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Lecture 6 ATOMIC SPECTROSCOPY Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display.

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Presentation on theme: "Lecture 6 ATOMIC SPECTROSCOPY Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display."— Presentation transcript:

1 Lecture 6 ATOMIC SPECTROSCOPY Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display.

2 Sample is atomized (atoms/ions) absorption or emission measured INTRODUCTION TO ATOMIC SPECTROMETRY

3 ENERGY LEVEL DIAGRAMS Every elements has unique set of atomic orbitals p,d,f... levels split by spin-orbit coupling Spin (s) and orbital (l) motion create magnetic fields that perturbeach other (couple) if fields parallel - slightly higher energy if fields antiparallel - slightly lower energy INTRODUCTION TO ATOMIC SPECTROMETRY

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6 ELECTRONIC TERM SYMBOLS INTRODUCTION TO ATOMIC SPECTROMETRY

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8 Similar pattern between atoms but different spacing Spectrum of ion different to atom Separations measured in electronvolts (eV) As # of electrons increases, # of levels increases Emission spectra become more complex Li 30 lines, Cs 645 lines, Cr 2277 lines INTRODUCTION TO ATOMIC SPECTROMETRY

9 As # of electrons increases, # of levels increases Emission spectra become more complex Li 30 lines, Cs 645 lines, Cr 2277 lines INTRODUCTION TO ATOMIC SPECTROMETRY

10 Desire narrow lines for accurate identification Broadened by (i) uncertainty principle (ii) pressure broadening (iii) Doppler effect (iv) (electric and magnetic fields) INTRODUCTION TO ATOMIC SPECTROMETRY

11 (i) Uncertainty Principle: Quantum mechanical idea states must measure for some minimum time to tell two frequencies apart ATOMIC LINE WIDTHS

12 Shows up in lifetime of excited state if lifetime infinitely long, E infinitely narrow if lifetime short, E is broadened INTRODUCTION TO ATOMIC SPECTROMETRY

13 Example Lifetime of Hg*=2x10 -8 s. What is uncertainty broadening for 254 nm line? INTRODUCTION TO ATOMIC SPECTROMETRY

14 Differentiating with respect to frequency: sometimes called natural linewidth. INTRODUCTION TO ATOMIC SPECTROMETRY

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16 (ii) Pressure broadening: Collisions with atoms/molecules transfers small quantities of vibrational energy (heat) - ill-defined ground state energy Effect worse at high pressures For low pressure hollow cathode lamps (1-10 torr) Å For high pressure Xe lamps (>10,000 torr) Å (turns lines into continua!) INTRODUCTION TO ATOMIC SPECTROMETRY

17 (iii) Doppler broadening: Change in frequency produced by motion relative to detector INTRODUCTION TO ATOMIC SPECTROMETRY

18 In gas, broadens line symmetrically Doppler broadening increases with T At room T ~ Å Total linewidth typically Å INTRODUCTION TO ATOMIC SPECTROMETRY

19 Other Effects of T on Atomic Spectrometry: T changes # of atoms in ground and excited states Boltzmann equation INTRODUCTION TO ATOMIC SPECTROMETRY

20 Important in emission measurements relying on thermal excitation Na atoms at 2500 K, only 0.02 % atoms in first excited state! Less important in absorption measurements % atoms in ground state! INTRODUCTION TO ATOMIC SPECTROMETRY

21 Methods for Atomizing and Introducing Sample Sample must be converted to atoms first INTRODUCTION TO ATOMIC SPECTROMETRY

22 Must transfer sample to atomizer - easy for gases /solutions but difficult for solids INTRODUCTION TO ATOMIC SPECTROMETRY

23 Lecture 7 ATOMIC EMMISION SPECTROSCOPY Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display.

24 ATOMIC EMISSION SPECTROSCOPY (AES) Identification of elements but not compounds INTRODUCTION TO ATOMIC SPECTROMETRY

25 Excitation and Atomization: Traditionally based on flame but arc and spark plasma excitation offers (i) increased atomization/excitation (ii) wider range of elements (iii) emission from multiple species simultaneously (iv) wide dynamic range ATOMIC EMISSION SPECTROSCOPY

26 Flame Excitation Sources: Primary Combustion Zone Interzonal Region Secondary Combustion Zone ATOMIC EMISSION SPECTROSCOPY

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28 Laminar Flow Burner: Cheap Simple Flame stability Low temperature ATOMIC EMISSION SPECTROSCOPY

