Spring 2017 CHEMISTRY 105
Instrumental Methods in Analytical Chemistry
Lecture: MW 9 AM 10 AM 219 Dwinelle
Labs: MTuWTh 1 5 PM 305 Latimer
Lecture 4. Atomic Spectroscopy
Prof. Ke Xu
1
How to generate a spectrum: spectrometer/monochromator
Refocuse in different position
Dispersion unit: Spread a
line-shaped light beam
into a band according to
wavelength
Recording the resultant
spectrum: directly, or slit +
scan
3
Characteristics of monochromators
Dispersion
Angular dispersion: DA = d / d
Linear dispersion: Dl = dl / d = fDA f=Focus length of the lens
1
Reciprocal linear dispersion: Dl = d / dl Unit: nm/mm
Resolving power
Unitless
R= Desired: >10,000 to separate Fe lines
Light-gathering capability
Output energy
L=
Input energy
4
Spectra at different spectral resolution 5
0.5 resolution
larger band width, lower resolution
Effect similar to
averaging/smoothing
Dispersive element: Prism
light interaction with te material differenetly dependent on the wavelength. the shorther the wavelenth is, the hight energy is, higher energy interact with te material
more strongly. the refract index would be higher. e.g. the blue ligh is baned more compare to read light.
Difference in refraction index n for different wavelengths
Higher n for shorter wavelength higher energy and stronger interaction: bends
more
6
Dispersive element: Diffraction gratings 7
n = d sin
n: order of diffraction
d: periodicity of grating
: angle
Grating, long lof light on lot of line gap, ligh can
only pass through those gap, the black dot line. the
light can travel to the screen, and at some spot the
light would be interference constructively, with Denser pattern = wider angle
the form nlambda=dsinetheta, if strateed with
dmultiple wavelentgh, there will be different Longer wavelength = wider angle
angle.
longer wavelength, father away from the center
Stronger dispersion and higher resolving power with denser grating
May be transmitting or reflecting
CDs as gratings 8
8
Detection and recording of spectrum 9
Take a real photo on photographic film! traditionally, people take the black and white photo
AgBr/AgI
Glass
CCD and other multi-pixel imagers, digital cameras
Arrays of light sensors
Single-element detectors for spectrum recording
moving the slit at the exit site with one detector to meausre the wavelength
Single-element detector:
Slit + scanning!
Rotating the freflection grating (grating mount,) and select the different output
Rotating the grating selects wavelength at the exit slit.
Record the full spectrum over time through scanning
Narrowing entrance and exit slits:
Resolution
Transmission 10
Photomultiplier (PMT) as a common single-element detector
Photoelectric effect
when light strike the cathode, the cathode emit the electron and pass through to the anode, and get detected
Emits electrons for wavelengths shorter than the threshold
11
12
Photomultiplier as a common single-element detector
Secondary emission
one electron is hard to get detected, using photomltiplier to amplify the the signal using multiple dynode.
PMT Film CCD
Dynamic Range >1000 <100 >10,000
Detection Speed fastest slow slow
Quantum Efficiency 5-20% 5-20% 25-95%
Multi-channel no yes yes
Real-time yes no yes
Spectral Sensitivity (nm) 300-900 200-1300 300-1100
Dark Signal good poor best
Read Noise good good best
13
Absorption methods
Absorbed energy converted into heat and/or light of other wavelengths and
directions
14
Emission methods
Bring the energy level of the system to excited state
Or, other forms of
energy input: thermal,
electrical, or chemical
Examples
Photoluminescence (fluorescence,
phosphorescence)
Atomic emission
Chemiluminescence
15
Scatter methods (e.g., Raman)
Monochromatic light
measure the side wavelength instead of the fornt
Measures the shift in wavelength due to molecular interactions
16
Atomic spectra: First noted in the solar spectrum
Fraunhofer lines: atomic absorption (AA)
Na! Na absorb particular wavelength of sun light
Solar spectrum in details
AA reveals many chemical elements in the solar atmosphere
Many spectral lines are in the UV-visible range
Atomic emission (AE) 18
Na K Li Ba
Flame test
Fireworks
Atomic spectra: transitions between atomic energy levels
Na AE
AA
Spectral lines are due to fixed energy levels
E = h = hc/
A few eV visible light range
Spin-orbit
coupling
[Ne] 3s1
Valence angstroms
electron Sodium lamp Electric Pickle
19
Atomic absorption (AA) vs. emission (AE) 20
Absorption lines: Atomic gas between a light source and the detector. Decrease
in the intensity of transmitted light at particular wavelengths due to absorption.
Thermal
energy
Emission lines: Detector sees photons emitted directly from a glowing gas
21
Energy levels: Na vs. Mg+
Na Mg+
Split of p-orbital
energy due to
spin-orbital
interaction
[Ne] 3s1
angstroms Valence electron
One single valence electron: Similar patterns for Na and Mg+
Actual energy is different by ~two folds
Energy levels for hydrogen-like atoms
Magnesium 22
angstroms
Two valence electrons: Singlet vs.
triplet sates
More complicated transitions
Take-home messages for atomic spectroscopy: 23
Not all transitions are allowed selection rules
Allowed transitions and spectral lines are still numerous.
Alkali metals: ~200 lines. Transition metals: 1,000+ lines!
Different spectral lines have different intensities. Population + selection rules
Resonance lines: transition between the ground state and first excited state.
Strongest!
Detection of specific spectral lines
existence and/or concentration
of an element
Flame emission of sodium
Sodium lamp
Examples:
Solar
spectrum
(AA)
Identification
of elements
in fireworks!
(AE)
24
AE of different elements
25
Population of energy levels
Boltzmann distribution
For a system at equilibrium:
Degeneracy Energy
Population
Nj gj ( E j E0 )
= exp
N0 g0 kT
Temperature
States with higher E Lower population
Most populated at any T: ground state
Second-most populated state: first excited state.
Resonance lines: Strongest signal
T Increased population for states with higher E
26
Population of energy levels: temperature effects
T Increased population for states with higher E
Still small fractions for excited states
Example 8-2 in textbook: First excited state of sodium
gj 6
E j E0 = h = =3
g0 2
Nj gj ( E j E0 )
= exp
N0 g0 kT
Use an averaged wavelength of 589.3 nm:
@2500K: 1.7210-4 @2510K: 1.7910-4
Q: Not considering degeneracy, when would the population of excited states
approach that of the ground state?
27
28
Implications for spectroscopy
Even at T = 2500 K, population of the first excited state is ~10-4
Sodium is easy to excite: = 589 nm
Other elements: shorter & higher E still lower population of excited states
For T = 10 K: Noticeable relative change of population for the excited state.
Small relative change for the ground state.
AE: signal from atoms in excited states
AA: signal from atoms in the ground state
Most atoms are in the ground state AA has better S/N?
Smaller T-dependence for ground-state population
Not necessarily!
AE: detects a positive signal over zero (or low) background
AE can be better!
AA: detects a negative signal on a large background
Stable T, however, is important for reliable measurement, in particular for AE
