Atomic Absorption Spectroscopy

Elemental analysis Dissolved metals Source

Hallow Cathode Lamp Cathode of specific element

Sample
Acetylene-air flame, nebulizer

Detector
PMT

Atomic absorption
Gas-phase elemental atoms Narrow absorption lines (0.01 nm) Element specific source Flame conditions control sensitivity 1-100 ppm (mg/L) varies with element

AA Spectrometer
PMT Hollow cathode lamp Flame

monochrometer Coating of element

Air

nebulizer sample

Acetylene

Experiment
Aspirate blank, set 100 % T Aspirate sample Matrix effects are common
Standard addition analysis

Standard Addition Analysis

Removal of Atomic Emission

Place a chopper before the flame The signal from the source is modulated by the chopper Thus, a AC signal is produced on top of a DC signal that originates from emission in the flame

Atomic Emission Spectroscopy

Emission of light from exited species ICP source Multi-element analysis
Fancy optics

Greater sensitivity for most elements

ICP source
Ar tourch
Very hot , 10000 K Abundance of e- inhibits ionization Lack of O2 inhibits oxide formation Excited atomic species predominate 5-20 L/min

Sample Introduction
Nebulizer Electrothermal vaporization Laser ablation In either case Ar gas in used to carry sample into the ICP

Scanning Instruments
Grating monochromator Slew-scan mode
Slew-The detector and slit is quickly moved to a specific wavelength for a given element Slowly scan across the wavelength window near a line in very small steps-0.001 nm Not limited to a set of specific elements

Echelle grating/prism
Higher orders, 2-D plane, better dispersion Slew-scan mode

Diffraction Equation
nl = d(sin i + sin r) Dispersion D = dy/dl = F (n/d cos r)

Multi-channel Instruments
Polychromators
60 photomultipliers in fixed positions

Array-based
Echelle and prism for 2-D dispersion plane Charge injection detector with 94672 different detector elements (8.7x6.6mm) A set of 39 elements makes up a read window for a given element CCD detectors

CCD detectors
Array of semiconductor detection elements 512x320 array =163840 individual detectors Charge of impinging photons are stored The charge accumulated on each detector element is registered one by one by sending the charge to a preamplifier and readout (emptying the registrar) Very sensitive

Fig 10-6 and Fig 10-7

10-6 is the slew can instrument 10-7 is the multi-channel instrument

Performance
Sensitivity: Ranges from 1-300 ng/mL Number of useful lines; 1-24 Calibration curves; almost 3 orders of magnitude Internal standards Self-absorption at higher concentrations

Other components of visible spectroscopy

Photon Counting
Each time a photon strikes the PMT, a pulse of electrons are produced Normally, an average current over time is integrated to produce the signal In photon counting each pulse is counted, and the total number of pulses in a time interval is summed Filters out noise Fluorescence and Raman Spec

Fiber Optics
Total Internal Reflections n1>n2>n3

Lasers
Qualities
High intensities Narrow band width coherence

Lasing medium
Solid state, gas, dye

Lasing mechanism
Figure 7.5