18/06/06

Atomic  Spectroscopy  

An  Overview  
•  The  determina6on  of  elemental  composi6on  
by  spectrometric  techniques.  

•  The  atomiza6on  of  sample  is  required  for  

measurement.  

•  Extremely  high  sensi6vity,  suitable  for  trace  

element  analysis.  

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Types  of  Atomic  Spectroscopy

•  Op6cal  atomic  spectroscopy  
 

D.  Harris,  Quan6ta6ve  Chemical  Analysis,  9t  ed.  

Types  of  Atomic  Spectroscopy

•  Op6cal  atomic  spectroscopy  

•  Atomic  mass  spectrometry  

Image  credit:  Bruce  Averill  and  Patricia  Eldredge,  General  Chemistry:  

Principles,  PaLerns,  and  Applica6ons,  FlatWorld  

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Atomic  Emission  and  Absorp6on  

•  Absorp6on  and  emission  peaks  are  extremely  
sharp  due  to  the  absence  of  vibra6onal  levels.  
 

H  

700   600   500   400   (nm)  

Image  credit:    Joshua  Halpern  et  al.,  Chemistry  LibreTexts,  UC  Davis  

Atomic  Emission  and  Absorp6on  

•  Absorp6on  and  emission  peaks  are  extremely  
sharp  due  to  the  absence  of  vibra6onal  levels.  

•  The  absorp6on  and  emission  spectra  

complement  Heach  other.  
 

Hydrogen  emission  spectrum  

Hydrogen  absorp6on  spectrum  

700   600   500   400   (nm)  

Image  credit:    Joshua  Halpern  et  al.,  Chemistry  LibreTexts,  UC  Davis  

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Atomiza6on  Methods  for  

Atomic  Absorp6on  
Spectroscopy  
•  Flame  atomizer •  Electrothermal  atomizer
Sample  flow  
(Short  residence  6me  in  the  op6cal  path)
Flame
Op6cal  Path

Sample  flow  
(Longer  residence  6me  in  the  op6cal  path)
1.  External  coolant  inlet          2.  External  coolant  outlet  
Temperature  around  2000  –  3000  K 3.  Sample  port  and  inert  gas  outlet    
4.  Inert  gas  inlet                                      5.  Op6cal  path

Image  credit:  H.  Rutledge  &  A.  Barron,  OpenStax,  Chemistry.  OpenStax  CNX.    

Atomiza6on  Methods  for  

Atomic  Emission  Spectroscopy  
•  Induc6vely  Coupled  
      Plasma  (ICP)
–  The  high  temperature  (~  10000  K)  
excites  most  atoms  for  emission  

–  Plasma  generated  by  e-­‐  collision  

with  Ar  
 
–  Ar  plasma  ionizes  analyte  as  well,  
thus  suitable  for  combina6on  
with  mass  spectrometry
Image  credit:  David  Harvey,  Chemistry  LibreTexts,  UC  Davis  

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Atomic  Fluorescence  
•  A  combina6on  of  atomic  absorp6on  and  
emission  spectroscopy  
Atomized  analyte  
Excita6on  light  source   Lower  
measurement  
background  
Fluorescence  emission  
Selec6ve  excita6on  of  a  
specific  atomic  species   Same  atomiza6on   De
tec
methods  as  atomic   to r
 
absorp6on  spectroscopy  

Interference
•  Spectral  interference  
–  Overlapping  of  analyte  and  unwanted  signals  

Blank  from  1%  HNO3  solu6on  

Krachler  &  Alvarez-­‐Sarandes,  Microchem.  J.,  2016  

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Interference
•  Spectral  interference  
 
•  Chemical  interference  
–  Reac6ons  that  reduce  the  extent  of  atomiza6on  

SO42-­‐  

CaSO4  
Ca2+   Nonvola6le  salt  

Interference
•  Spectral  interference  
 
•  Chemical  interference  

•  Ioniza6on  interference  
–  Ioniza6on  of  analyte  reduces  the  number  of  
neutral  analyte  

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X-­‐ray  Fluorescence  
•  An  elemental  analysis  method  for  solid  samples

Uo  et  al.,  Jpn.  Dent.  Sci.  Rev.,  2015   Photo  provided  by  the  U.S.  Army  

Take-­‐home  Message  

Atomic  spectroscopy  are  elemental  

analysis  methods  that  exploits  the  
electromagne6c  interac6on  with  atoms!