Atomic Spectroscopy:

Atomic Emission Spectroscopy

Atomic Absorption Spectroscopy
Atomic Fluorescence Spectroscopy
* Elemental Analysis
* Sample is atomized
* Absorption, emission or fluorescence of atoms or ions in the
gas phase
Atomic Emission Spectroscopy
Ingle and Crouch,
Spectrochemical Analysis
Electronic Levels for Individual Electrons
Ingle and Crouch, Spectrochemical Analysis
Electronic Configuration of Atoms
Al: 1s
2
2s
2
2p
6
3s
2
3p
1
Electronic Configuration of Atoms
l = 0
s-orbital
m
l
= 0
l = 1
p-orbital
m
l
= 0, 1
l = 2
d-orbital
m
l
= 0, 1, 2
1s
2s 2p
3s 3p 3d
4s 4p 4d 4f
5s 5p 5d 5f
6s 6p 6d 6f
Aufbau Order
Electronic Configuration of Atoms
Al: 1s
2
2s
2
2p
6
3s
2
3p
1
Electronic States of Atoms
Quantum numbers for electrons Quantum numbers for many-electron atoms
l: orbital angular momentum quantum L: orbital angular momentum quantum number
number (0,1, n-1 e.g., for 2 e-: L =l
1
+l
2
, l
1
+l
2
-1, l
1
+l
2
-2, ,| l
1
-l
2
|
where 0=s, 1=p, 2=d, 3=f) 0 =S, 1 =P, 2 =D, 3 =F
m
l
: orbital magnetic quantum number M
L
: orbital magnetic quantum number (m
l
)
(l, l-1, , 0, , -l ) 2L+1 possible values
s: electron spin quantum number (1/2) S: total spin quantum number
S = s
1
+s
2
, s
1
+s
2
-1, ,| s
1
-s
2
|
S =0 singlet, S =1 doublet, S =2 triplet
m
s
: spin magnetic quantum number M
S
: spin magnetic quantum number (m
s
)
(+1/2, -1/2) 2S+1 possible values
J: total angular quantum number
J = L+S, L+S-1, , | L-S|
Spectroscopic Description of
Atomic Electronic States Term Symbols
Multiplicity (2S +1) describes the number of possible orientations
of total spin angular momentum where S is the resultant spin
quantum number (1/2 x # unpaired electrons)
Resultant Angular Momentum (L) describes the coupling of the
orbital angular momenta of each electron (add the m
L
values for
each electron)
Total Angular Momentum (J) combines orbital angular momentum
and intrinsic angular momentum (i.e., spin).
To Assign J Value:
if less than half of the subshell is occupied, take the minimum
value J = | L S | ;
if more than half-filled, take the maximum value J = L + S;
if the subshell is half-filled, L = 0 and then J = S.
Spectroscopic Description of
Ground Electronic States Term Symbols
Term Symbol Form:
2S+1
{L}
J
2S+1 multiplicity
L resultant angular momentum quantum number
J total angular momentum quantum number
Ground state has maximal S and L values.
Example: Ground State of Sodium 1s
2
2s
2
2p
6
3s
1
Consider only the one valence electron (3s
1
)
L = l = 0,
S = s = ,
J = L + S =
so, the term symbol is
2
S

Are you getting the concept?

Write the ground state term symbol for fluorine.
C 1s
2
2s
2
2p
2
Step 1:Consider two valence p electrons
1
st
2p electron has n = 2, l = 1, m
l
= 0, 1, m
s
= 6 possible sets of
quantum numbers
2
nd
2p electron has 5 possible sets of quantum numbers (Pauli Exclusion
Principle)
For both electrons, (6x5)/2 = 15 possible assignments since the electrons
are indistinguishable
Spectroscopic Description of
All Possible Electronic States Term Symbols
Step 2: Draw all possible
microstates. Calculate M
L
and
M
S
for each state.
C 1s
2
2s
2
2p
2
Step 3: Count the number of microstates for each M
L
M
S
possible
combination
Spectroscopic Description of
All Possible Electronic States Term Symbols
Step 4: Extract smaller tables representing each possible term
C 1s
2
2s
2
2p
2
Step 5: Use Hunds Rules to determine the relative energies of all
possible states.
1. The highest multiplicity term within a configuration is of lowest
energy.
2. For terms of the same multiplicity, the highest L value has the
lowest energy (D < P < S).
3. For subshells that are less than half-filled, the minimum J-value
state is of lower energy than higher J-value states.
4. For subshells that are more than half-filled, the state of maximum
J-value is the lowest energy.
Based on these rules, the ground electronic configuration for carbon has
the following energy order:
3
P
0
<
3
P
1
<
3
P
2
<
1
D
2
<
1
S
0
Spectroscopic Description of
All Possible Electronic States Term Symbols
Write term symbols in analogous manner except consider the
orbital to which an electron is promoted.
For example, excitation of Na promotes one valence electron
into the 3p orbital. In this case, n = 3, S = , 2S+1 = 2, L
= 1 (P term), J = 3/2, 1/2.
There are two closely spaced levels in the excited term of
sodium with term symbols
2
P
1/2
and
2
P
3/2
Spectroscopic Description of
Excited States Term Symbols
This type of splitting (same L but
different J) is called fine structure.
Transition from
2
P
1/2

