Photoacoustic Spectroscopy
(PAS)
Overview
• History of photoacoustic spectroscopy
• How the assay works
• Sampling techniques for:
– Gases
– Liquids and solids
– Powders, smears and gels
• Advantages of PAS
• Applications and the future
History of PAS
• Observed first in solids
by Bell in 1880.
• Method of
photoacoustic
spectroscopy Alexander Graham Bell
developed upon
invention of sensitive
microphones.
• Method of PAS was
formally introduced in
1973.
McPherson Photoacoustic Spectrometer
How PAS Works
• The photoacoustic effect is a translation of optical
energy in to mechanical energy by the sample.
• When illuminated by light of specific wavelength,
the analyte’s electrons become excited.
• The deexcitation process produces kinetic energy
or heat.
• Depending on the sample, the detector measures
the kinetic wave produced by the sample.
How PAS Works
• Sample placed into transparent cell.
• Beam intensity is modulated by beam splitter.
• Microphone detects sample signal.
Sources of Light
• Tungsten lamp
• High-pressure xenon lamp.
• Carbon arc lamp.
• Nearnst glower (for mid and near IR)
• Lasers (exemplary for detection at a specific
wavelength)
Sampling of Gases
• The sample gas fills a sealed cell.
• Optical energy exposure initiates internal heating of the
sample.
• A displacement sensitive microphone detects the
expansion in volume and the increased activity of the gas
particles.
• The microphone can detect a temperature change in the gas
of 10^-6 °C.
• The response time of gas is limited by the time it takes for
the kinetic wave to travel through the gas sample.
Sampling of Liquids and Solids
• Sample cell preparations are different from gas.
• Optical radiation produces kinetic vibration which causes a
detectable wave to travel through the sample.
• Piezoelectric detectors can measure the mechanical signal.
• Can detect a 10^-6 °C change in the sample.
Sampling of Atypical Matter
• Powders, gels and smears cannot be prepared like either
gaseous or nongaseous substances.
• Atypical matter is put into the sampling cell, which is
sealed and filled with a non-reactive gas.
• The heat generated by the substance will transfer to the
gas.
• This signal is detectable by a displacement sensitive
microphone.
• Detection limit: 10^-6 – 10^-5 °C
Advantages of PAS Limitations
• Indirect energy is measured as •Source of energy must be
opposed to optical radiation. sufficient (10 µW/cm^2).
– Can analyze opaque samples.
•The window of the
– Insensitive to scattered radiation.
sampling cell must be
• Variety of samples. transparent.
• No need for a photoelectric
•Background noise can
detector.
hamper the acoustic
• Sensitivity is only limited by the
measurements.
power source and the capacity of
the sample to absorb.
Applications of PAS
• Chemical study of amorphous substances:
– Oils
– Suspensions
– Powders
• One unique function is a nondestructive
depth profile analysis.
• Photoinduced reaction kinetic assays.
Future Trends
• Use of a wider spectrum of wavelengths for
analyzing samples.
• Non-invasive spectroscopic technique in
medicine
• Techniques to discover the intricate folding
patterns of complex proteins.
Sources
Rosencwaig, Allan. Photoacoustic Spectroscopy. John Wiley &
Sons, New York. 1980.
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