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    CT Mrii Anachem2

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    Philippine Copyright 2018 by MANILA REVIEW INSTITUTE, INC. 3/F Consuelo Building, 929 Nicanor Reyes St. (formerly Morayta), Manila Tel. Nos. 735-0112 + 736-MRII (6744) www.manilareviewinstitute.com All rights reserved. These handouts/review materials or portions thereof may not be reproduced in any form whatsoever without written permission from MRI. CHEMICAL TECHNICIAN ANALYTICAL’ Classification of Analytical Methods HEMISTRY 2 Classical “Instrumental Separation Precipitation Evtraction, Distillation h Pressure Liquid Chromatography, 5 ene Ges Chromaograph Guallatve | ~Spot tests, Boling Point Melting Point Solbil of Odour, Refractive index! “Light absorption or emission, mass-to-charge rato, Guanitaive Gravimetios. ‘Y conducivty, electrode potential, luoresoence Volumetric i Comparison between Chemical and Instrumental Methods of Analysis Classical Instrumental ‘+ Generally cheaper r “Gan perform multvaiate analysis + Generally of higher precision Sometimes dependent on classical method ie. sample )preparetion “Ceti measure lower concentraion:10-2— 10° M “ Greater throughput of samples, shorter analysis time, less personnel ‘+ Amenable o automation, compatible with computers ‘+. Gan perform analysis that are diffcult or impossible using classical methods ‘Types of Instrumental Methods and their employed Analytical Signals ‘A Spectroscopic Methods Enrission of radiation Emission spectroscopy (Xray, UV, Visible, Electton, Auger); fluorescence, phosphorescence, and luminescence ‘Aesorplion of radiation Spectrophotometty and photometry (ray, UV. Visible, IR); pholo acoustic spectroscopy nuclear ‘magnetic resonance, and electron spin spectroscopy ear ‘Scattering of radiation “Turbidimetry, nephelometry, Raman spectroscop) Refraction of radiation Refractomety interferometry Difrection of radiation Xray and electron diffraction methods Rotation of radiation Polarimetry, Optical Rotary Dispersion, Circular Dichroism B._ Chromatographic Methods Peak signal HPLC, GC, Supercit uid Chromatography Page 2 of 20 C. Electrochemical Methods Elect potential Pojentiometry and Chronopotentiometiy Electric charge Coulometry Electic current Polarography, Aniperomety Electric resistance Conductomet) D._Other Methods ‘Nass-to-charge rato Wass Spectromety Rate of reaction Kinet Methods ‘Thermal Properties Thermal Conductivity and Enthalpy Methods = Racioactvity ‘Activation and Isotope Dilution Methods Design Philosophy of Analytical instruments ' JAnalytical electrical! output Signal Sgr) Transducer =, ean Signal. ional +} Read-Out Generator ae Processing produces signal that converts non-electrical, ““hyoaes signal to converts processed reflects presence and sional to lect sind” makéitconvenient signalto signal usually concentration o Understandable by of analyte user 1, Accuracy ~ indicates losenessof speared! true value Absolute error: 2. Precision — agreement among data obtained from several méasurements o ‘Repeatability - precision of several successive runs (within. day, one instrument, one analyst one laboratory) Fuggednass - precision of one lab over muliplé days, inducing mutple analysts, ripe insbuments, diferent reagents, ec. * Reproducibility ~ precision of several separate deleminations on cne sample, by different labs (several days, ‘ifferent reagents, one method or different methods, fc) Different Statistical Terminologies 2, Absolute Standard Deviation , s oro for N> 20 for Ne 20 f = ae Variance, s? or a? Relative Standard Deviation (%RSD) %GRSD=£190 4. Coefcient of Variation (cov) — eliminates the effect of magnitude ofthe values of the dat in the sel, and can be used in comparison of tvo methods . Standard deviation ofthe mean, sm sma iN {Spread of range — difference between the largest and smaliest value inthe set of meesurement. Range = Xnax— nia Tow accuracy High Precision Figh Acouraoy High Accuracy Low Precision Low Accuracy Low Precision igh Precision Page 3 of 20 3. _ Sensitivity - abiity to dsciminate between small ferences in analyte concentration; determined by slope ofthe calibration curve and precision aR (change in resp GC (change in concentration) ‘The higher the slop, the greater the sensitivity 4, Limit of Detection (LOD) - the minimum concentration or amount of analyte that can be detected at a known ‘confidence level; ‘the minimum concentration that will produce a measurement signal which is significantly different from the signal obtained from the background (or blank) solution. 