elemental spectroscopy icp-oes. 2 content: icp-oes fundamentals of icp-oes instrument components
Post on 16-Dec-2015
504 Views
Preview:
TRANSCRIPT
Elemental Spectroscopy ICP-OES
2
Content: ICP-OES
• Fundamentals of ICP-OES
• Instrument Components
Theory of Inductively Coupled PlasmaOptical Emission Spectroscopy
4
ICP is shorthand for ICP-AES or ICP-OES.
What is ICP-AES? It is:Inductively Coupled Plasma Atomic Emission Spectrometer.
ICP Basics
What is ICP-OES? It is:Inductively Coupled Plasma Optical Emission Spectrometer.
5
Atomic Emission Theory
• Atomic emission spectroscopy (AES or OES) uses quantitative measurement of the optical emission from excited atoms to determine analyte concentration
• Analyte atoms in solution are aspirated into the excitation region where they are desolvated, vaporized, and atomised by a plasma
6
Atomic Emission Theory
Plasma Polychromator Detector
Inductively Coupled Plasma Atomic Emission Spectrometer
7
Excitation
E x c i t e d S t a t eG r o u n d S t a t e
ER e l a x a t i o n
E x c i t a t i o n
Electrons can be in their ground state (unexcited) or enter one of the upper level orbitals when energy is applied to them. This is the excited state
8
Atomic Emission
PhotonExcited State Ground State
+ hv
A photon of light is emitted when an electron falls from its excited state to its ground state
9
Element Wavelengths
• Each element has a unique set of wavelengths that it
can emit
180nm 800nm400nm <-- visible --><-- uv -->
1 2 3 4 5
10
Atomic Emission explained
• Atomic Emission – the wavelength regions
Spectral Region
Vacuum UV Ultra-Violet Visible Near IR
Wavelength = nm 160 190 360 760 900
Lower wavelengths are shorter and have more energy, higher wavelengths e.g. in the Visible region, are longer and have less energy
11
Effect of Temperature on Emission
Wavelength increasing ->
2000 k
3000 k
5000 k
Ca Na Li
K
Ca
Na Li
K
KLiNa
Ca Ba
Ba
CuMg
Mg CuAs Pb Mn
200 300 400 600 800
12
Emission sources
• Flames
• Arcs / Sparks
• Direct Current Plasmas (DCP)
• Inductively Coupled Plasmas (ICP)
13
Inductively Coupled Plasma (ICP) – source, plasma formation, plasma zones
• Quartz torch surrounded by induction coil
• Magnetic coupling to ionized gas
• High temperature – equivalent to 10,000k
14
Plasma Advantages
• High Temperature – allows for full dissociation of sample components
• Argon is Inert – non reactive with sample• Linearity – analysis of samples from ppb to ppm range in the same
method• Matrix tolerance – robust and flexible design with Duo and Radial
options
15
Plasma Torch
16
Plasma Zones
Plasma Zones
sample
6000 k
6500 k
7000 k
8000 k
10000 k
0
15
20
25
observationregion (mm) TEMPERATURE ~ 2X
NITROUS OXIDE ACETYLENE FLAME
RESIDENCE TIME ~ 2MS
17
Instrument Components
There are six basic components to an ICP
1. Sample Introduction
2. Energy Source
3. Spectrometer
4. Detector
5. Electronics
6. Computer and Software
18
Instrument Components
6. Computer and Software
1. Sample Introduction
2. Energy Source
3. Spectrometer
4. Detector5. Electronics
19
1. Sample Introduction The sample solution
cannot be put into the energy source directly. The solution must first be converted to an aerosol.
The function of the sample introduction system is to produce a steady aerosol of very fine droplets.
Instrument Components
20
1. Sample Introduction
There are three basic parts to the sample introduction system.
i. the Peristaltic pumpdraws up sample solution and delivers it to
ii.the Nebulizerwhich converts the solution to an aerosol that is sent to
iii. the Spray chamberwhich filters out the large, uneven droplets from the aerosol.
Instrument Components
21
1. Sample Introduction
i. the Peristaltic pump
ii. the Nebulizer
iii. the Spray chamber
Instrument Components
22
Concentric Nebuliser
23
2. Energy Source The sample aerosol
is directed into the center of the plasma. The energy of the plasma is transferred to the aerosol.
