine, bromine, nd sulphur content of the polymer stndrd ERM EC68k determined using combustion ion chromtogrphy. ERM-EC68k Certified content (mg/kg) Instrumenttion: The combustion unit is from Anlytic Jen, while the liquid hndling nd IC re from Metrohm. The softwre used ws MgIC Net from Metrohm. Combusion IC b Content (mg/kg) RSD (%) Recovery (%) Chlorine Bromine Sulphur Certified polyethylene stndrd from the Institute of Reference Mterils, Geel, Belgium b Fluoride Bromide Sulphte Appliction Ares The ppliction res described in this rticle illustrte the precision nd ccurcy of CIC. The smples nlyzed were plstic nd fuel smples s well s ltex nd vinyl gloves. Plstic Smples: The combustion of orgnic mterils contining hlogen nd sulphur produces toxic gses tht re hrmful to humns nd mterils. To gurntee tht plstics re hlogen- nd sulphur-free, quick nd relible nlysis is required. A certifed polymer stndrd, ERM EC68k (Institute for Reference Mterils nd Mesurements, Geel, Belgium), is used to check the precision nd ccurcy of CIC. It is low-density polyethylene grnulte contining known quntities of chlorine, bromine, nd sulphur. Figure illustrtes the nlysis of hlogen nd sulphur content of the reference stndrd by CIC. The recovery rtes, rnging between % nd 1.4% (Tble ), demonstrte tht the plstic hs quntittively combusted nd tht the combustion gses hve been completely collected by the bsorption solution. Liquid Fuels: Burning fuels tht contin sulphur produces sulphur dioxide tht is hrmful to the environment. In ddition, high sulphur content dectivtes ctlysts in combustion engines nd ffects both the storge stbility nd ignition behviour of fuels. The hlogen content lso plys n importnt role, s chloride in prticulr ccelertes corrosion in the refnery process nd in engines. The qulity requirements for gsoline re defned in DIN EN 8 nd DIN

The Column Figure 3: Determintion of sulphur nd hlogen content in gsoline. Column: Metrosep A Supp 5-15/4., eluent: 3. mmol/l sodium crbonte, 1 mmol/l sodium hydrogen crbonte,.

4 The Column Figure 3: Determintion of sulphur nd hlogen content in gsoline. Column: Metrosep A Supp 5-15/4., eluent: 3. mmol/l sodium crbonte, 1 mmol/l sodium hydrogen crbonte,. ml/min, column temperture: 3 C Fluoride Sulphte Advnces in GC-MS Anlysis of Pesticides In this new e-book, uthors from the US Deprtment of Agriculture, cdemi, nd Europen Union Reference Lbortory discuss dvnces in the nlysis of pesticide residues using gs chromtogrphy mss spectrometry (GC MS) methods. E-Book Eductionl Series Advnces in GC-MS Anlysis of Pesticides Tble 3: Determintion of sulphur content in gsoline. Content (mg/kg) RSD (%) Fluorine.8.46 Chlorine.5.34 Sulphur.88.4 The sulphur content must not exceed limit vlue of 1 mg/kg. Figure 3 shows tht in the gsoline smple under investigtion, the sulphur content ws just below this limit vlue t.88 mg/kg. Solid Fuels: It is lso possible to nlyze hlogens nd sulphur in solid fuels such s wood pellets nd brown or blck col (Figure 4). In the cse of the nlyzed col smple, the results demonstrted similr precision to those for the liquid fuel. Recovery rtes in the col smple were 6.8% for sulphur nd 13.4% for chlorine. Representtive nd, therefore, homogeneous smples re prerequisite for reproducible results. In the cse of solid smples, however, these re something of n exception, which is why ny irregulrities A formt for everyone This new e-book is vilble for the ipd or for stndrd computer web browser DOWNLOAD PDF TODAY! SPONSORED BY The world leder in serving science ARTICLES INCLUDE DISCUSSIONS OF: How to improve detection limits nd reduce mtrix interferences to extend the rnge of pesticides tht cn be nlyzed with GC The dvntges of negtive chemicl ioniztion (NCI) insted of electron ioniztion (ESI) Using tndem mss spectrometry in SRM mode to improve selectivity Lowering detection limits through lrge-volume injection (LVI) using cold on-column injection or progrmmble-temperture vporizer The benefits of using n ccurte-mss dtbse for screening pesticides by GC-TOF-MS A comprison of qulittive nd quntittive results obtined using GC TOF-MS nd GC-triple-qudrupole MS Smple preprtion using QuEChERS with cetonitrile extrction nd dispersive solid-phse extrction (dspe) An evlution nd comprison of three dspe sorbent combintions, compring clenup efficiency nd contminnt recovery

The Column Shimdzu_TheColumn_.13.qxd 16.1.13 11:6 Uhr Seite 1 Figure 4: Determintion of hlogen nd sulphur in col smple. Column: Metrosep A Supp 5-15/4., eluent: 3.

