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Instrumental Analysis
Instrumental analysis
50
Chemistry
Undergraduate 4
11/05/2012

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Term
moseley's law
Definition
relationship between atomic # and wavelengths (E) of the emitted x-ray photons. *Equation*
Term
fluorescence yield
Definition
Efficiency of the emission of x-ray photons. Yield is higher in the order of K series> L series > M series (higher for more inner orbital transitions)
Competition between x-ray fluorescnece and auger process keeeps fluorescence yield low.
Higher for heavier elements.
Term
XRF instrumentation
Definition
1.WDXRF
2.EDXRF
Term
WDXRF
Definition
crystal spins in relation to beam, maintaining angle between crystal at specimen at 2x angle between crystal and detector.
counting progresses until sufficient counts for precise results. source is polychromatic tube.
scanning range allows the complete spectrum to be acquired. the detector rotates at twice the speed of the crystal to maintain 2x angle.
Term
EDXRF
Definition
crystal not needed (don't need to disperse emitted e-). source is radioactive material or polychromatic tube. Si(Li) detector. Source is closer to detecter: increase in E reaching detector, weaker source can be used. Increased sensitivity, no moving parts, all wavelengths measured simultaneously.
Term
X-ray tube
Definition
Continuum source. x-ray can be generated with wide range E. Electrons are accelerated from a heated filament to a metal where x-rays are generated and deflected out window. Extremely inefficient. Energy of x-rays proportional to voltage used. heater controls xray intensity.
Term
continuum and line spectra from electron beam sources
Definition
-comtinuum radiation from an electron beam source results from collissions between the e- of the beam, and atoms of target material.
-line spectra result from electronic transitions that involve the innermost atomic orbitals
Term
duane hunt law
Definition
energy of photon is equal to the differences in kinetic energies before and after collission. max photon E when E of e = 0, representing the instant deaccel of e- to zero.
Term
dispersion for WDXRF instruments
Definition
1. spacing between layers of atoms must approx. = wavelength of radiation
2. centers must be spaced in highly regular way
Term
Gas filled detector as X-ray transducer
Definition
1. ionization chamber (not used for xrays)
2. gieger tube
3. proportional counter
Term
how gas filled x-ray detector works
Definition
x-ray enters detector and interacts with gas inside to produce a cloud of ionization. # e- reaching anode is proportional to total # formed by single photon.
Term
Geiger tube
Definition
amplifycation is high and independent of the type and E of radiation. slower response.
Term
Proportional counter
Definition
amplifycation is lower and depends on the E of radiation. faster repsonse. widely used. used with pulse height analyzer.
Term
X-ray detectors operated as photon counters. Photon counting.
Definition
arrival of individual photons are accurately transduced and recorded for low intensity beams.
Photons generate e-, which accumulate on C and give pulses. (this is how individual pulses produced as quanta of radiation are absorbed and counted by transducers)
Term
advantages of photon counting over analog signal processing
Definition
1. improved signal to noise ratio
2. Sensitivity to low radiation levels
3. improved precision for a given measurement time
Term
Proportional counter
Definition
Number of photoelectrons is proportional to the energy of the photon and then the pulse height.
Term
Multichannel pulse heigh analyzer
Definition
1000 separate channels. Each channel detects a height with a different V window. Can tell # of photons with particular energy.
Term
Scintillation counter
Definition
x-ray loses energy to scintillator. Flashes of light are transmitted to photocathode of a photomultiplier. # of fluorescence photons is proportional to the x-ray energy. electrons at photomultiplier tube (amplified)*photoelectric effect to convery photons into electrons.Converts height of peak into E of x-ray photons.
Term
EDXRF instrument
Definition
1. proportional Si(Li) detector gives a distribution of voltage pulses proportional to the spectrum of X-ray photons.
2. Multichannel analyzer is used to locate the voltage pulses into discrete intervals. Consecutive output of MCA intervals allows complete spectrum to be displayed.
Term
Si(Li) Detector
Definition
e- used to separate charge in detector. Improves resolution using semiconductor.
Term
UV-Spec single beam
Definition
need blank to measure Po (incident radiant power), then measure sample, then do correction
Term
UV-spec double beam
Definition
reference and sample irradiated simultaneously. Advantage that fluctuations in source intensity are cancelec and is electronic drift.
