Вы находитесь на странице: 1из 6

Technical knowledge o Do you know the material?

Can you: describe the types of atomic spectroscopy, answer basic and advanced questions

about the instrument, describing components and operation, and contrast this instrument with others we discussed such as an flame-AAS? o Do you know what you dont know, i.e., when to use the all important Im sorry, I dont know? communication skills o Can you demonstrate to the interviewer that you are knowledgeable? o Are you using the appropriate terminology (e.g., photomultiplier tube versus detection thingie)? o Are you interested, attentive, and responsive? o Is your interview conducted in a professional manner? Tell me a little bit about atomic spectroscopy o Technique to determine elemental composition of an analyte through electromagnetic or mass spectrum investigate properties of atoms or ions in gaseous state o Types: optical ionize sample to gaseous atoms or ions where absorption, emission or fluorescence, mass-ions separated by mass to charge ratios, x-ray where absorption, emission, or fluorescence for quantitative and qualitative analysis o 3 types: atomic absorption, atomic emission, and atomic fluorescence Absorption - measure energy absorbed in excitation process, provide thermal energy to sample to break bonds into free atoms by send sample through flame, then light beam measure absorption of atoms in gaeous state

Atomic emission - measure energy emitted in decay process, high energy and thermal environment to produce excited state atoms, energy source is electrical arc, flame, or plasma, allowed energy state from singlet singlet, triplet triplet, lifetime shorter excite atom using flame, plasma, arc, or spark

Atomic fluorescence use flame split sample into ground state atoms, excite atoms by light into atomic vapor, source of light is at angle so light detector sees only fluorescence in flame and not light from source, maximize source intensity since sensitivity directly related to number of excited atoms, forbidden energy state transitions from triplet singlet or singlet triplet, lifetime longer excite atom with light that has wavelength close to major transition

o Atoms absorb electron to excited state and then emit energy as light of certain wavelengths

Types of atomic spectroscopy/atomization-flame, electrothermal, inductively coupled o Atomic absorption (AA) ground state atom absorbs energy in form of light of specific wavelength and elevated to excited state, measure amount of light absorbs to determine concentrations Requires a primary light source, atom source, monochromator to isolate specific range of wavelengths of light, detector to measure light, electronics to process data signal o Flame - simplest, excellent reproducibility, low sensitively, easy to switch samples Flame atomic absorption spectroscopy Flame is usually heat, with acetylene/nitrous-oxide Sample introduced as aerosol into flame by nebulizer in spray chamber Light beam passes through flame where light absorbed Limitation inefficient since small fraction of sample reaches flame, atomized sample passes quickly through light path Single element, low sensitivity-high ppb, few samples, large volume >5 mL, detection limit of 1-100 ppb, signal intensity of 4 High sample throughput when large number of samples for limited number of elements, single element requires 3-10 seconds, requires specific light sources and optical parameters for each element, singleelement, low cost/relatively inexpensive Ideal for large number of samples for limited number of elements, determine major constituents and higher concentration analytes Cannot be left unattended because of flammable gas o Electrothermal - graphite furnace sample in furnace with flowing inert gas, high current applied, sample long time in tube, high sensitivity, easy to contaminate, have to clean but wait to cool, takes a long time to do a sample, horrible throughput Graphite furnace atomic absorption spectroscopy (GFAA) Sample introduced into graphite tube, heated to remove solvent, analyte atomized, atoms remain in tube and light path for extended period of time Electrothermal vaporization Sensitivity and detection improved over flame AA, 100 to 1000 times better Limitations takes longer than flame AA Few elements, more sensitive sub ppb, few samples, any volume <12mL or >5 mL, detection limit of .01-1 ppb, signal intensity of 2.5 Single-element technique, low sample throughput since remove solvent and matrix components, requires 2-3 minutes per element, medium cost, limited analytical working range, sample throughput less Analyze limited number of elements and require excellent detection limits Can be left unattended

o Inductively Coupled Plasma radio frequency field through induction coils, ionizes carrier gas creating plasma, flow of plasma because of magnetic field from coils, high temperature of 8,000-10,000K, atomization and ionization of stuff, LOD (limit of detection) better than flame AAS Argon plasma ionized argon gas High temperatures as high as 10,000 K allows complete atomization of elements and minimize potential chemical interferences Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES) Measurement of light emitted from elements, compare emission intensities to standards of known concentrations to obtain concentrations Charge-coupled devices (CCD) solid-state detectors Many elements, sensitive-high ppb to sub ppb-ppm, many samples, large volume >5 mL, detection limit of 0.1 to 100 ppb, signal intensity of 6-7 Multi-element technique with high sample throughput of 73 elements per minutes, if few elements require time for equilibration of plasma so 15-30 seconds for each new sample, high cost High sample throughput, wide analytical range, may be left unattended Multiple elements in moderate or large number of samples Inductively Coupled Plasma Mass Spectrometry (ICP-MS) Argon ICP generates singly charged ions from sample, directed nto mass spectrometer, separated according to mass-to-charge ratio, ions directed to detector to determine number of ions present Good detections limits similar to GFAA Allow quantification of elemental isotopic concentrations and ratios, can use with HPLC or GC allow determine exact form of species, not just total concentration Limitations how much sample Many elements, more sensitive- sub ppb-ppm to sub ppt, many samples, large volume >5 mL, detection limit of .001-1 ppb, signal intensity of 9 Multi-element technique, more than 63 elements per minute, wide working range, upper linear concentration range less than ICP-OES so samples diluted, most expensive Detection limits equal or better than GFAA with higher productivity, may be left unattended, limited solids in sample Multiple elements in large number of samples and require system capable of determining trace and ultra-trace analyte concentrations o ICP AES-high sample throughput ICP-OES high resolution, AAS quantitative, not qualitative, most easily done for solutions, Atomic fluorescence good but nobody does it, no huge advantage over AAS

