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Atomic absorption spectroscopy was limited in usefulness by poor sensitivity, and the
inability to perform multi-element analysis.
A flame, even the hottest, will only reach a temperature of about 3000K. This will
only excite elements in the first two groups.
For high temperatures, electrical discharges must be used. A DC arc will reach up to
10,000K. These can be used with solid samples, and are used during the analysis of
manufactured steel. Spark sources can also be used. However, these electrical
discharge sources are relatively unstable.
An atomisation source was needed that would give a detection limit of less than 1ppm
for multi-element solutions. In 1965, the inductively coupled plasma (ICP) was
developed. This is the most efficient atomiser known. It was initially used in ICP-
AES, and more lately in ICP-MS.
The intensity of the emission is related to the Einstein Transition Probability for
spontaneous emission (Aki) - the probability per second that an excited atom will emit
a photon and return to the ground state. Aki is equal to the inverse of the half-life of
the excited state.
Better to relate to number of atoms per cubic metre - closer to chemical concentration.
Let N = number of atoms per cubic metre.
This equation gives watts into all space which we cannot measure.
Amount of light is determined by the area of the slit and the solid angle.
, but ΔV = ΔA x L
so,
Thermodynamic Equilibrium
Gas temperature
For LTE:
Self-Absorption
The emitted photon may be absorbed by atoms of the same kind in the source. The
higher the density of atoms in the source, the process of self-absorption is more likely.
Consequences
(a)
WHMH stays the same to a limit. The peak intensity gets stuck at the black body
limit. P is now a function of temperature only. This limit is called the Planck
temperature, same as an incandescent metal bar, P ∝ c.
The line also gets broader. Peaks are Gaussian - they extend to ±∞. Although the
middle limit has been reached, the “wings” continue to increase in intensity.
B’(ν) = B0[1-exp(-kνL)]
Aν = 1-exp(-kνL) absorptivity
(b) As long as the bandpass is sufficient to see everything, the slope changes from 1 to
1
/2 as P ∝ c → P ∝ √c.
If narrow bandpass :
i) LINE BROADENING
ii) LOSS OF LINEARITY
iii) RADIATION TRAPPING
The increased velocity of atoms in the hottest part of the sources causes the frequency
to be doppler-shifted.
Self-reversal arises since only the hottest part significantly emits but all, especially
cool, atoms will absorb.
Hot atoms emit photons which are absorbed by cool atoms. This is bad news. Extreme
example :
Inductively Coupled Plasma (ICP)
A torroidal plasma.
Particles are injected at about 2 m s-1, and they cannot move sideways because it is
too hot.
Any compound with a diameter less than 10µm is blown into free atoms.
ICP is the best ever source for atomisation. It is also a pretty good excitation source -
will excite atomic spectra and ionic spectra.
Injection will not interrupt power coupling as the injection zone is only indirectly
heated. Can inject gases, liquids and solids. Can even insert a carbon rod with the
sample on the end into the central channel.
So ICP is:
The temperature distribution is the analytical region is pretty flat. Flat temperature
field, so no self-reversal. The optical depth, L, is small.
Atoms expand out a bit, but not a lot.
Dynamic range is large - 6 orders of magnitude.
Ionisation Equilibrium
• Ionisation mechanism
• Recombination
Ar+ + e- + e- ⎯→ Ar + e*
Power Requirements
Power
for =2.77 x 10-4 kg s-1 (10 l min-1 Ar) and ΔT = 5000K, P = 720W assuming 100%
coupling efficiency.
Plasma Zones
PHZ : Pre-heating zone.
- desolvation, vapourisation, partial atomisation.
Tailflame
- reappearance of low energy atomic lines and band emission from
atmospheric
entrainment.
e.g. Li, Na, K, CaI, BaI, SrI, CuI up to Cd 288.8nm (atomic line)
Summary
Instrumentation
Comprises:
Source unit
Sample introduction system
Spectrometer
Computer for control and data manipulation
Source Unit
RF Generator
(i) Two types :- - free running oscillator (frequency alters as the plasma does -
load coil is part of the generator)
- crystal oscillator and power amp (more common, can be
miniaturised, and can now be separated)
(In plasma, temperatures are not in thermal equilibrium (but nearly). Above 100MHz
Tthermal is not much hotter than a flame - start to get interferences).
Torches
(ii) Gas consumption can be reduced using smaller annular gap, but cost of the torch
increases, or, use mini-torch, 13mm i.d. outer tube (5-10 l min-1).
(iii) Molecular gas plasma can be operated at slightly higher powers, e.g. Ar + 10%
N2 (outer flow), gives increased performance but not used commercially.
Air plasma has been used for process control - start with argon.
ICP is very robust with respect to sample introduction and can accept samples as
solids, liquids or gases. However, particle size d ≤ 6µm.
(i) Nebulisation
Pneumatic nebuliser operating at 1 l min-1 Ar (injector flow) and 1-2ml min-1 sample
→ polydispersers and aerosol., 0.1 < d < 100µm.
Spray chamber removes large (and small) particles, allowing particles d < 6µm to the
plasma.
Types of nebuliser:
Concentric flow and cross flow - good for low matrix samples.
Babbington - essential for slurries.