6 4 6 8 1 14 4 4 6 8 1 14 16 Tble 4: Determintion of chlorine nd sulphur in solid fuels. Content (mg/kg) RSD (%) Chlorine 1 5.5 Sulphur 143 1.5 must be tken into considertion when selecting smples.

5 The Column Shimdzu_TheColumn_.13.qxd :6 Uhr Seite 1 Figure 4: Determintion of hlogen nd sulphur in col smple. Column: Metrosep A Supp 5-15/4., eluent: 3. mmol/l sodium crbonte, 1 mmol/l sodium hydrogen crbonte,. ml/min, column temperture: 3 C. Sulphte Tble 4: Determintion of chlorine nd sulphur in solid fuels. Content (mg/kg) RSD (%) Chlorine Sulphur must be tken into considertion when selecting smples. Gloves in Clen Room Environments: Gloves re used in clen room environments to hold bck the ionic contmintion found in perspirtion from 16 hnds. Only mterils with low mounts of hlogen nd sulphur my be used in the wter-stem cycle of power plnts nd the primry circuit of pressurized wter rectors, so tht no corrosive hlogenides or sulphtes cn get into these systems. Hlogen nd sulphur content is therefore key considertion when selecting pproprite mterils for use in clen room environments. In this cse, vinyl gloves re the better choice becuse of their significntly lower hlogen nd sulphur content (Figure 5 nd Tble 5). mgent cyn yellow blck _3165.pgs :8 4 ADVANSTAR_PDF/X-1

The Column Figure 5: Determintion of chloride nd sulphte in ltex gloves. Column: Metrosep A Supp 5-15/4., eluent: 3. mmol/l sodium crbonte, 1 mmol/l sodium hydrogen crbonte,.

6 The Column Figure 5: Determintion of chloride nd sulphte in ltex gloves. Column: Metrosep A Supp 5-15/4., eluent: 3. mmol/l sodium crbonte, 1 mmol/l sodium hydrogen crbonte,. ml/min, column temperture: 3 C. Tble 5: Chlorine nd sulphur content in ltex nd vinyl gloves. Chlorine Sulphur Content (ppm) RSD (%) Content (ppm) RSD (%) Summry The CIC technique presented here provides fully utomted method of determining individul hlogens nd sulphur in multitude of orgnic mtrices regrdless of whether Ltex Sulphte Vinyl they re in liquid, solid, or gseous form. Following combustion digestion of the smples, the combustion products contining hlogens nd sulphur re collected in n oxidizing bsorption solution nd determined s hlogenides nd sulphte during the subsequent ion chromtogrphy process. By mesuring the light intensity, sensor trcks the progress of the combustion digestion nd ensures tht the smples combust fully. Complex smples no longer require method development becuse the optimum prmeters for combustion digestion re selected ccording to the type nd quntity of the smple. References 1. A. Wgner, B. Rue, H.-J. Bruch, E. Worch, nd T. Lnge, J. Chromt. A 5, 8 8 (13).. M. Leubli, C. Emmenegger, nd B. Bogenschütz, Ion chromtogrphic determintion of hlogens nd sulphur in solids using combustion s inline smple preprtion, th Conference on Ion Anlysis, Berlin, Germny, 13 (downlodble from metrohm.com/com/applictions/, serch for 8..61). Dniel Hemmler is n MSc student t Alen University, Germny. His mjor felds of study re nlyticl nd bionlyticl chemistry. Within his studies, he did n internship in the R&D Deprtment of Ion Chromtogrphy t Metrohm Interntionl Hedqurters, bsed in Herisu, Switzerlnd. Sophi Kufmnn is n R&D ssistnt in the Anlyticl Instrumenttion Deprtment of Anlytik Jen AG in Lngewiesen, Germny. She studied environmentl chemistry t the Friedrich-Schiller-University in Jen, Germny, where she lso obtined her diplom. Before joining Anlytik Jen AG in 1, she worked s scientifc ssistnt t Srlnd University, Germny, where she erned her Ph.D. in nlyticl chemistry. Christin Emmenegger is product mnger ion chromtogrphy in the Competence Center Ion Chromtogrphy t Metrohm Interntionl Hedqurters. After his diplom in chemistry, he obtined his Ph.D. in nlyticl environmentl chemistry t the Swiss Federl Institute of Technology in Zürich, Switzerlnd. Dirk Schmitz is project mnger in the Ion Chromtogrphy Development of Metrohm Interntionl Hedqurters. Dirk studied chemicl engineering t the Fchhochschule Achen in Germny. Alfred Steinbch is scientifc technicl writer nd editor in the Mrketing Deprtment t the Metrohm Interntionl Hedqurters. He obtined his MSc in nucler chemistry from the University of Cologne, Germny, nd his Ph.D. in environmentl nd nlyticl biogeochemistry from the University of Hmburg, Germny. E-mil: Website: st@metrohm.com

JUMO MIDAS C18 SW. OEM seawater pressure transmitter. Applications. Brief description. Customer benefits. Special features. Approvals/approval marks

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