BASIEGAS; de‘TECHNIQUES IN ANALYTICAL CHEMISTRY SERIES BAKER + CAPILLARY ELECTROPHORESIS CUNNINGHAM +» INTRODUCTION TO BIOSENSORS LACOURSE + PULSED ELECTROCHEMICAL DETECTORS IN HPLC MCNAIR AND MILLER + BASIC GAS CHROMATOGRAPHY METCALF + APPLIED pH AND CONDUCTIVITY MEASUREMENTS MIRABELLA » MODERN TECHNIQUES IN APPLIED MOLECULAR SPECTROSCOPY SCHULMAN and SHARMA + INTRODUCTION TO MOLECULAR, LUMINESCENCE SPECTROSCOPY STEWART and EBEL. + CHEMICAL MEASUREMENTS IN BIOLOGICAL SYSTEMS TAYLOR » SUPERCRITICAL FLUID EXTRACTION Basic Gas Chromatography HAROLD M. MeNAIR, Ph.D. Virginia Posteshnie Tsite and State University JAMES M. MILLER, PRD. Drew University ® A Wiley aterscience Publication JOHN WILEY & SONS, INC. [New York + Chichester * Weinheim + Brisbane + Singapore * Toronto‘er GC pop epi by emi 024 Sent Pet Spon nthe nero Coe mau Taste pedo ie pape @ [At ah rene. ui imac hae {ht permite ty Sto? olathe 196 Unaed Seu Chr A Se pmon ft aye tte Cr min tte ‘asic gn cromtoraphy / Harold M. MeN Sues ies, a os SSS mes aS Contents Series Preface Preface 1 tntrodcton A Bric Hitoy Overview: Advantages and Disadvantages 2 Imirument Overview cases Gas Flow Control and Measurement Sample nts and Sampling Devies Colas “Temperature Zones Deters Data Stems 3 asi Concepts and Terms lintons, Terms, and SymborsThe Rate Theory A Redetition of H The Achievement of Separation 4 Stationary Phases Selecting & Colum ‘Castiation of Stationary Phases fr GLE Liga Stationary Phases (GLC) © Sold Stationary Phases (GSC) 5 Packed Columas and Ines Solid Suppers iid Stationary Phases Sod Stationary Phases (SC) Gai Anais Inet for Liu Samples and Solutions Special Columns parading for Capitay Colma (6 Capitary Columns “Types of OT Colunas OT Colum Tobing ‘Advantages of OT Colamns Colom Selection Capillary Inlet Systems Indes 7 Detectors Cawifcation of Detectors Detector Characteristics Flame foieaton Detector (FID) ‘Thermal Conductivity Detector (TCD) etron Capture Detector (ECD) (Omer Detectors 8 Qualitative and Quantitative Anais Ouattaive Anais ‘Quantitative Analysis conten si 2 s a S2SEeR foResaoe 1 1s 12 6 ug rs 6 16 an Contents 9 Programmed Tempertore Temperature Etfets Advantages and Disadvantages of PTGC Requirements of PIGC “Theory of PTGC Sper Topics 10 Special Topics oc-ms (Chiral Anais by GC Special Sampling Methods Derivatization 11 Troubleshooting GC Systems Appendizes 1. List of Symbols and Acronyms 1 Guidelines for Selecting Cepilary Colunas LIL GC: How to Avoid Problems 1. Calculation of Split Ratio for Spt injection on (OT Camas LV. Operating Conditions for Coplay Columns VE OV Ligud Phases Physical Property Data VIL Some Pressure Corection Factors ()) IIL List of Some Chromatographic Suply Houses TX. Other Resourses Aces of Applications Ades rn 14 46 ue 150 153 163 164 1 0 1s vo 18 191 1 3 4Series Preface “Ties ia the Techniques in Analytical Chemistry Seis address current Technics in general se by analal abortions. The series intends (0 Serve roa audizce ofboth prationers and cent of chem analysis “Tis audenceinclods not only aalicl chemists but abo professionals in other areas of chemi) and a otber dciplines eying 0 information Cervelo chemin analysis, Tu, the srs shoud be uct fo both Inoeatory and management personnel. ‘Writen for readers mith varying levels of edation and laboratory expertise tiles the series donot presome prior Knowledge ofthe subject, [nga the eae step by stop ough each tchngue- Numerous apt Cations and diagrams emphasize practi, applied approach to chem: “The specie objectives ofthe series ae + toprovide the reaer wth overviews of methods of naljsisthat inctue {bass inedcton to peniples But emphasie such practical aes {etechniue selection, ample preparation, measurement procedues, ‘ata analy quality contol a quay assurance: + to give the eeader a sense ofthe capbilties and linitatons ofeach techie. and fel fore appa to specie problems “to cover the wide rage of uf techniques, from mature ones 10 newer methods that are coming into common us: and + to communicate past loration in a readable, comprehensible Sle Reaer from he tecnica through the PAD sett o bora. Series Prece tory manager should come away with cate and coatdence about the {ee of the techniques Forticoming books inthe Techniques ix