AS deals with e transfer transition of valence electron between electronic states

Sequential ICP-AES
Instrumentation
 Major Components of ICP-AES

Sample Delivery System - pump, nebulizer,

spray chamber

Inductively Coupled Plasma - torch, RF generator

Spectrometer - Monochrometer, photomultiplier tube

Sample Delivery System

Nebulizer:
Concentric-tube converts sample to
pneumatic aerosol by a jet of gas
nebulizer
(compressed Ar)
Common types:
Pneumatic - concentric
tube, cross flow
Cross flow nebulizer Ultrasonic
Ultrasonic nebulizer with desolvation
 Inductively Coupled Plasma

What is a Plasma?

Plasma source provides atomization

Plasma: a gas-like phase of matter that consists of
charged particles
ICP-AES plasma source is from the carrier gas

Typically argon is used

Drawback
Solid and liquid samples must be prepared
so that they can be easily evaporated and
ionized by the instrument1
ICP-AES is a destructive technique, but only
a small bit of sample is necessary
Sample introduction into the instrument: the
thorn in the side of ICP-AES
Plasma
Plasma source provides atomization
Plasma: a gas-like phase of matter that
consists of charged particles2
ICP-AES plasma source is from the carrier
gas
Inductively coupled plasma (ICP)
torch design
Radiofrequency Generator
ICP torch
ICP temperatures
etection 2 Types of Detection
Positions:
1. Radial Viewing
2. Axial Viewing

Radial
Viewing
 How to perform Simultaneous Analysis
Simultaneous analysis was carried out until
today by using:
polychromators, which are Paschen-Runge

optics coupled to high sensitivity detectors known

as Photomultiplers (PMT)
Echelle-Grating optics, coupled to Solid State
Detectors , (CCD, SCD & CID types), also known
as Charge Transfer Devices (CTDs)
Detail of a Paschen-Runge optics with PMT detectors

Diffraction
Grating
Optical Fibers

Photo multipliers
 Advantages:
Grating High light throughput
Wide spectral range
Rowland circle
Few optical components
Low stray light level
Robust

Entrance Exit slits

slit
Photomultiplier
Tubes
Photographic Film
 X
Y
PMT

SCANNING + PMT
Optics and Detectors
Typical Echellogram
ICP optical emission spectrometry
ICP-OES
Capable of true simultaneous multielement
analysis
Minimal chemical interferences
Spectral interferences overcome with use of
alternate lines or intensity corrections on
either side of analytical line
Axial and side-on viewing systems available
ICP-OES operation
Variety of sample introduction approaches
available (pneumatic nebulizer with ~ 1
mL/min uptake is most common)
Sensitivities better than FAA and often
comparable with GFAA when using axial
viewing
Varying degrees of automation available
Background Noise Sources
Argon emission lines
Carbon and silicon lines
Oscillation by the plasma
itself and oscillations
caused during aerosol
production and sample
delivery
Such intensities are
practically constant and
easily recognized
Poor Detection Limits on Certain Trace
Elements

Examples of interferences include:

40Ar16O on the determination of 56Fe

38
ArH on the determination of 39K
40Ar on the determination of 40Ca

40Ar40Ar on the determination of 80Se

Solution: the cold/cool plasma

 Limits of Detection
Decrease in limits of detection over the course
of time using examples of Perkinelmer ICP emission
Spectrometers ICP/5000 (1980), Optima 3000 (1993),
Optima 3000 XL (1997)

All detection limits were

determined by the blank
method using the statistical
factor K = 3
[concentrations in ppb]
DCP
Inductively coupled plasma mass spectrometry
ICPMS
ICPMS characteristics
Simultaneous multielemental analysis
5-6 orders of magnitude in dynamic range(need
fewer standards for calibration)
ppt and even ppq LODs available
Isotopic information available
Spectral interferences occur and involve
polyatomic ions or isotopes of other elements
Interferences involving ion optics (e.g., space
charge) and ionization efficiency are unique to
ICPMS