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Lecture 6

ATOMIC SPECTROSCOPY

Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display.

Sample is atomized (atoms/ions)

absorption or emission measured

INTRODUCTION TO ATOMIC SPECTROMETRY

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

INTRODUCTION TO ATOMIC SPECTROMETRY

INTRODUCTION TO ATOMIC SPECTROMETRY

ELECTRONIC TERM SYMBOLS

INTRODUCTION TO ATOMIC SPECTROMETRY

INTRODUCTION TO ATOMIC SPECTROMETRY

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

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

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

(i)

Uncertainty Principle:

Quantum mechanical idea states must measure for some minimum time to tell two frequencies apart

ATOMIC LINE WIDTHS

Shows up in lifetime of excited state

if lifetime infinitely long, E infinitely narrow if lifetime short, E is broadened

INTRODUCTION TO ATOMIC SPECTROMETRY

Example

Lifetime of Hg*=2x10-8 s. What is uncertainty broadening for 254 nm line?

INTRODUCTION TO ATOMIC SPECTROMETRY

Differentiating with respect to frequency:

sometimes called natural linewidth.

INTRODUCTION TO ATOMIC SPECTROMETRY

INTRODUCTION TO ATOMIC SPECTROMETRY

(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) 101-10-2 For high pressure Xe lamps (>10,000 torr) 100-1000 (turns lines into continua!) INTRODUCTION TO ATOMIC SPECTROMETRY

(iii) Doppler broadening: Change in frequency produced by motion relative to detector

INTRODUCTION TO ATOMIC SPECTROMETRY

In gas, broadens line symmetrically

Doppler broadening increases with T At room T ~10-2-10-3 Total linewidth typically 0.01-0.1

INTRODUCTION TO ATOMIC SPECTROMETRY

Other Effects of T on Atomic Spectrometry:

T changes # of atoms in ground and excited states


Boltzmann equation

INTRODUCTION TO ATOMIC SPECTROMETRY

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 - 99.98 % atoms in ground state!

INTRODUCTION TO ATOMIC SPECTROMETRY

Methods for Atomizing and Introducing Sample

Sample must be converted to atoms first

INTRODUCTION TO ATOMIC SPECTROMETRY

Must transfer sample to atomizer - easy for gases /solutions but difficult for solids

INTRODUCTION TO ATOMIC SPECTROMETRY

Lecture 7

ATOMIC EMMISION SPECTROSCOPY

Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display.

ATOMIC EMISSION SPECTROSCOPY (AES)

Identification of elements but not compounds

INTRODUCTION TO ATOMIC SPECTROMETRY

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

Flame Excitation Sources:

Primary Combustion Zone Interzonal Region Secondary Combustion Zone

ATOMIC EMISSION SPECTROSCOPY

ATOMIC EMISSION SPECTROSCOPY

Laminar Flow Burner: Cheap Simple Flame stability Low temperature

ATOMIC EMISSION SPECTROSCOPY

ATOMIC EMISSION SPECTROSCOPY

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

Electric current flowing between two C electrodes

Sample pressed into electrode or mixed with Cu powder and pressed briquetting
Cyanogen bands (CN) 350-420 nm occur with C electrodes in air He, Ar atmosphere ATOMIC EMISSION SPECTROSCOPY

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

ATOMIC EMISSION SPECTROSCOPY

ATOMIC EMISSION SPECTROSCOPY

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

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

ATOMIC EMISSION SPECTROSCOPY

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

ATOMIC EMISSION SPECTROSCOPY

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

(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

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

Three instrument types:


sequential

(scanning and slew-scanning)

Multichannel (Fourier

transform FT-AES)

ATOMIC EMISSION SPECTROSCOPY

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

Multichannel AES:

ATOMIC EMISSION SPECTROSCOPY

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

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

ATOMIC EMISSION SPECTROSCOPY

(2) Nebulizer - convert solution to fine spray or aerosol


a)

Ultrasonic nebulizer uses ultrasound waves to "boil" solution flowing across disc
Pneumatic nebulizer uses high pressure gas to entrain solution

b)

ATOMIC EMISSION SPECTROSCOPY

Cross-flow Nebulizer

ATOMIC EMISSION SPECTROSCOPY

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

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

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

ATOMIC EMISSION SPECTROSCOPY

Lecture 8

ATOMIC ABSORPTION SPECTROSCOPY

Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display.

ATOMIC ABSORPTION SPECTROSCOPY (AAS)

ATOMIC ABSORPTION SPECTROSCOPY (AAS)

ATOMIC ABSORPTION SPECTROSCOPY (AAS)

ATOMIC ABSORPTION SPECTROSCOPY (AAS)

ATOMIC ABSORPTION SPECTROSCOPY (AAS)

ATOMIC ABSORPTION SPECTROSCOPY (AAS)

ATOMIC ABSORPTION SPECTROSCOPY (AAS)

ATOMIC ABSORPTION SPECTROSCOPY (AAS)

ATOMIC ABSORPTION SPECTROSCOPY (AAS)

ATOMIC ABSORPTION SPECTROSCOPY (AAS)

ATOMIC ABSORPTION SPECTROSCOPY (AAS)

ATOMIC ABSORPTION SPECTROSCOPY (AAS)

ATOMIC ABSORPTION SPECTROSCOPY (AAS)

ATOMIC ABSORPTION SPECTROSCOPY (AAS)

ATOMIC ABSORPTION SPECTROSCOPY (AAS)

ATOMIC ABSORPTION SPECTROSCOPY (AAS)

ATOMIC ABSORPTION SPECTROSCOPY (AAS)

