General ICP-AES

Basic ICP-ES Excitation

Plasma
Sample introduction Optics RF

Gas control
Data acquistion and communications

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Basic ICP-ES

Inductively Coupled Plasma spectrometers are scientific instruments that use emission spectroscopy to quantify or qualify elements in a sample. Atomic emission spectroscopy is the technique for detecting and measuring chemical elements in analytical samples. The technique measures the intensity of light emitted by atoms or ions of the elements of interest at a specific wavelength. The sample to be analyzed must first be heated to a very high temperature. This is done by introducing a sample into an excitation source

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Excitation

Atoms become excited by absorbing energy, usually by collision with other atoms (that is by heat). The absorbed energy causes an electron in the outer shell to move to a higher energy orbit.

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Excitation

Such excited atoms are unstable, and the electron quickly returns to a less energetic orbit The energy difference between the two orbits is ejected from the atom in the form of light The light is of a wavelength that is characteristic of the atom and therefore the element A spectrometer that is set to a wavelength of interest will then measure the intensity of the light emitted at that wavelength The intensity of the light is proportional to the number of atoms in the excitation source of the element of interest

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Plasma

A plasma is a gas that contains a significant fraction of ions and free electrons.

Melts

Boils or Vaporizes

Ionizes

Solid

Liquid

Gas

Plasma

Temperature (

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Plasma

A gas is an electrical insulator

A plasma conducts electricity

Only a small fraction of the atoms in a gas need to be ionized to form a plasma. Argon gas in the ICP plasma normally has less than 1% ions An inductively coupled plasma is achieved by the ionization of argon gas in a radio frequency magnetic field An ion is an atom that carries a charge due to the loss or gain of an electron

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Plasma

Ionization in a plasma is triggered when argon is passed through a rapidly changing magnetic field and is then seeded with electrons from a spark discharge The electrons from of the spark discharge accelerate through the gas and the changing magnetic field The accelerated electrons collide with argon atoms and knock electrons from them

The electron collisions with the argon atoms cause the release of more electrons from other argon atoms, resulting in argon ions
These collisions are sustained by the influence of the magnetic field Through the influence of the magnetic field the argon atoms and ions continue to collide forming more ions. The formation of ions allow a plasma state to form and become self sustained

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Plasma

Ar , Ar + , e -

M ag ne ti c F ield

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Plasma

When ions re-combine with free electrons, the approaching electron loses energy by emitting light over a wide range of wavelengths. The emission over the wide range of wavelengths is known as a continuum. The plasma generates a baseline of continuum emission that comes mainly from the re-combination of ion pairs Once the free electron is trapped by the ion it is constrained to exist in specific orbits Upon recombination of an electron with a singly-charged ion the atom no longer carries a charge and is no longer an ion

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Ionic emission

Ions also emit light through ionic emission.

An ion will absorb energy, usually by collision with other ions and atoms.
The absorbed energy causes an electron of the ion to move to a higher energy orbit The electron in the ion quickly returns to a lower orbit level The energy difference between the two orbits is ejected from the ion in the form of light The light is of a wavelength that is characteristic of the ion and therefore the element

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Ionic emission

As the atomic structure of an ion of a certain element is physically different from the atomic structure of an atom of the same element, an ion of a certain element will emit light at different wavelengths than an atom of the same element. The background emission of the plasma consists of the continuum emission of ion recombination, the ionic emission from the argon ions and atomic emission of the excited argon atoms.

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Atomization

Atomization is the physical process where gaseous molecules are broken down into simple elements Molecules are atomized by heat Argon ions and electrons, under the influence of the magnetic field flow in the horizontal plane of the RF coil The ions and electrons collide with the neutral argon atoms. The collisions with the neutral argon atoms result in the generation of temperatures of up to 10,000K In theory, the point of the greatest activity between ions, electrons and neutral atoms will be the point of the highest temperature.

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Atomization

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Atomization

As the magnetic field becomes less of an influence on the ions, electrons and neutral argon atoms, fewer recombinations and collisions occur As excitation decreases so does the temperature of the plasma This causes a formation of a temperature gradient over the area of the plasma An inductively coupled plasma tends to become hollow in the middle The plasma is an electrical conductor. The outer parts of the plasma shield the inner parts from the influence of the induction coil. The interaction between the plasma and the changing magnetic field of the coil is concentrated in the outer parts of the plasma. This is known as the skin depth effect

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Atomization

The gas flow pattern produced by the torch creates a region of lower pressure in the center of the plasma The skin effect and gas flow sustain a plasma that is more effective in the outer regions of the plasma The stream of gas from the nebulizer passes through the torch injector and punches a channel through the center of the plasma The central channel is cooler than the surrounding plasma (5000-7000 K) Through the central channel particles in the form of an aerosol are carried for excitation to atomic and ionic states

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Hard and soft emission lines