The main function of the energy source is to get atoms sufficiently energized such that they emit light.
Instrument Components
= plasma
24
2. Energy Source
There are three basic parts to the energy source.
i. the Radio frequency generatorwhich generates an oscillating electo-magnetic field at a frequency of 27.12 million cycles per second. This radiation is directed to
ii.the Load coilwhich delivers the radiation to
iii. the Torchwhich has argon flowing through it which will form a plasma in the RF field.
Instrument Components
25
2. Energy Source
i. the Radio Frequency generator
ii. the Load coil
iii. the Torch
Instrument Components
26
Plasma Configuration
• Axial
• Radial
• Axial and Radial
27
Radial or Axial Configuration
• Radial design – Robust, fewer interferences • Petrochemical• Metallurgy
• Axial design – best sensitivity,
lowest detection limits • Environmental• Chemical
28
Axial Advantage
• Much more light available. This gives you the opportunity to achieve Lower Detection Limits than Radial Plasma
• BUT- unfortunately, you also get...
• More Matrix Interferences
• Slightly Reduced Dynamic Range
29
Duo viewing
• Axial view plasma looks down the central channel of the plasma, this provides the best sensitivity and detection limits
• DUO – this is an axially configured plasma that also allows for radial view through a hole in the side of the axial torch
30
Dual View Optics
Axial view
Radial view
31
Instrument Components
3. SpectrometerOnce the atoms in a sample have been energized by the plasma, they will emit light at specific wavelengths. No two elements will emit light at the same wavelengths.
The function of the spectrometer is to diffract the white light from the plasma into wavelengths.
32
Simultaneous Optics – Echelle Spectrometer
ICP-Source
Detector
PrismGrating
33
Instrument Components
3. Spectrometer
There are several types of spectrometers used for ICP. Regardless of type, all of them use a diffraction grating.
For the iCAP, an echelle spectrometer is used. The components in this spectrometer are shown at left.
CID Detector
FocusingMirror
Prism
CollimatingMirror
Shutter
Slit(dual)
Echellegrating
34
iCAP Optics - Polychromator
• High resolution• 7pm @ 200nm
• High image quality & low stray light• aberration compensation over whole CID
• High energy throughput• double pass prism
• All lines on chip• anamorphic magnification
• Stable• thermal insulation & heater control to 0.10C
35
Instrument Components
4. DetectorNow that there are individual wavelengths, their intensities can be measured using a detector. The intensity of a given wavelength is proportional to the concentration of the element.
The function of the detector is to measure the intensity of the wavelengths.
36
Charge Injection Device Array Detector
• >291,600 addressable silicon-based
photo detectors
• Full Spectrum Imaging
• Random Access Integration (RAI)
• Inherently Anti-blooming
– Non Destructive Readout (NDRO), allows the S/N ratio to be improved by repeatedly reading each pixel
37
Instrument Components
4. Detector The detector is a silicon chip that is composed of many individual photo-active sections called “picture elements”. These picture elements, or pixels, will build up charge as photons impinge on them. Individual pixels are of a size such that they can be used to measure individual wavelengths.
38
Emission lines appear as points of light
177 nm
800 nm 740 nm
178 nm
39
Readout Subarray - CID
Intensity
Wavelength
28 by 28 mdetector element
40
What you get
Full, continuous wavelength coverage; never miss an analyte
41
Power and flexibility
• Rapid qualitative analysis• Ability to analyze for elements in the
future without rerunning samples• Fingerprinting• Matrix or spectral subtraction
42
Instrument Components
5. ElectronicsThe output from the detector is processed by a set of electronics. The electronics control the detector as well as collect the readings from the pixels
The function of the electronics is to measure and process the output of the detector.
43
Instrument Components
6. Computer and Software The software, via a computer, controls and runs the instrument. Not only are measurements made but the other five components of the instrument are controlled and monitored by the computer and software,
The function of the computer and software is to operate, monitor, and collect data from the instrument.
44
ICP Basics
ICP Performance
• Typical analysis time for ICP is ~2-3 minutes. This includes flush time, multiple repeats, printing, etc. (Analysis time is independent of the number of elements being determined)
• Typical precision, amongst repeats within an analysis, is ~0.5%
• Typical drift is ≤ 2% per hour
• Typical detection limits are ~ 1-10 parts per billion
top related