5. Limit of Quantification (LOG) — lower limit for reliable quenttatve measurements “8 > <0D ‘6. Dynamic (or linea) range ~ gives the range of concentration over which a linear cliration curve is obtained; within this range, the response is linearly related to the analyte concentration. ‘© The wider the linear range, the better ‘+ Alinear calibration range is preferred because itis easy o determine the "best" line and carry out an interpolation to determine the concentration corresponding fo & esponse. The degree of inearity is measured using the ent (R2) Cenaton for inert RE > 0.960 SOE 7. Selectivity - gives the relative spate reos ‘o'speties 8 a cared 8. Robustness or Reliability — refers to how sensitive a as the size sample, the temperate, pH of souto Other Characterist idered in Choice Math Speed S ‘Case and convenience Skil required of operatof Cost and availabilty of eat Per samplecost. Signal and Noise s ‘s = Twocomponents of analytical measurements ‘Signal - component which carries the information about th Noise ~ extraneous component that unwanted because it degrades the amount ofthe analyte that can be detecte = Signalto-Noise rato (SIN) 4 _ "mean (signal) ‘td deviation (noise) | The goal in analytic! instrumentation isto reduce the noise and enhance the signal Introduction to Electro analytical Chemistry Electrochemistry is the study of reduction — oxidation reactions (redox reactions) in which electrons are transferred from one reactant to another. Fes + Vie Fete Vor ‘A chemical species that loses electrons in a redox reaction is OXIDIZED or undergoes Oxidation which is also a Reducing Agent. (LEORA) ‘A chemical species that gains electrons in a redox reaction is REDUCED or undergoes Reduction which is also an Oxidizing Agent. (GEROA) Page 4 of 20 Useful Terms and Relationships: Electric Charge, Q—is measured in Coulombs Relation between charge end moles: q=n + F Electric current, | ~the quantity of charge owing each second through a circuit unitin Amperes Electic Potential, E - the work needed to move an electric charge from one point to another unitin Volts Relation between work and voltage: W = E + q Relation between free energy diference and electic potential diference: AG = -nFE Ohm's Law: 1 = = Power: P= E+! Electro analytical Chemisty - group of quantitative methods that relate some measured elecical signal to actly or concentration of an ‘analyte species when itis made part ofan electrochemical cel Features ofelectroanalytical methods 1. Capable of measuring exceptionally low detection limits 2. Produce ways of describing analytical system e.g. sis Stoichiometry ae Rate of interfacial charge transfer See be, os a b ©. Rate of mass transfer te 4 e f Extent of mass adsorption/ Rate of chemical reaction Ecuiirium constant of ch 3 4. Instrumentation is relatively ines 5 ‘Summary of Electroanalytical Tect fume 2B Bs Technique) Convoed Parana Eat eared Conduciometry E { Voltage,V (AC) 2 ance, G = 1R ‘Conduciometric Titration Voltage, V(AG) i ie Veli. Conuaance Potentiometry Cutrentsi= 0; | “Potential, E Potentiometric Tiration Le aGurentii= Oy Tirént Volume ve. E | Cyalc Votametry =i Potential ivs.€ Polarography "SP Potetiial Es —_18.E | Anodic Stipping Valemety “Potential, ive Coulometry Eon Charge, q (integrated current) Electogravimety Eorl ‘Weight deposited ‘Coulometrc Tiraton im i e Tine, Electrochemical Cells -consisis of 2 electrical conductors (caled electrodes), each immersed ina sable elactroyte solution “CORE aes Example of Galvanic Gel (ponianouscheicl escton to generate elect) Cletielp fic non ip Requirements fr cunt dereop in ace 1. Electrodes connected externally by metal conductor 2. Two electrolyte solutions in contact to permit movernent of ons from ane to another 3. Election transfer reaction can occur at each ofthe 2 electrodes Page 5 of 20 Salt bridge — isolate contents of two halves of the cel while maintaining electrical contact between them Line Notations: | Phase boundary || salt bridge Standard reduction potential (E®) means that the ideal concentrations of