Emission from nearby lines source modulation Small changed in temperature, big changes in species in exited state problematic for emission, but not absorption since absorption most in ground state anyways Solutions: Nebulizer pneumatic concentric most common but susceptible to clogging, Babington less susceptible to blogging but waste solution but more uniform drop size and higher pressure Solids: direct insertion, vaporization, ablation Light source excitation of sample Atomizer vaporize sample using flame or gas Monochromator allow select narrow band of wavelengths composed of entrance slit, collimating mirror, diffraction grating or prisms, focusing mirror, then exit slit Wavelength selector/filters monochromator or diffraction grating Radiation transducer (detectors) want amplification, low noise (dark count/current), high sensitivity, high S/N, fast response photomultiplier tube (PMT), photovoltaic cell, liner diode arrays or photodiode, charge-transfer devices like charge coupled device o Diffraction grating used to disperse light o Analyze the o The higher the resolution, the smaller the difference between distinguishable wavelengths Photomultiplier tube pre-selected wavelengths Spectrometer separate individual wavelengths of light

ICP-AES: inductively-coupled plasma atomic emission spectroscopy Interlock-series of clips make contact, electronics know door is closed, system confirms when door is closed Cooling water supply cool machine parts nearby, such as monochromator Flow gas through induction coil, big radio current, as gas moves in huge magnetic field rips atoms apart to form cations and electrons, then cool induction coil Plasma fire take material (solution), get rid of solvent, atomize-break into atoms, Plasma not enough fuel/oxygen for combustion Nebulize make into fine mist Plasma atomize, excites atoms to excited state, want as many as possible, strongly temperature dependent spit out photons Photons amplify; sample with lots of metals generate lots of photons, determine who emits photos differentiate based on wavelength, based on energies pick out photons with monochromator really good monochromator or disperse system because very narrow wavelength range and need to disperse well; detect Wheel rotates, rollers squeeze tube, pull solution through, stock nitric acid and waste Nitric acid wash nebulizer, prevent contamination Metals ionic form dont want form oxide or hydroxide particles, nitric acid keep elements in ionized form

Nitric acid strong acid, strong oxidizing agent, keeps metals in oxidized and ionized form Need gas Ar made into plasma, good at generate plasma, Ar also nebulize since need high pressure gas Gas from nebulizer and solution combine to go to induction coil Ar more expensive than N2 Blue flame - Ar generate in excited state, Ar relax, strongest emission line we can see N2-used to get rid of air in optical bench, get rid of oxygen and other trace elements that absorb photosn that generate in plasma Cone-shaped plasma is 8000 to 10000 K Shear gas shear off tip of plasma, air forced down at high rate, prevent plasma affect optics since heat will contract and expand optics and change aligments ICP-AES allows us to move quickly between samples much faster than graphite furnace electrothermal atomizer (very slow, good detection limits) Vent gases from heavy metals DI water clean out nitric acid since bad to keep strong acid that is corrosive ICP-AES allow parallelize measurements lots of measurements at once, screen lots of metals at same time Look at specific regions of spectrum Resolution nice optical components, disperse ligh twice eshelle grating and prism separate by order 2-dimensional grating better resolution - get one by fixed grating for each data point for eschelle, real all in region care about to faster Data: Wavelength on x-axis and intensity (cps) counts per second signal on y axis Wavelength x-axis, range is small like ~.2 nm, 30 data points fo every .01 nm High resolution pick out element interested in Standard diluted serially-what signal correlate to what concentration- look at calibration curve/standard curve Amount of signal as function of concentration Based on intensity compare to curve, as long as signal fall along calibration curve, not below limit of detection/quantification and below limit of linearity, somewhere within linear range, find concentration of sample Peaks from other elements not match emission line for metal Relative sensitivity Biggest peak bigger S/N not always good since may be too sensitive, or emission line from other element interfere/obscure this line, choose smaller peak with smaller S/N Preference order based on intensity, likelihood see interference from other metals, sequence of suggested emission lines DL mg/L ppm detection limit, cant see below DL Bad baselines default

http://www.perkinelmer.com/Content/RelatedMaterials/Brochures/BRO_WorldLeaderAAICPM SICPMS.pdf