1. Chem. 133 – 4/4 Lecture

2. Announcements I Strike – If the strike occurs, it will affect classes April 14 th and 18 th (unless ended early) – Lab: would result in less time for term project (grading of projects would reflect that) – Lecture: less content covered Exam 2: – This Thursday – Will cover Electrochem. (from Nernst equation on), Ch. 17 and Ch. 19, plus part of Ch. 20 (through theory, but not atomization) – Forgot about help session, but can have extra office hours tomorrow (9 to 10?) Lab – Starting Set 2:4 starting next Tues. – Term project work starts April 19 th (if no strike)

3. Announcements II HW Set 2 Additional Problem 2 due Thursday (sorry but no key posted until after exam) Today’s Lecture – Atomic Spectroscopy Overview Theory Atomization

4. Atomic Spectroscopy Overview Main Purpose – Determine elemental composition (or concentration of specific elements) Main Performance Concerns – Sensitivity – Multi-element vs. single element – List of useful elements (most methods work well with most metals, poorly with non-metals) – Speed – Interferences (for different matrices) – Precision – Required sample preparation

5. Atomic Spectroscopy Overview Instrument Types – Analysis for liquid samples (main focus of text + lecture discussion) – Systems for solid samples Modified instruments for liquids (involving conversion to gas phase first) – 2 examples in book: graphite furnace with solid sample placed in tube (see p. 485) and laser ablation (see p. 495) – laser ablation allows microanalysis X-ray Fluorescence Spectroscopy and X-ray Emission Detection attachments coupled to electron microscopy – Both based on spectral (or energy-dispersive) analysis of emitted X-rays to determine elements present

6. Atomic Spectroscopy Overview Instrument Types – Systems for Solids – cont. – XRF – cont. – Emitted X-rays have wavelengths dependent upon element (but generally not element’s charge or surroundings) – Accurate quantification is more difficult due to limited penetration of sample by X-rays or electrons and by attenuation of emitted X- rays due to absorption (matrix effects) – Sensitivity and selectivity somewhat less than standard methods Instrument Types – For Analysis of Liquids – Atomization Systems: to convert elements to gaseous atoms or ions (MS detection) Flame Electrothermal (Graphite Furnace) Inductively Coupled Plasma (ICP)

7. Atomic Spectroscopy Overview Instrument Types – For Analysis of Liquids – Atom Detection: to detect atoms (or ions in MS) Atomic Absorption Spectroscopy (with flame or electrothermal) Atomic Emission Spectroscopy (mainly with ICP) Mass Spectrometry (with ICP) – only detects ions

8. Atomic Spectroscopy Theory Spectroscopy is performed on atoms in gas phase Transitions are very simple (well defined energy states with no vibration/rotation /solvent interactions) Allowed transitions depend on selection rules (not covered here) E Na(g) o (3s) 4s 4p 5s 5p absorption

9. Atomic Spectroscopy Theory Consequence of well defined energy levels: – very narrow absorption peaks – few interferences from other atoms – very good sensitivity (all absorption occurs at narrow range) – but can not use standard monochromator where  (from monochromator) >>  due to extreme deviations to Beer ’ s law – requires greater wavelength discrimination for absorption measurements A Spectrum from high resolutions spectrometer (not typical for AA) atomic transition molecular transition very narrow natural peak width (  ~ 0.001 nm) broader width

10. Atomic Spectroscopy Theory For emission measurements, a key is to populate higher energy levels In most cases, this occurs through the thermal methods also responsible for atomization Fraction of excited energy levels populated is given by Boltzmann Distribution More emission at higher temperatures and for longer wavelengths (smaller  E) Na(g) o (3s) 4p E N = number atoms in ground (0) and excited (*) states g = degeneracy (# equivalent states) = 3 in above example k = Boltzmann constant = 1.38 x 10 -23 J/K

11. Atomic Spectroscopy Theory Example problem: Calcium absorbs light at 422 nm. Calculate the ratio of Ca atoms in the excited state to the ground state at 3200 K (temperature in N 2 O fueled flame). g*/g 0 = 3 (3 5p orbitals to 1 4s orbital).