Term
Deuterium lamp; continuum source.
Definition
energy of the radiation (difference between quantized E levels of excited molecule and the kinetic E of atoms) can vary continuously over the same range.
Term
Tungsten and tungsten/halogen lamps
Definition
1. most common source of vis and near IR radiation. includes small amt of iodine prolongs lamp life (sublimes with metal and causes it to be redeposited)
Term
dark current
Definition
small current that exists in radiation tansducer in the absence of radiation. *noise*
Term
multichannel spectrometer
Definition
detect entire spectral range simultaneously and quickly produce spectrum. Speed and long term reliability.
Term
effects of instrumental noise on spectrometric analyses
Definition
Term
spectrofluorometer
Definition
monochromators for wavelength selection
two monochromators needed- one for each spectrim (emission and excitation)
Term
difference btw. excitation and emission spectra FLuorescence
Definition
Emission- excitation wavelength held constant against a varying emission wavelength
Excitation- emission wavelength held constant while excitation wavelengths are scanned. Excitation looks like absorption.
Term
fluorometer
Definition
has filters for wavlength selection (can only use if you know your fluorphore/ emission/ excitatino properties) *restricted to a few wavelengths. *microscope: choose filter to pass specified stain.
Term
IR
Definition
measures absorption, chemical nature and molecular struc.
Term
rotational/vibrational IR differences
Definition
rotational- far IR
vibrational- mid IR
Term
IR gas spectrum
Definition
series of closely spaced lines
1. due to excitation of rotational motion during a vibrational transition
2, well defined lines are observed because both vibrational and rotational levels are quantized as char. by vibrational and rotational quantum #s.
Term
IR broadening in liquid and solid samples
Definition
because molecular rotation is highly restricted in solids and intramolecular collissions and interactions are more frequent than period of rotation in liquids.
Term
group/ finger print regions
Definition
Term
force constant
Definition
calculated from IR spectra- represent stiffness of the bond. affected by balance of nuclear repulsions, electron repulsions, and electron-nuclear repulsions, NOT mass.
Term
anharmonic oscillator model for molecular vibrations is more realistic because
Definition
1. coloumbic repulsion between nuclei, potential energy raises more rapidly than the harnomic oscillator predicts
2. dissociation of atoms take place at high enough interatomic distances.
3. change in E becomes smaller at higher quantum #s
Term
IR selection rules
Definition
change in dipole during vibration in order for a molecule to absorb infrared
2. fundamental absorption occurs with deltav= -/+1 and e=hv(m)
3. change E becomes smaller at higher quantum numbers and the selection rule is not rigorously followed.
Term
# of vibration modes
Definition
3N-6 nonlinear
3N-5 linear
Term
less experimental IR bands found when
Definition
1. dipole is same in normal mode
2. energies of two or more vibrational modes are nearly Idential
3. absorption intensity too weak or beyond instrument range
Term
more experimental nodes found when
Definition
1. overtone bands observed
2. two vibrational bands are excited to give a combination band
Term
vibrational coupling
Definition
strong coupling when two vibrationa have an atom in common
between two bending vibrations with a commmon bond between them
strongest when energies are equal
no coupling if groups are separated by 2+ bonds
Term
FTIR
Definition
whole spectrum measured at once- no dispersion. Uses interferometer. mirror position precisely monitored.
Term
IR transducers
Definition
1. photon- individual photons change electrical properties
2. thermal- absorption of photons leads to temperature change
Term
photoconductive detectors
Definition
semiconductor that decreases resistance when photons are absorbed
Term
pyroelectric transducers
Definition
capacitor that can be charges by an influx of heat
Term
pyroelectric material
Definition
spontaneous t dependent polarization
Term
FTIR
Definition
intereferometer from a laser fringe reference system provides sampling interval information to enable precise signal sampling, precise signal averaging based on mirror postion. Then cycles are superimposed to give noise corrected spectrum.
Term
FTIR
Definition
monitor mirror position from -1 to 1. give timing of sample based on frequency. superimpose spectra from cycles to get noise reduced total spectrum. *cycles must be lined up precisely*
Term
ATR
Definition
how to illuminate with Ir: decay of evanescent wave (penetrates to a certain depth based on material)
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