all solutes are 1 M and all gases are 1 aim: otter solids or liquids are pure. Activity is equivalent to unity — (deeb etermining the st lectrode potential ofthe Cu/Cu(tt ion hal-cell, ——-. atm or 101 KPa + 2e7h Ha@)—> 2H) Bh 4h er dot AH) . balled Ihe S.H.E (standard hydrogen electrode) The letthal-el, connected tothe negatl neSH Re sianaate half. cel reaction. ‘The right hal-cel, connected to the posit Nemst Equation é ~ expression forthe net cing force for For the hatt-reaction: The Nernst equation gi Nemst equation at 250: Nernst Equation for a Complete Reaction Nemst Equation for a complete cel Nernst Equation for a complete ce Here is procedure for writing a nel cell reaction a finding its voltage: Step 1. Write reduction haif-reactions for both half-cells end find:E? for each in standard reduction potentials table, Multiply the half-teactions as neoessary so that they contain the same number of electrons. When you multiply a reaction, you do not ‘multiply E°. ‘Step 2. Write a Nernst equation for the right half-cell, which is attached to the positive terminal of the potentiometer. This is E+. ‘Step 3. Write a Nest equation for the left half-cell, which is attached to the negative terminal of the potentiometer. This is E-. ‘Step 4. Find the net cell voltage by subtraction: E = E.-E. Stop 5. To write a balanced net cel reaction, subtract the lft hall-reaction from the right halt-eaction. (Subtraction is equivalent to reversing the lft nal-cell reaction and adding ) Page 6 of 20 Potentiometric Methods analyses are based on measuring the potential of electrochemical cel without crawing appreciable cure reference electrode | sl bridge | analyte solution | indicator electrode Eref Fj Eind -known electrode potential that Potential constant Varies in concentration (anode) (cathode) Ecell = Eind - Eref + Ej Reference Electrodes Properties of ideal reference electrodes: 41. has known potential 2. exhibits a potential thats constant with time 5. _has potential thats insensitive to the composition of the solution under study 4, reversible end obeys the Nemst equation: 5. returns to its original potential after being subjected to small curents | is eke ; : . : Exhibits ite hysteresis with temperature cycing Standard Hydrogen... AgiAgCl Electrode Electode (SHH a - ks desciption oF st widely marketed reference code and can be used at perature greater than 60°C, cy and environmental ws problem ‘composition Consists of Pt wire or foil, coated Force of Hg inant ‘with 2 Contists of Ag electrode with Pt bok, immersed if | Solution that i satirated with HgiCie | immersed in a solution of KCI hypothetical solution of Uni | (caloms) and also‘contains a known | that has < been ‘saturated with id equilibriuih cohcertration of KCI Agci itpartal pressure! 7) g representation Pie (P= fam), H'(e=1) sara Kai) ARIAGC sate) KOA) | Half-cell reaction DH + ee Hi Searels) 2 AgCi+e —>Ag(s)+ Ch Nernst Equation Eye E0088 Za 0.05 Ee=£-0,05916log(Cl-] Type of calomel electrode Eval vii SHE, V AOC Ase 0 MCaiomel 0.3359 Ky =| ‘35M Calomel 0.252 0.250 Saluraied (4.17 M) Calomel 02g Se 0.2444 Type of AgCl electrode Eeel vs. SHE, V.AT2BO SSM AGAgC! 0205 Saturated AgiAgCl 0.199 J Indicator Electrodes ~ Ideally, indicator etectrodes responds rapidly and reproducibly to changes in activity ofthe analyte ion |,__Metalic indicator Electrodes Metalic electrodes ofthe kind ~consisis of mela electode immersed ins cationic solufon -tesponds tothe actly or concentration) ofthe cation solution -pure metal electrode = not widely used because not very selective, easly oxidized, cen be only used in neutral cr basic solution cause they dissolve in presence of acids 0.05826 Eng Eo SEES py = 0.9. AglAg* , HalHig®, CulCut, Zni2nt, CalCd, BiB, TUT, PbiPb™ Page 7 of 20 Nelalic electrodes ofthe 2 kind “consist of metal electrode in contact with an anion with which forms z precipate or stable complex ion, -tesponds fo the activity (ot concentration) of the anion that form sparingly soluble precipitates or stable complexes with such ions. Ege BO OBE py Meialic redox elecirodes consists of inert metal electodes (eg. Pt, Au, Pd, or C) immersed in an oxidaton/reduction system 2. Plelectiode immersed in a solution containing Cel) and Ce(IV) J Il, Membrane Indicator Electrodes = Also referred as ion-selective electrodes = __ Develops kind of junction potential across the membrane thal separates the analyte solution from a reference solution Properties of ion-selective membranes 1, Selective reactivity with analyte 2 Minimal solubitty 3.