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

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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

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Characteristics of monochromators

Dispersion

Angular dispersion: DA = d / d

Linear dispersion: Dl = dl / d = fDA f=Focus length of the lens

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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
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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

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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

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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

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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
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Absorption methods

Absorbed energy converted into heat and/or light of other wavelengths and
directions
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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
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Scatter methods (e.g., Raman)

Monochromatic light

measure the side wavelength instead of the fornt

Measures the shift in wavelength due to molecular interactions

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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
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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
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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)

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AE of different elements

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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

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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?
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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