12. Atomic Spectroscopy Atomization Flame Atomization – used for liquid samples – liquid pulled by action of nebulizer – nebulizer produces spray of sample liquid – droplets evaporate in spray chamber leaving particles – fuel added and ignited in flame – atomization of remaining particles and spray droplets occurs in flame – optical beam through region of best atomization sample in fuel (HCCH) oxidant (air or N 2 O) burner head spray chamber nebulizer light beam nebulizerair liquid

13. Atomic Spectroscopy Atomization Atomization in flames – Processes – nebulization of liquid: MgCl 2 (aq) → MgCl 2 (spray droplet) – evaporation of solvent: MgCl 2 (spray droplet) → MgCl 2 (s) – Volatilization in flame: MgCl 2 (s) → MgCl 2 (g) – Atomization (in hotter part of flame): MgCl 2 (g) → Mg(g) + Cl 2 (g) Target species for absorption measurement

14. Atomic Spectroscopy Atomization Electrothermal Atomization – Atomization occurs in a graphite furnace – Process is different in that a small sample is placed in a graphite tube and atomization occurs rapidly but in a discontinuous manner – Electrothermal atomization is more efficient; atoms spend more time in the beam path, and less sample is required resulting in much greater sensitivity Concentration LODs are typically ~100 times lower (e.g. 100 ppt for EA vs. 10 ppb for flame) Mass LODs are even lower (100 pg/mL*0.01 mL = 1 pg for EA vs. 10 ng/mL*2 mL = 20 ng for flame)

15. Atomic Spectroscopy Atomization Electrothermal Atomization (Process) – Sample is placed through hole onto L ’ vov platform – Graphite tube is heated by resistive heating – This occurs in steps (dry, char, atomize, clean) Graphite Tube in Chamber (not shown) L’vov Platform Sample in T time drychar atomize Clean + cool down Ar in chamber flow stops and optical measurements made

16. Atomic Spectroscopy Atomization Inductively Coupled Plasma (ICP) – A plasma is induced by radio frequency currents in surrounding coil – Once a spark occurs in Ar gas, some electrons leave Ar producing Ar + + e - – The sample is introduced by nebulization in the Ar stream – The accelerations of Ar + and e - induce further production of ions and great heat production – Much higher temperatures are created (6000 K to 10000 K vs. flames) ICP Torch Quartz tube Argon + Sample RF Coil

17. Atomic Spectroscopy Atomization Advantages of ICP Atomization – Greater atomization efficiency than in flame AA (partly because better nebulizers are used than with flames due to higher total instrument cost and partly due to higher temperatures) – Fewer matrix effects because atomization is more complete at higher temperatures – High temperature atomization allows much greater emission flux + more ionization allowing coupling with emission spectrophotometers and mass spectrometers – Emission and MS allow faster multi-element analysis

18. Chapter 20 Questions 1.Why would it be difficult to use a broadband light source and monochromator to produce light used in AA spectrometers? 2.List three methods for atomizing elements. 3.List two processes that can decrease atomization efficiency in flame atomization. 4.What is an advantage in using electrothermal atomization in AAS? 5.Which atomization method tends to result in the most complete breakdown of elements to atoms in the gas phase? 6.Why is ICP better for emission measurements than flame?

19. Atomic Spectroscopy Atomization Complications/Losses – Ideally, every atom entering nebulizer ends up as gaseous atom – In practice, at best only a few % of atoms become atoms in flame – The nebulization process is not that efficient (much of water hits walls and goes out drain) – Poor volatilization also occurs with less volatile salts (e.g. many phosphates)

20. Atomic Spectroscopy Atomization Complications/Losses (continued) – Poor atomization also can occur due to secondary processes such as: Formation of oxides + hydroxides (e.g. 2Mg (g) + O 2 (g) → 2MgO (g)) Ionization (Na (g) + Cl (g) → Na + (g) + Cl - (g)) – If the atomization is affected by other compounds in sample matrix (e.g. the presence of phosphates), this is called a matrix effect (discussed more later