Anata Chemity Series wll over variety of techniques including chememetric methods, bcweso Sarface and interace analysis, measurements in bloga yes nde Sly coupled plasma-mass spectrometry. gas chromatopraphy -mas spe {eomcry, Four tansform infared spetoncopy, aad ther Sinica topics. The ers weleome your comments and sugestions tozaing atten ad future tiles and hope you find the erie stu rane A. Sern, Preface [A series of hooks om the Techniques n Analecal Chemis would be incomplete without a volume on gs chromatography (GC). undoubtedly the most widely used analytical technique. Over 0 yeas in development ‘Gc has become a mature method of analysis and one that Is thy 10 fade in pops. Tn the euly years of development of GC, many books were writen 10 lngom analysts ofthe latest developments. ew of them have been kept uptodate and few new anes have appeared, so tat satisfactory single inteoductry text dacs no exist. Ths book attempt 10 mest hat aed. Tt ‘bse in part onthe caler work bythe same ie, Basie Gas Chromaog- ‘rap, coauthored hy MeNairand Borell and published by Varia Instr ‘ments Some mater ako drawn from the eater Wiley book by Nil, (Chromatography: Coneps and Contras. ‘Weave atempied to write brie basi introduction to GC following the objectives fortes in this serie, It should sppeal to readers with ‘arying levels of education and emphasizes «praca, aplied approach to te subjec. Some background inches i required manly perl ‘tganic chemistry and some phy chemisry For ein forms cas ‘work, the Book should besiable for undergraduate anal chemisty Courses ad for intensive short courses of he type offered bythe America {Chemical Society and others. Analysts entering the Held should fad ‘ndapensable, and nds chemist working in GC should adit aut ‘elereace and guide.a Preface ‘Because the TUPAC ha recently published is nomenclature recommen ations for eheoatograpiy. we hive ted to use them comatenty (0 promot aunied set of detniions and symbols. Abo, we have endeavored {Dvnteinaschs way tht the book wouldhave the carasteisi ofa ile utor, asl especaly important for beinners in the el. Otherwise, he Content and coverage ae appropriately conventions "While open tabular (OT) sola ae the mot popular type both open ‘pula and packed columns ae tented throughout. ad the advantages, ‘tsodvantages, and apphieatonsarecomeasted, nado, pil chapter re devoted w each pe of column. Chpte 2 introduces the ise asta ‘mentation and Chapter 7 elaborates on detectors Other chapter cover Stationary phases (Chapter 4), qualitative and quantitative analy (Chop 'er8), programmed temperature (Chapee9), and woublesootng (Chapter 1), Chapter 10 riefy coves the important special topes af GC-MS, ile Ta + Oe z en where ds the distance betwen the peak maxi fortwo solutes, A and '. Figure 37 iustats the way la which resolution eaesnted. Taogens ‘ce dawn tothe inflection points i order to determine the with of the as at their base. Normally adjacent peas of eal aes wll hve the Same peak widths, and (will equal (yy. Therefore, uation 21 is reduced to aod @ a ge 3, net ae jt ching 0 = md = 10 Te Ie ve oo he tr pro om, tg ‘uno equiers ion a Sty ing enn nd 2 wld nly when th ih ot eo pnb sha Fi 37a ome et jak ep gery Se a al bse fe enpar ee eeo asic Concepts and Terms ro 4 \/ V ‘m3 Two auth pss ng heels of rena, Fo Me, Sema Cina cS “able 32 contains «summary of the most important chromatoprphic esftions and eauaton, anda complete Ist of Symbols and acronyms ined ia Append ‘THE RATE THEORY “The cast attempts to explain chromatographic band broadening were thsed on en equiv todel which eam To be known asthe Plate "Theory, While twas of son vale, 0t dal withthe nonegulis maton that ately extn the coum ad id nt addres the cases of band brosdeiag, Homever, a erative approach deserting the kinetic {acon way soon prevented it became Know asthe Rate Tory “The Orignal van Deemter Equation “The most afeetial paper using the Kinetic approach was published by sh Deemer, Klnketberg, and Zager i 1986 [3] Tented thee ‘ete that contribute to tand broadening in packed columns di So (the A-trn,Jongitodinal meleclar itfson (the Berm), and mass tanfr inthe sonar id phase (Te Cte), The broadening was xpress interme ofthe plate eight, H, as function of