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30 Arc and Spark Excitation Sources: Limited to semiquantitative/qualitative analysis (arc flicker) Usually performed on solids Largely displaced by plasma-AES Electric current flowing between two C electrodes ATOMIC EMISSION SPECTROSCOPY

31 Electric current flowing between two C electrodes ATOMIC EMISSION SPECTROSCOPY Sample pressed into electrode or mixed with Cu powder and pressed briquetting Cyanogen bands (CN) nm occur with C electrodes in air - He, Ar atmosphere

32 Arc/spark unstable - each line measured >20 s (needs multichannel detection) photographic film: Cheap Long integration times Difficult to develop/analyze Non-linearity of line "darkness" ATOMIC EMISSION SPECTROSCOPY

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35 multichannel PMT instruments: for rapid determinations (<20 lines) but not versatile routine analysis of solids - metals, alloys, ores, rocks, soils portable instruments ATOMIC EMISSION SPECTROSCOPY

36 Plasma Excitation Sources: gas containing high proportion of cations and electrons (1) Inductively Coupled Plasma (ICP) ATOMIC EMISSION SPECTROSCOPY

37 Torch up to 1" diameter Ar cools outer tube, defines plasma shape Radio-frequency (RF) up to 2 kW Ar flow up to 20 L/min

38 Plasma Structure: Brilliant white core - Ar continuum and lines Flame-like tail up to 2 cm Transparent region - measurements made Hotter than flame (10,000 K) - more complete atomization/excitation Atomized in "inert" atmosphere Little ionization - too many electrons in plasma ATOMIC EMISSION SPECTROSCOPY

39 (2) Direct Current (DC) Plasma DC current (10-15 A) flows between C anodes and W cathode Plasma core at 10,000 K, viewing region at ~5,000 K Simpler, less Ar than ICP - less expensive ATOMIC EMISSION SPECTROSCOPY

40 Atomic Emission Spectrometers May be >1,000 visible lines (<1 Å) on continuum Need high resolution (<0.1 Å) high throughput low stray light wide dynamic range (>106) precise and accurate wavelength calibration/intensities stability computer controlled ATOMIC EMISSION SPECTROSCOPY

41 Three instrument types: sequential (scanning and slew-scanning) Multichannel (Fourier transform FT-AES) ATOMIC EMISSION SPECTROSCOPY

42 Sequential monochromators: Slew-scan spectrometers - even with many lines, much spectrum contains no information rapidly scanned (slewed) across blank regions slowly scanned across lines computer control/preselected lines to scan ATOMIC EMISSION SPECTROSCOPY

43 Multichannel AES: ATOMIC EMISSION SPECTROSCOPY

44 Sequential instrument - PMT moved behind aperture plate, or grating+prism moved to focus new on exit slit Cheaper Slower Pre-configured exit slits to detect up to 20 lines, slew scan Multichannel instrument - multiple PMT's Expensive Faster ATOMIC EMISSION SPECTROSCOPY

45 Solution Sample Introduction: (1) Electrothermal vaporizer* (ETV) electric current rapidly heats crucible containing sample sample carried to atomizer by gas (Ar, He) only for introduction, not atomization ATOMIC EMISSION SPECTROSCOPY

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47 (2) Nebulizer - convert solution to fine spray or aerosol a) Ultrasonic nebulizer uses ultrasound waves to "boil" solution flowing across disc b) Pneumatic nebulizer uses high pressure gas to entrain solution ATOMIC EMISSION SPECTROSCOPY

48 Cross-flow Nebulizer ATOMIC EMISSION SPECTROSCOPY

49 Solid Sample Introduction: (1) Electrothermal vaporizer* (2) Direct Insertion(*) uses powder placed inside flame, plasma, arc or spark atomizer (atomizer acts as vaporizer) Coating on electrode in atomizer (3) Ablation uses coating of electrodes in discharge cell and sample entrained in Ar or He gas Laser ablation uses laser to vaporize sample ATOMIC EMISSION SPECTROSCOPY

50 APPLICATION OF AES AES relatively insensitive (small excited state population at moderate temperature) AAS still used more than AES (i) less expensive/complex instrumentation (ii) lower operating costs (iii) greater precision ATOMIC EMISSION SPECTROSCOPY

51 In practice ~60 elements detectable 10 ppb range most metals Li, K, Rb, Cs strongest lines in IR Large # of lines, increase chance of overlap ATOMIC EMISSION SPECTROSCOPY

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53 Lecture 8 ATOMIC ABSORPTION SPECTROSCOPY Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display.