__Electrical Conductivity ‘Classification of fon- Seleaive Membrane Elecrodes ‘A Non erysialine membrane BEES. 8. Cystaline Membrane 1. Glass ©, Sica glass or H an 2 Liquid Junction Potentials = ae 2a ~ Develops across the boundary between fio electrolyte solutions yt eosin | = The magnitude of Ej Ceres by een a st nite e pH Meter { = The pH meter measur ofa sol sing an | se i respon tration tenon = The pH electrode produce tage that is roportional to the cohen 1e H¥ concentration. - The pH electrode is attachedto,contro ele ec Instrumentation ‘meter wih contol electronics and display. Some attached to the pH meter. Sees t joe electrode, an external reference electrode, and a ‘lectrodes usually combine al electrodes into one unit that are then ‘Summary of erors affecting pH measurements with glass electrodes: ‘Alkaline error (pH >14) ‘Acid error (pH < 05) Dehydration Error in pH of standard buffer Potentiometric Titrations Errors in low ionic strength solution (low buffering capacity) Variation injunction potentials (impurities) = involves measuring the potential ofa suitable indicator electrode as a function of tant volume Page 8 of 20 Features: Provide data that are more reliable than data from trations that use chemical reagents Useful with colored or turbid soluons and for detecting unsuspected species Can be easily automated Disadvantage mare time consuming cemt.my Endpoint Interpretation + tition cine has a cherectrste sid ure, The partof tn curve that hs the meximum change marks the equillene point of the tration, +The frst derivative, QEIAV, 1s th Slope ofthe curve, and the endpoint occurs at the volume, V, where AEIAV has the ‘maximum value. om Introduction to Spectroscopic Methods, es Fundamental Properties of Electromagnetic Radiation (EMR) Electromagnetic radiation — type of energy that is transmitted through space at enormous velocities; takes the for of light, radiant heat, X-ray, gamma ray, ultraviolet, miorowave, and radio-frequency radation. Models for Electromagnetic radiation: 4. Wave model -descrbes EMR 2s an elect field that undergoes sinusoidal oscilaton as it moves through space; itis characterized by parameters such as wavelength, frequency, velocity, amplitude etc rect TBAB tw Thigh Henseve Phase Dey 7 Corehen Page 9 of 20 Interaction of EMR with matter as wave ‘Superposition (constructive and destructive interference) b. Diffraction ©. Refraction 2. Particle mode! wave cannot completely explain the absorption or emission of radiation, where there is a permanent energy transfer to the absorbing medium or from the emitting object. -EMR is viewed 28 a stream of ciscrete particles or wave packets of energy called photons (or quant), withthe energy of a photon being proportional to the frequency ofthe radiation. ee ecu Mateos hy, Hoe tnt The visible spectrum Wavelength regioh. im 400 ~ 4355 435 — 480.5 480 = 4908 490-500 “i 500 — 560 ‘560 — 580 smentray color Yeiow— green i Wellow “Orange = Red Purple Violet aa 580= 595 Blue 595 - 650 Blue ~ green 650-750, Green - blue Interaction of EMR with matter ie Absorption of Radiation i. ‘Absorption ~ process in which a chemical species in a transparent medium Seléctvely attenuates certain frequencies of electromagnetic radiation IM (ground state) + hy —» M* (excited state) Relaxation ~ occurs when the excited species gives up its excess energy and returns toa lower energy. Ansorbing ‘huton of "Note: Tis transmittance whichis the fraction of incident radiation that is transmitted by a sample. Page 10 of 20, Atomic Absorption + Involves attenuation of only afew frequencies of radiation = Leads toelecronic transition only = Can be brought about by UV.VIS or X-ray radiation Molecular Absorption ‘Molecules undergo three types of quantized transitions when excited by uv, vis and IR 1. Electronic transition — transition of electrons between two orbitals 2 Vibrational transiton- @ molecule has @ mulitude of quantized energy levels associated with the ‘bonds that holds the molecule together. 