the average Inca ens vel, Init spe form, the van Deemer Eguaion is The Rave Theory a naman ghp newer (2) = (2) =550 ad @ Slace plate hea is inversely proportional o plate aumber small value Ingiates a narrow peak-the dstalecondidon. Ths, cat ofthe three ‘omstants. A, Band C should be minimized inorder to maximize cot ‘mn efseny. ‘The Golay Equation Since open tubular or capillary columns do not have any packing. het fate equation docs not have a9 term. Ths conclunion sam pointed oUt by Gola [i who aso propoed anew tem to deal withthe dillon ces in the gas pas of open tubular cols. His equation had 0 {Cserms.one for mass transfer in the stationary phase, Cy (sir to van| a Baie Concepts and Terms ‘Deere, and one for mas transfer in he mobile phase, Ga, The spe Gola equation is a G4 Gu) eH ‘The Beem of equation 2 acount forthe well Anown molecular dts sion The equation governing moleslareitfason i B=2De ee, where De the dition coffin forthe saute nthe cries Fire $e ilustates how s zone of molecules dfs from the repon of igh oncetetion to that of over concentration wit ine. The equation tel ‘thats salve forthe difson coefficient desirable otha diffusion | minimized, yielding a sl val for Band for 1. In general, om Atson coeticeat can be achieved by using carter uses with larger ‘molecular weights ik nope o argon nthe Golay equation equation 20), this term i vied bythe linear velocity, 0a large velit or fom ‘te wil ako minimize the contrbation ofthe Berm to the eneal pele Sroadcring, That igh velocity wl decrease the ime a sole spends ‘nthe column spd thus derese the Une avilable foe mozcla diffeion. ‘The Cems inthe Golay equation relate to mass transfer of he sole, citer inthe stonary phase ori the mobile pase deal fast ste ‘keri Chomp oepand ora Soe icy S.No ‘You Sep Recs cnneny abe Wey oe The Rate Theory s sorption and desorption will Keep the solute molecules close together and keep the tand brosdning to 2 mimi, Mass traafer i he stationary phase ean be decribed by reference 19 Fare 39. In both parts ofthe gue, the upper peak represents the ‘stebutio ofa solute inthe mobile phase andthe lower peak he dsb tion inthe stationary phase. dtbuion constant of? is wed i this txample so the lower peak has twice the afea ofthe upper ae. At equi ‘um the solute achieves lative distributions ike thos shown in part (a), but an instant ater the mobile gas moves the upper carve dowasiean sSvingise othe situation shown n(8.Te solute molecules inthe station ty pase are stationary the solute molecules in the gas phase have moved ‘shed of thes nthe stationary ise tho broadening the overall zone of ‘molec. The solute molecule which have moved aad mist now pert tin ito the saonary phase and vce vere for those that are it the ‘Ssionaty phate, a sha by the sow The fate they an make this lunsfr the es wil be the band roading "The C-term in the Goly equation i 2k CTT 25) where the average film thicknes ofthe gid stationary phase end Dp is the eifeso soeficent ofthe solute inthe sationry pha. To rnimize the coniaton ofthis term, the fm thickness boul be small 'nd the tion cetcet large. Rapid difeson through thin salons the solute molecules to stay closer together. Thin fm can be achieved by coating smal amounts of liquid om the capillary wal, but diasion efficients cannot usally be controlled except by selecting low vss ‘tionary lig, ‘Minimization of the Cerm resale when mas transfer into and ot of| the stationary guid isa fast as posible An analogy would be to coasier 4 person jampng into and out of «swimming pool ite water hallo, the proces can be done quickly: itis dep. cant ithe stationary phase a sé, modifeatios in the Cem ate neces: sary to relt i 10 the appropriate adsorption desorption Kinet Asin, {he aster the kinetics, the loser the process sto equlibum, and he es Js the hand broadening. “The ater pat ofthe Cyr the ratio hi +k Large vale of ‘est rom high sluts in the stationary phase This ratios inimized atlnge alucs of £ but very lle decease gecus beyond a kale of Stout 20 Since lg vals of tention factor esl in long analysis ties, Tite advantage fs gained by K-values lager than 20. "Mass arse inthe mobile phase can be visualized by reference to Figue 3.10 which shows the pre of s solute zone ay» consequence of