54 ATOMIC ABSORPTION SPECTROSCOPY (AAS)

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72 AAS intrinsically more sensitive than AES similar atomization techniques to AES addition of radiation source high temperature for atomization necessary flame and electrothermal atomization very high temperature for excitation not necessary / generally no plasma/arc/spark AAS ATOMIC ABSORPTION SPECTROSCOPY (AAS)

73 FLAME AAS: simplest atomization of gas/solution/solid laminar flow burner - stable "sheet" of flame flame atomization best for reproducibility (precision) (<1%) relatively insensitive - incomplete volatilization, short time in beam ATOMIC ABSORPTION SPECTROSCOPY (AAS)

74 ATOMIC ABSORPTION SPECTROSCOPY

75 Primary combustion zone - initial decomposition, molecular fragments, cool Interzonal region - hottest, most atomic fragments, used for emission/fluorescence Secondary combustion zone - cooler, conversion of atoms to stable molecules, oxides element rapidly oxidizes - largest [atom] near burner element poorly oxidizes - largest [atom] away from burner ATOMIC ABSORPTION SPECTROSCOPY

76 most sensitive part of flame for AAS varies with analyte ATOMIC ABSORPTION SPECTROSCOPY Consequences? sensitivity varies with element must maximize burner position makes multielement detection difficult

77 Electrothermal Atomizers: entire sample atomized short time ( °C) sample spends up to 1 s in analysis volume superior sensitivity ( g analyte) less reproducible (5-10 %) ATOMIC EMISSION SPECTROSCOPY

78 Graphite furnace ETA ATOMIC ABSORPTION SPECTROSCOPY

79 external Ar gas prevents tube destruction internal Ar gas circulates gaseous analyte ATOMIC ABSORPTION SPECTROSCOPY

80 Three step sample preparation for graphite furnace: 1)Dry - evaporation of solvents (10->100 s) 2)Ash - removal of volatile hydroxides, sulfates, carbonates ( s) 3)Fire/Atomize - atomization of remaining analyte (1 s) ATOMIC ABSORPTION SPECTROSCOPY

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82 Atomic Absorption Instrumentation: AAS should be very selective - each element has different set of energy levels and lines very narrow BUT for linear calibration curve (Beers' Law) need bandwidth of absorbing species to be broader than that of light source difficult with ordinary monochromator ATOMIC ABSORPTION SPECTROSCOPY

83 Solved by using very narrow line radiation sources minimize Doppler broadening pressure broadening lower P and T than atomizerand using resonant absorption Na emission 3p2s at nm used to probe Na in analyte ATOMIC ABSORPTION SPECTROSCOPY

84 Hollow Cathode Lamp: ATOMIC ABSORPTION SPECTROSCOPY

85 300 V applied between anode (+) and metal cathode (-) Ar ions bombard cathode and sputter cathode atoms Fraction of sputtered atoms excited, then fluoresce Cathode made of metal of interest (Na, Ca, K, Fe...) different lamp for each element restricts multielement detection Hollow cathode to maximize probability of redeposition on cathode restricts light direction ATOMIC ABSORPTION SPECTROSCOPY

86 ELECTRODELESS DISCHARGE LAMP ATOMIC ABSORPTION SPECTROSCOPY

87 AAS Spectrophotometers: ATOMIC ABSORPTION SPECTROSCOPY

88 Signal at one wavelength often contains luminescence from interferents in flame Chemical interference: (i) reverses atomization equilibria (ii) reacts with analyte to form low volatility compound releasing agent - cations that react preferentially with interferent - Sr acts as releasing agent for Ca with phosphate protecting agent - form stable but volatile compounds with analyte (metal-EDTA formation constants) ATOMIC ABSORPTION SPECTROSCOPY

89 IONIZATION ATOMIC ABSORPTION SPECTROSCOPY

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91 hotter atomization means: more ionization emission from interferents ATOMIC ABSORPTION SPECTROSCOPY

92 Spectral interference - emission or absorption from interferent overlaps analyte ATOMIC ABSORPTION SPECTROSCOPY Beam usually chopped or modulated at known frequency Signal then contains constant (background) and dynamic (time varying) signals

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94 DETECTION LIMITS for AAS/AES? AA/AE comparable (ppb in flame) AAS less suitable for weak absorbers (forbidden transitions) metalloids and non-metals (absorb in UV) metals with low IP (alkali metals) ATOMIC ABSORPTION SPECTROSCOPY

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111 ATOMIC EMISSION SPECTROSCOPY

112 INTRODUCTION TO ATOMIC SPECTROMETRY

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