3. Rotational transitions - associated withthe rotational motion of a molecule around its center of gravity Eiaal * Eamvoe + Evtratont + Erctaond AE eceie> AE vivatona > AE etn “Type of Spectroscon Type of Quantum Transitions Gamma ray emission Nuciear ‘cay absorption, emission, Nuorescence r ‘and diffraction Inner electron Uiteviolet visible absorpion, emission, average lifetimes 1018 seconds i) ene Non rive roan tes Has been of another electonic state, The one is \ é er level of af exctd electrons state mite ‘upper vibrational level en 10° 10°! hisless effclent ee Flouresvence and Phosporescence emission proces etestomagneti radiation letules ate ‘excited by the absorption of a beam of i meter feos yp Types of Emission Spectra ‘ 1, Line spectra ~ atoms or elements, well - resolved 2, Band spectra —_mclecules 3. Continuous spectra - not resolved, interaction of solvent with solute Relationship between absorbance and concentration (Beer - Lambert's Law) The absorption of radiant energy by matter can be described using Beer's Law. Consider a block of an absorbing material of concentraton, ¢ and thickness, b: Ae EOC k#——_ b ——__ [E-acfide -n£ = abe he P , Pp ——} P A=logi = cbc A=log—= abe where T= transmittance, A = absorbance A A Concorso berber, Page 11 of 20 Application of Beer's Law to Mixtures ~ Fora solution containing more than one kind of absorbing species, the total absorbance is given as follows provided that there isno interaction among the species. total = Ag + Ag + Ay = £,be, + &ybeg ++" &,bC, Limitations of Applicability of Beer's Law ~ Act YP bl Le Gceetodd = Deviations rom direct proportonality between ed and concentration exis. Real imitation — applicable ony fr dite solutions yo leg Gracin freer Instrumental deviation with polychromat radiation Instrumental deviation in the presence of stray racation Instrumentation for Optical Spectroscopy ae General components for spectroscopic instruments Souroe of radiant energy 2. Wavelength selector ij 3. Sample container baby P 4, Radiation detector or transducer P 5, Signal Processor nd readout Instrument Lay-out for Absorption Instrument Lay-out for Emission (1) Souree ll Co, f Signal processor = ag anf readout G) Sample Instrument Lay-out for Flourescence, Phosphorescence, and Scattering 13) Sample @ [Wavelength en eile fo Lo Seed pooner woneans tn retdon t [_j source Page 12 of 20 Raciation Sources = Provides energy for excitation = Output needs to be constant, stable, and intense enough = _ Requires a regulated power-supply (minimize errors) ‘Types of radiation sources ‘1, Continuous source ~ emit radiation over wide band of wavelength e.g, D2 lamp, high pressure gas filed arc lamp. 2 Line source ~ emit a limited numiver of bands of radiation. Wavelength Selectors = Device that restricts the radiation being meesured to a narrow band tht is absorbed or emitted by the enalyt, Narrow wavelength of raciation = Enhances sensitivity of absorbance = Provide selectivity to both emission and absorption method (effective bandwidth) = Required for obtaining a linear relation between the optical signal and concentration Th gor peso wong ecb Files ~ operate by absorbing al but a resticted band of 2 Norocvonetre Conger: Entrance sit CColimating lens or mirror tof prog Prism or grating to dispers Focusing element tht refol theimege Exit si inthe focal plane oe isolates Radiation Detector = conver electromagnetic raciation energy into elecical energy (voltage, current, or charge) Ideal Characteristics: fast response high senstivty respond to low level of radiant energy high signa-o-noise ratio constant response over a wide wavelength range ‘minimal output signal in the absence of ilumination produce electrical signal directy proportional to radiant power Page 13 of 20 Photon Detector Heat or Thermal Detectors ~besed upon the interaction of radiation with reacive surface to | -based upon the eating effect of reciaon and consists of Eny emit electrons resulting in the development of photocurrent | blackened surface that absorbs infared radiation and increases in (photoemission) or to promote electrons to energy states in which | temperature; whichis converted to an electrical signal ‘hey can conduct eleciciy (photaconduction) -useful for detecting UV, VIS and NIR, not IR useful for measurement of IR radeon a Types: Types: Photolube Thermocouple Photomuitiplier Bolometer Siicon Photodiodes Preumatc Detector Photodiode Array (PDA) Photovoltaic Ces, Photoconductivity Sample Contsiners ‘als0 called as cls or cwettes = transparent container fr holding the sample; must have wind region of interest : = cals need to be matched and cal = carelcleaning ~ no fingerprints, {yale rom material that tensparentin the spect Types: ‘a. quartz or fused silica — requir in the IR b. slcate glass — suitable betweer ©. plastic — applicable inthe visible egion * 4d. crysaline NaCl, KBr— "4. fe. flame ~in AAS. Molecular UV-VIS Absorption she Seay | ~ Widely used for identifeation of myriad no ~ Setetonem Tae 5 aghast ets ‘corélated wit Types of molecular species that: absor uvivis ae 4. Organic compounds - shared electrons that participate in bond orate a ‘ , 2 tea ie a 3. Charge transfer complexes “ ‘Atomic Absorption Spectroscopy (AAS) = Isbesed upon the principe that free atoms inthe ground state can absorb ght of a certain wavelength. = Absorption for each element is specific; no other elements absorb ths wavelength, AAS is a single-slement method used for trace metal analysis of.g., biological, metallurgical, pharmaceutical and atmospheric samples. = Spectroscopic deternination of atomic species can only be performed on a gasitied sample in which the individual atoms such 8 Ag, Al, Au, Fe and Ig are well-separated from each other. be Bug ~ Geen Pome guy Page 14 of 20 Sample Anaysis Heat is needed to gasify the sample. ~The heat is generated from a flame or a graphite furnace. - Flame AAS can only analyse solutions, while grahite furnace AAS can analyze solutions, slurries end solid samples + Aflame atomizer consists of a nebulizer which converts the sample ino an aerosol that i fed into the burner. The atomization takes place inthe lame commonly fed by the fuel gases acetylene and nitrous onde. = Anelecto thermal atomizer gives high sensitvty because it atorizes the sample rapidly. = Atomization occurs in a cylindrical graphite furnace that is open in both ends and has a central hole forthe introduction of the samples. + Two inert gas streams are used. The extemal stream prevents ai to entry the furnace and the intemal stream ensures that ‘vapours generated from the sample matrix re quickly removed from the oven. The most widely used gas isargn. Chromatography ~ Components are seperated based upon rates at which they are carried through a stationary phase by a gaseous or liquid mobile phase. ‘Components of Chromatography: 4, Stationary phase - does not move 2. Mobile phase ~ does move i Chasteion ad onshica nal Calutin Chromatoa ‘Stationary Phase isheldin narrow tiba. ‘Mobile Phase Is foroed througfthe tube un Classification based upon the ;, Super cic i uid chromatography Mobile phase Eau [2 Siperrtial uid HE arn ‘The Separation Process (Elution) Elution ~ solutes are washed through a Slatonary Eluent ~ solvent used to carry conn of mixture! addlton of solvent cary solute molecules down the column in a continuous series of transfers between the two phases -rate of solute migration depends upon the fraction of time solute spands in mobile phase -components strongly retained by the stafonary phase will have long elution times Page 15 of 20 Band Broadening and Band Separation -diuton of analyte nearly aivays accompanies separation 1.5 complete resoluton Reco TSincompote separation | "OWE the expense of increased anajs ne RS= 1.0 around 4.0% overlap we =i (a ar @ — ind B, with B s the slower moving species y oy Thunber of plates needed ahi fg given resotufon < ule two specieS with a resolution Pranee, B Edy Gfision ip | -similar diameter packing avoid loose packing 5 Molecular Difsion— Incfease flow rete to decrease f analysis time c Resisianoe to mess transfer Resistance to mass transfer “use thin coating use less viscous phase keeping flow 28 ow Optimization is therefore important Optimization Techniques NOES Piate Height To decrease Reduce paride size/packing Reduce Diameter of Column Reduce thickness of fim Retenton Facior Toincrease Optimize temperature Optimize SP thickness ‘Selectivity Factor To norease Change composition of MP Change column temperature Change composition of SP Use special chemical efecis RYN ec VL Page 17 of 20 Gas Chromatography components of vaporized sample are separated by partioning Instrumentation Carrier Gas = Inert, He, Ar, Nz commonly used = Compatible withthe detector = Lite interaction between sample and Fiow rate controlled by pressirettegilators Canter Gas @tmaa” 5 O Helium fea zh Wikoger a= af Hydrogen 1 e ‘Argon! Methaie, fe Sample injection System i =the sarnpe is injected as discrete plug of — eae. Gee i b i: ubber septurn = + Septum purge outlet ==> Spit outiet ‘Vapourisation chamber Column . | + injection port temperature must be at least5 degrees above boiling point of the most volatile | ‘component we) 1 Types of injection system: Vena Heated metal black 4, On column injection system 2 Spit-spittess (cepilary) 3. Headspace analysis epld ~ ly br toncuodovfn Splt lie “Leu conn ftw Glass liner Column Page 18 of 20 ‘Types of Column 41, Packed column ~ glass or stainless tubes ID = 1.5 mm), length (1-3), coed to inside the column oven 2 Open tubular (or capilary) = made from fused slica (ID = 30 ~ 500um) length (3-10m) with greater seperation efficiency than packed columns. ee | alata) aie - ——— eae nano orto For [> WOOT > SCOT > Faded Fused Sica Wall Coated Open Tubular Open Tubular -puifed sea “Banos steal glass Diaiomacoous no meta oxide sap Ear packings mage oe OPT cuter oe 3 |__polyaie Column Oven i : Optmum temperature cetetinedby ling point - ener ener /sneage ng Types of temperature contro Pa iad 1. Isothermal elution, 2. Temperature programmed elution a -lo improve resolution for all components oe a Detectors Type Mode of Detection Disadvantages ‘Applications “Thermal Conductivity | Change in resistance of wire based on | Low sensiivly Organic inorganic Teo variations in thermal conductviy of valving gas in column Flame lonizaion FID | Production of ions in fame resuting te | destructive Hydrocarbons meesurable current Elecon Caplure ECD [absorption of beta parldes by species | Radoaclve Halogens, nities, emitted by Ni83 “Limited near response | niaies, conjugated -ions end electrons are created double bonds Thermoionie TID -plasma is fomed around class bead fo NP produce radicals ~tadicals react with Rb vapour to produce | alkali ion -bured by electrons GAO Pant ge F filter Page 19 of 20 Fal ~iixed wih reaction gas Falogen, §, -products are dissolved in liquid which produces conductive solution -change in conductivity Flame Phoiometic FPO | -compounds are partially combusted SP emission of fight is produced and measured by PMT Photoionizaton -photoionized by UV radiation ‘Aromatic, easily -lons and electrons collected by electrodes ionized compounds -resultng currents measured ‘Atomic Emission AED | -atomizaton and emission ocours Dh 20% error OPS -ciode array photometer was used High Pressure Liquid Chromatography ‘Block diagram showing the components ofan HPLC instrument <3 Ciasifiaton of HPLC Methods ae Ak f ey a ‘Staioray Phase [Mobile Phase Normal Phase oa Polat ff YE INon- Polar Reversed Phase Nohzpolat Fy Polar: 2 Eluied last b Sova IEluted frst ‘Other HPLC Methods PERE ¥ ? WEEE [-Appications “07 f ‘Adsarplion Solid Gasiiqul =sanipl molecules that can react with -SIOH groups a |}-ten-onizing weter insoluble ‘molecules which maybe : isomers Ton Exchange wold Tiga -Separation of weak acids and bases and inorganic ons Partlion Tiquic “guid Size exclusion gel Gasfiquid “ra sigh molecular weight species ‘Aiiy sold liquid | Sinvolves covatently bond reagent Chiral sold liquid Rand § ennatiomers Solvent! Mobile Phase + filtered and degassed before being placed in solvent reservoir Solvent Delivery System provides a constant pulse free flow of MP deliver a reproducibe flow rate Pump System Isocratio- one solvent Gradient Elution ~ continuous change of solvent composition to increase eluent strength ‘Sample Injection System introduces sample into the high-pressure eluent as a discrete low volume plug Page 20 of 20 Columns Guard Columns — placed between injection system nd analytical column ‘Analyicel Packed Colurmns- commonly made of siiniess steel fp ~~Detectors aa, = Measures a physica or chemical property of each sample component ast elutes om the column, + Provides both quantitative and qualitative information Type Mode of Detection sais ‘Applications Wis ees Sarigad oolahing chromophores Diode array ~radlation from source pa or Ms a a . ‘eochp cides none of Fuoresoence git fra wasiengiae fe rit essed through ae in oo gaa an ght ogee angles to the ep

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