The temperature gradient and shape of the plasma allows for the excitation of both hard and soft emission lines Hard lines react to power settings, gas flows and nebulizer pressure differently than soft lines The energy difference emitted by electrons changing orbit levels in both atoms and ions is characteristic of the wavelength of the light emitted The shorter the wavelength the greater the amount of energy released as the electron returns to the less energetic orbit. The greater the amount of energy released the larger the amount of energy required to achieve the excited state. Hard lines are classified as wavelengths lower than 235 nm

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Hard and soft emission lines

Soft lines are classified as wavelengths above 235 nm

Higher power levels will tend to increase the intensity of hard lines, while higher power levels tend to have little effect on soft lines
Reducing the flow of the stream of gas through the central channel will also increase the amount of time that particles will preside in the plasma Reduction in the flow gas will tend to increase the intensity of hard lines while changes in the flow of gas will have little effect on the soft lines

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Sample introduction

The function of the sample introduction system is to deliver uniform sample amounts to the plasma for excitation of atomic/ionic emission The sample introduction system combines a sample together with a carrier gas and transports it to the plasmas central channel As the sample passes through the plasma it rapidly changes state. The plasma as an excitation source offers two physical means for emission Atomization Ionization

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Sample introduction

Most elements when excited by a plasma source emit radiation in both ways. Emission lines that result from atomic excitation are classified as a type I lines. Emission lines that from ionic excitation are classified as type II lines.

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Sample introduction

ICP-ES offers three commercially available solutions for sampling. Gas Solid Liquid ICP-ES primarily is used to analyze liquids.

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Sample introduction

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Sample introduction

The process of delivering a liquid sample into the plasma involves the breaking up of a stream of liquid with a carrier gas The liquid droplets and carrier gas combine to produce an aerosol This process is carried out by a device known as a nebulizer The flow of the liquid sample into a nebulizer is controlled by tubing fitted on a peristaltic pump which rotates at user specified speeds The speed of the pump and the physical size of the tubing regulates the amount of sample that enters the nebulizer

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Sample introduction

The nebulizer forms an aerosol by pneumatic or ultrasonic means.

There are two basic types of pneumatic nebulizers. V-groove Concentric

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Sample introduction

V-groove

Most V-groove nebulizers are made from inert materials such as specially selected plastic

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Sample introduction

V-groove

Sample is pumped through a 1 to 2 mm hole

Carrier gas is fed through a second hole which is located close to the sample output hole The sample and carrier gas holes are positioned so that the output of each is aligned on the same axis in a V-shaped trough The sample flows along a V-shaped channel where it is captured by the venturi effect created by the carrier gas The carrier gas and sample combine to form an aerosol

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Sample introduction

Concentric

A typical glass concentric nebulizer uses a venturi effect.

sample

in

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Sample introduction

Concentric

Sample solution is drawn through a central capillary that is surrounded by an outer channel that a carrier gas is fed through
The carrier gas forced through the outer channel, passes by the end of the sample capillary, lowering the pressure surrounding the tip of the capillary extracting the sample

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Sample introduction

Ultrasonic

A typical ultrasonic nebulizer uses the vibration of a piezo-electric transducer to form an aerosol.
coolant out

coolant in desolvated aerosol to ICP drain RF 1.4 MHz

condenser Argon in aerosol chamber

heated (140C) U-tube

sample inlet transducer drain

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Sample introduction

Ultrasonic

The sample flows over a glass plate fixed to the transducer where the ultrasonic vibrations cause the aerosol to form.
The carrier gas sweeps the sample aerosol into a heated tube that is connected to a desolvator. The dried sample is then introduced into the plasma.

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Sample introduction

Spraychamber

The aerosol must be injected into the plasma at a uniform rate without causing plasma destabilisation
In addition to this the aerosol that is injected into the plasma must also contain a sufficient number of small droplets that are reproducible and representative of the sample A spraychamber is used to remove the larger droplets from the aerosol while providing a uniform flow of aerosol to the torch The aerosol is sprayed directly into a spray chamber which removes the larger droplets from the aerosol The spraychamber allows the aerosol to travel to the transfer tube and torch through an indirect route

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Sample introduction

Spraychamber

While passing through the chamber the larger droplets fall out of the aerosol and are removed through a drain, tubing and peristaltic pump to waste.

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Sample introduction

Torch

The torch confines ionized argon gas in the RF field of the induction coil and introduces the fine sample aerosol from the spraychamber to the plasma preheating zone.
A standard torch assembly consists of three concentric tubes. The outer wall forms the channel that carries the plasma gas flow The plasma flow keeps the plasma from overheating the torch

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Sample introduction

Torch

The intermediate tube separates the auxiliary flow from the plasma.
The auxiliary gas flow provides a positive pressure at the base of the plasma which lifts the plasma and keeps it from interacting with the top of the auxiliary and injector tubes.

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Sample introduction

Torch

The injector tube is the inner most tube and carries the sample aerosol to the plasma
The flow of the sample aerosol is determined by the carrier gas flow rate The design of the torch produces low pressure at the center of the plasma By design the sample is fed through this low pressure region

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Sample introduction

Torch

The four processes a liquid sample undergoes are: Desolvation Vaporization Molecular decomposition into elements (Atomization) Excitation and ionization The sample aerosol under goes the same transitions as the argon that forms the plasma

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Sample introduction

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Optics
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Optics

An ICP-ES optics system gathers the radiated emissions from the plasma. The emissions are then separated into their characteristic wavelengths. The characteristic wavelengths of interest are then analyzed.