ATOMIC ABSORPTION SPECTROSCOPY (AAS)

AAS

intrinsically more sensitive than AES atomization techniques to AES of radiation source

similar

addition

high

temperature for atomization necessary flame and electrothermal atomization


high temperature for excitation not necessary / generally no plasma/arc/spark AAS

very

ATOMIC ABSORPTION SPECTROSCOPY (AAS)

FLAME AAS: simplest atomization of gas/solution/solid


laminar

flow burner - stable "sheet" of flame

flame

atomization best for reproducibility (precision) (<1%)


insensitive - incomplete volatilization, short time in beam ATOMIC ABSORPTION SPECTROSCOPY (AAS)

relatively

ATOMIC ABSORPTION SPECTROSCOPY

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

most sensitive part of flame for AAS varies with analyte


Consequences?

sensitivity varies with element


must maximize burner position

makes multielement detection difficult

ATOMIC ABSORPTION SPECTROSCOPY

Electrothermal Atomizers:

entire sample atomized short time (2000-3000 C)

sample spends up to 1 s in analysis volume


superior sensitivity (10-10-10-13 g analyte)

less reproducible (5-10 %)

ATOMIC EMISSION SPECTROSCOPY

Graphite furnace ETA

ATOMIC ABSORPTION SPECTROSCOPY

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

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

ATOMIC ABSORPTION SPECTROSCOPY

ATOMIC ABSORPTION SPECTROSCOPY

Atomic Absorption Instrumentation:


AAS

should be very selective - each element has different set of energy levels and lines very narrow
for linear calibration curve (Beers' Law) need bandwidth of absorbing species to be broader than that of light source difficult with ordinary monochromator

BUT

ATOMIC ABSORPTION SPECTROSCOPY

Solved by using very narrow line radiation sources


minimize

Doppler broadening

pressure
lower

broadening

P and T than atomizerand using resonant absorption

Na emission 3p2s at 589.6 nm used to probe Na in analyte

ATOMIC ABSORPTION SPECTROSCOPY

Hollow Cathode Lamp:

ATOMIC ABSORPTION SPECTROSCOPY

300 Ar

V applied between anode (+) and metal cathode (-)

ions bombard cathode and sputter cathode atoms

Fraction Cathode

of sputtered atoms excited, then fluoresce


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

ELECTRODELESS DISCHARGE LAMP

ATOMIC ABSORPTION SPECTROSCOPY

AAS Spectrophotometers:

ATOMIC ABSORPTION SPECTROSCOPY

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

IONIZATION

ATOMIC ABSORPTION SPECTROSCOPY

ATOMIC ABSORPTION SPECTROSCOPY

hotter atomization means:


more

ionization
from interferents

emission

ATOMIC ABSORPTION SPECTROSCOPY

Spectral interference - emission or absorption from interferent overlaps analyte


Beam usually chopped or modulated at known frequency Signal then contains constant (background) and dynamic (time varying) signals

ATOMIC ABSORPTION SPECTROSCOPY

ATOMIC ABSORPTION SPECTROSCOPY

DETECTION LIMITS for AAS/AES?

AA/AE comparable (ppb in flame)


AAS less suitable for
weak

absorbers (forbidden transitions)


and non-metals (absorb in UV) with low IP (alkali metals)

metalloids metals

ATOMIC ABSORPTION SPECTROSCOPY

ATOMIC ABSORPTION SPECTROSCOPY

ATOMIC ABSORPTION SPECTROSCOPY

ATOMIC ABSORPTION SPECTROSCOPY

ATOMIC ABSORPTION SPECTROSCOPY

ATOMIC ABSORPTION SPECTROSCOPY

ATOMIC ABSORPTION SPECTROSCOPY

ATOMIC ABSORPTION SPECTROSCOPY

ATOMIC ABSORPTION SPECTROSCOPY

ATOMIC ABSORPTION SPECTROSCOPY

ATOMIC ABSORPTION SPECTROSCOPY

ATOMIC ABSORPTION SPECTROSCOPY

ATOMIC ABSORPTION SPECTROSCOPY

ATOMIC ABSORPTION SPECTROSCOPY

ATOMIC ABSORPTION SPECTROSCOPY

ATOMIC ABSORPTION SPECTROSCOPY

ATOMIC ABSORPTION SPECTROSCOPY

ATOMIC EMISSION SPECTROSCOPY

INTRODUCTION TO ATOMIC SPECTROMETRY

INTRODUCTION TO ATOMIC SPECTROMETRY

INTRODUCTION TO ATOMIC SPECTROMETRY

INTRODUCTION TO ATOMIC SPECTROMETRY

INTRODUCTION TO ATOMIC SPECTROMETRY

INTRODUCTION TO ATOMIC SPECTROMETRY

INTRODUCTION TO ATOMIC SPECTROMETRY

INTRODUCTION TO ATOMIC SPECTROMETRY

INTRODUCTION TO ATOMIC SPECTROMETRY

INTRODUCTION TO ATOMIC SPECTROMETRY

INTRODUCTION TO ATOMIC SPECTROMETRY

INTRODUCTION TO ATOMIC SPECTROMETRY

INTRODUCTION TO ATOMIC SPECTROMETRY

INTRODUCTION TO ATOMIC SPECTROMETRY

INTRODUCTION TO ATOMIC SPECTROMETRY

INTRODUCTION TO ATOMIC SPECTROMETRY

INTRODUCTION TO ATOMIC SPECTROMETRY

INTRODUCTION TO ATOMIC SPECTROMETRY

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