Slurries are aqueous suspensions of powdered (d < 6µm) solids and surfactant, usually
< 4g / 100 conc.
Volatile elements, e.g. As, Se, Sb, Pb, Te : not good detection limits using
nebulisation.
A gas liquid separator is used to separate the hydride from the aqueous phase and the
hydride swept into the plasma using the injector flow.
Advantages:
Disadvantages:
Laser Ablation
NB. Solid sampling techniques require standards that are closely matched in chemical
content and physical form to the sample.
Spectrometers
Atomic lines are very narrow, e.g. 0.003nm. Many thousands of lines in spectrum so
can get many lines in 1nm of the spectrum, so need bandpass about 0.01nm. Can get
up to 4800 lines per millimetre on modern gratings.
Advantages:
(a) Flexibility of line selection, 200nm, flushing with e.g. nitrogen can get lower. Up
to
1600nm (sulfur / phosphorus / aluminium lines are found below 200nm).
Disadvantages:
(a) Speed of analysis is slow, e.g. spray sample into chamber, move to e.g. Cd line for
20 secs, move to next line etc. Must keep spraying sample - 10/15 ml for 10
elements.
Uses : moderate throughput of samples (e.g. 12-20 per day), type of analysis not
known in advance, high resolution required.
Based on curved grating (part of Rowland circle). Costs about £1000 to install each
line.
Scan spectrum at each exit slit - place on stepper motor slide, move back and forward
≈ 1mm to ensure no overlapping lines.
Advantages:
(a) Speed of analysis - spray 20secs to stabilise signal, then 20secs to measure all
lines.
(b) Minimal sample consumption - spray once. Powerful system for small samples if
coupled with ETV.
Can couple to HPLC in speciation studies (or CE), e.g. HPLC for vitamin B12, see
large Co peak.
(e) Ease of applying matrix corrections - account from interferences from sample.
Disadvantages:
Uses: high throughput (e.g. 200 samples per day), routine samples, not too severe
spectral interferences.
- Echelle Grating Spectrometer : uses coarsely ruled grating at high order to achieve
high resolution, need 2nd disperser to sort orders,
expensive, low light throughput.
- Fourier Transform : very expensive (£230k), research only.
CCD, 10mm x 10mm chip and large spectrum, need advanced optics (available). PE
developed CCD chips, have 1,000,000 points and takes a computer a long time to read
all the points, so have 1200 regions of interest. Cost ≈ £100,000, but CCD/CID are
very powerful.
Interfernces
- The effect is to add an increment to the analyte emission signal. The increment is
constant provided that the concentration of the interferrent is constant.
a) Spectral Overlap
This is a physical problem, get a merging of the two peaks to give a double hump in
the scanned peak.
b) Line Interference
c) Background Interferences
Large interfering line (e.g. Al). Observed peak is larger than true peak.
Line Overlap
- use an alternative line. Always best, but sometimes can’t because of sensitivity
problems.
The success of this approach depends on the overlap and relative magnitude of the
two lines. The interfering line contributing noise and CL increases by 0.1x magnitude
of the correction.
Line Interference
- narrow slits give S/N problems. Can go down to 3µm. Lose too much light.
- work in a different order.
Background Interferences
But often don’t know the problem, so don't know what to measure.
ICP used as an ion source for a quadrapole mass spectrometer ( a tuneable mass filter
with a resolution of 0.5-1.0 amu).
A three stage interface is used to couple the plasma at atmospheric pressure to the MS
at 10-7 torr.
Ion lenses are cylinders with different positive voltages on them. They re-focus the
ion beam.
Analytical Advantages
1. Very high sensitivity < 1ppt (pg ml-1) for some elements - partially due to the low
background, ≈ 10cps or better compared with analyte count rates of 5x106cps per
ppm.
2. Wide element coverage, nearly all periodic table except inert gases can be
determined (quadrapole can scan complete mass range in ≈ 50µs - appears to be
simultaneous).
5. Simple spectra, only 211 isotopes for all the periodic table.
6. Uniform sensitivity - sensitivity varies by a factor of 2-3 across the periodic table
(heavy elements are more sensitive). The mass-bias can be calculated and then semi-
quantitative (±10%) “what is in it” analysis carried out following single element
calibration, e.g. indium.
Disadvantages
3. Sample enters the interface and some deposits in the machine, ∴ regular cleaning is
required (particular problem for radioactive materials). Try not to have to clean
quadrapole - sensitive to alignment.
4. Purchase price (£200k) and running costs are higher than ICP-OES.
Interferences
2 types :
- spectral
- matrix
Spectral Interferences
2 main types :
Isobaric Interferences
- caused by isotopes having very similar m/z ratios that are not resolved by the
quadrapole.
Most serious example is 40Ar-40Ca. 40Ca is the most abundant isotope (96.97%) of Ca.
Ar, O, N, H
- Rare earths give rise to very strong oxide bonds, e.g. CeO, but optimising operating
conditions reduce them to 1-3% of element signal.
Matrix Interferences
- high matrix levels → high ion currents, because of space charge effects, ions are
ejected from the ion beam.
- effect is most serious for a heavy element matrix, e.g. Pb and a light element analyte,
e.g. B.