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Optics

There are basically two different types of ICP-ES spectrometers on the market: sequential simultaneous These terms relate to the way optics separate the characteristic wavelengths for analysis

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Optics

Sequential

A sequential ICP-ES uses a scanning monochromator that gathers the radiant emissions and focuses this incident light onto a diffraction grating.
The grating is rotated into a position to direct only the characteristic wavelength of interest onto a detector for analysis. Most commercially available sequential ICP-ES instruments use a Czerny-Turner configuration.

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Optics

Sequential
PMT

Exit slit Entry slit Plasma torch Window

Grating
M5

M4

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Optics

Simultaneous

There are two basic simultaneous configurations currently commercially available: Rowland circle Echelle

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Optics

Simultaneous

Rowland circle
PMTs

Exit slits

Plasma torch Window

Entry slit

Fixed Grating

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Optics

Simultaneous

Rowland circle A Rowland simultaneous ICP-ES uses a stationary monochromator that gathers radiant emissions and focuses incident light onto a single spherical diffraction grating
The grating is designed to direct the spectrum of light to a number of PMT detectors which are arranged in a circle. Each PMT is physically placed for each characteristic wavelength that is to be analyzed. Therefore for each wavelength of interest a detector in a specific location must be used.

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Optics

Simultaneous

Echelle
Lens

Detector

Grating

Plasma torch
Prism
Entry slit

Window

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Optics

Simultaneous

Echelle An Echelle simultaneous ICP-ES uses a polychromator that gathers the radiant emissions and focuses this incident light onto two stationary dispersive elements The first dispersive element is a grating. The grating is usually ruled to disperse the incident light into a spectrum across the vertical optics plane The second dispersive element is generally a prism. The prism is manufactured and mounted to project the vertical spectrum from the grating into a two dimensional optical matrix

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Optics

Simultaneous

Echelle The prism does this by further dispersing the vertically orientated full spectrum across the horizontal optics plane Having been dispersed in two planes the resulting image now represents a two dimensional optical matrix The matrix is composed of a composite of the entire spectrum where lowest wavelength is positioned in one extreme, (ie lower right hand corner) and the highest wavelength is positioned in the opposite extreme, (ie upper left hand corner) The two dimensional spectrum is then observed by a solid state detector

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RF
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RF

The function of the plasma generation system is to deliver high energy RF current through the induction coil. The alternating current through the induction coil provides the magnetic fields required to produce and sustain a plasma as an excitation source Plasma generation systems for commercially available ICP-ES instruments are generally PC controlled. The software allows the operator of the instrument to select the level of RF power required by the type of analysis of interest Plasma generation systems consist of an RF system and control circuitry

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RF

There are two frequencies currently commercially available

27 MHz
40 MHz

40 MHz RF systems are seen to have reduced background and provide greater plasma stability, particularly for organic analysis ICP-ES RF systems are required to produce uniform power levels under the varying conditions of sample loading Two main requirements have to be met to reduce these effects: Impedance matching level control

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Impedance matching

Impedance matching is required to maintain oscillations in a tuned circuit

Impedance is the measure of resistance in a given circuit to an alternating current at a particular frequency
The free electrons in the plasma acquire energy from the inductive coupling of the high energy RF magnetic field The amount of inductance between the electrons and the fields vary

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Impedance matching

The inductive coupling varies particularly at ignition

The coupling also varies during operation according to what type of sample is being analyzed
As the inductance changes the impedance match becomes less efficient at that given frequency To improve the matching and maintain the oscillations in the circuit, the frequency or the coupling must be varied.

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Level control

In order to control the amount of RF power supplied to the plasma a sample of the RF energy must be made The level of alternating current passing through the induction coil or the amplitude of the RF signal being transferred to the coil provide an indication of the amount of RF energy available to the plasma This level must then be compared with the operator selected power level The difference of the desired value to the known value then results in the control circuitry increasing or decreasing the amount of energy applied to the RF system

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RF Control circuitry

The control circuitry provides a computer interface for the level control of the RF system It also provides an interlock monitoring system for operator safety and equipment protection

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Gas control
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Gas control

The purpose of a gas control assembly is to regulate and control the supply of required gas flows throughout the ICP-ES Most gas control assemblies supply the gas required for torch/plasma nebulizer optics

Commercial ICP-ES instruments use argon for the plasma

Nitrogen is used on some instruments as an optics purge Oxygen is often used as carrier gas additive when organic solvents are being analyzed

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Data Acquisition / communication

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Data Acquisition

The purpose of the data acquisition assembly is to convert the proportional electrical current from the optical detector into suitable digital information for data processing by the controlling PC software Communications The purpose of the communications system is provide a means for command and control of all the internal assemblies while providing an interface for the instrument to communicate with the PC software and the various instrument accessories.