2
S
1/2
To calculate the energy of a single electron atom with
quantum numbers L, S, and J:
E
L,S,J
= hc[J(J+1) - L(L+1) S(S+1)]
where is the spin-orbit coupling constant
Calculating Energies for Transitions
Atomic emission spectra show a doublet in the Na spectrum
due to spin-orbit coupling of the
2
P state. Given that =
11.4 cm
-1
, find the energy spacing (in cm
-1
) between the
upper
2
P
3/2
and
2
P
1/2
states.
Are you getting the concept?
2
P
3/2
2
P
1/2
2
S
1/2
1 eV = 8065.5 cm
-1
Allowed and Forbidden Transitions
Only a fraction of all possible transitions are observed.
Allowed transitions
-high probability, high intensity, electric dipole
interaction
Forbidden transitions
-low probability, weak intensity, non-electric dipole
interaction
Selection rules for allowed transitions:
* The parity of the upper and lower level must be
different. (The parity is even if l
i
is even. The parity is
odd if l
i
is odd.)
* l = 1
* J = 0 or 1, but J = 0 to J = 0 is forbidden.
Additional Splitting Effects
Hyperfine splitting due to magnetic coupling of spin and orbital
motion of electrons with the nuclear spin.
Isotope shift. Sufficient to determine isotope ratios.
Splitting in an electric field (Stark effect): Relevant for arc and
spark techniques.
Splitting in a magnetic field (Zeeman effect):
* In absence of a magnetic field, states that differ
only by their M
J
values are degenerate, i.e., they
have equivalent energies.
* In presence of a magnetic field, this is not true
anymore.
* Can be used for background correction.
Pretsch/Buhlmann/Affolter/Badertscher, Structure Determination of Organic Compounds
Pretsch/Buhlmann/Affolter/Badertscher,
Structure Determination of
Organic Compounds
Stark Splitting
www.wikipedia.org
For H:
split E
For others:
split (E)
2
Zeeman Splitting
Ingle and Crouch,
Spectrochemical Analysis
M
J
Resultant total
magnetic quantum
number
M
J
= J , J -1, , -J
2J +1 possible values
Normal Anomalous
Sample Introduction and Atomization
Atomization:
Convert solution vapor-phase free atoms
Measurements usually made in hot gas or enclosed furnace:
flames
plasmas
electrical discharges (arcs, sparks)
heated furnaces
Free
Atoms
Ions Mole-
cules
Nebulization
Desolvation
Volitalization
Adapted from Ingle and Crouch
Atomic Emission Spectroscopy (AES)
See also: Fundamental reviews in Analytical Chemistry
e.g. Bings, N. H.; Bogaerts, A.; Broekaert, J . A. C. Anal.
Chem. 2002, 74, 2691-2712 (Atomic Spectroscopy)
Beginning 19th century: alcohol flame (Brewster, Herschel, Talbot,
Foucault)
mid 1800s: Discovery of Cs, Tl, In, Ga by atomic spectroscopy
(Bunsen, Kirchhoff)
1877: Gouy designs pneumatic nebulizer
1920s: Arcs and sparks used for AES
1930s: First commercial AES spectrometer (Siemens-Zeiss)
1960s: Plasma sources (commercial in 1970s)
Atomic Emission Spectroscopy (AES)
2
S
1/2
2
D
3/2, 5/2
2
P
3/2
2
P
1/2
2
S
1/2
At RT, nearly all
electrons in 3s
orbital
Excite with flame,
electric arc, or
spark
Common electronic
transitions
http://raptor.physics.wisc.edu/data/e_sodium.gif
Example AE Spectra
http://www.technology.niagarac.on.ca/lasers/Chapter2.html
H
2
Hg
He
An Ideal AES Source
1. complete atomization of all elements
2. controllable excitation energy
3. sufficient excitation energy to excite all elements
4. inert chemical environment
5. no background
6. accepts solutions, gases, or solids
7. tolerant to various solution conditions and solvents
8. simultaneous multi-element analysis
9. reproducible atomization and excitation conditions
10. accurate and precise analytical results
11. inexpensive to maintain
12. ease of operation
Flame AES
Background signals due to flame fuel and oxidants line spectra:
OH

281.1, 306.4, 342.8 nm

from O + H
2
H + OH
H + O
2
O + OH
O
2
250, 400 nm
CH431.5, 390.0, 314.3 nm
CObands between 205 to 245 nm
CN, C
2
, CH, NH bands between 300 to 700 nm
Unlike bands of atomic origin, these molecular bands are fairly broad.
Continuum emission from recombination reactions
e.g. H + OH H
2
O + h CO + O CO
2
+ h
Flames used in AES nowadays only for few elements. Cheap but
limited. {Flame AES often replaced by flame AAS.}
Ingle and Crouch
Inductively Coupled Plasma AES
Spectral interference more likely for plasma than for flame due to larger
population of energetically higher states.
Modern ICP power: 15 kW (4 to 50 MHz)
4000 to 10,000 K: Very few molecules
Long residence time (23 ms)
results in high desolvation
and volatilization rate
High electron density suppresses
ionization interference effects
Background: Ar atomic lines and,
in hottest plasma region,
Bremsstrahlung (continuum radiation
from slowing of charged particles)
Price > $ 50 k
Operating cost relatively high due
to Ar cost (1015 mL/min) and
training.
www.wikipedia.org, Ingle and Crouch
Microwave Plasma AES
Power 25 to 1000 W (ICP 10002000 W)
Frequency 2450 MHz (ICP 4 to 50 MHz)
Argon, helium or nitrogen
Temperature estimated to be 2000 - 3000 K
Low temperature causes problems with liquids
Useful for gases: GCmicrowave plasma AES
Arcs and Sparks
Arc = An electrical discharge between two or more
conducting electrodes (1-30 A)
Spark = An intermittent high-voltage discharge (few
sec)
Limited to qualitative and semi-quantitative use (arc
flicker)
Particularly useful for solid samples (pressed into
electrode)
The burn takes > 20 sec (need multichannel detector)
Ingle and Crouch