Lecture 4

CHEM F313

Flame emission, Atomic absorption spectrometry

And UV-Vis Spectroscopy
28-10-21
 RECAP
Atomic Absorption Transitions
Measuring Atomic Absorption
Sources
Hollow Cathode Lamp

Types of Burners
➢ Premix chamber or laminar flow burner
➢ Total consumption burner

Flames
Electrothermal Atomization
 Interferences –Spectral and Non Spectral
Interference is a phenomena that leads to changes in intensity of the analyte’s signal in spectroscopy

In the case of atomic emission analyses, it

occurs when an additional emission line/band
is close to the emission line of the test
element and is not resolved from it by the
monochromator.

Similar interference can occur in atomic

Types of Interferences: absorption if a DC instrument is used. This
• Spectral can be eliminated by using an AC instrument.
• Non-Spectral/Ionization
• Chemical The probable danger is from molecular
• Physical emission, such as from oxides of other
elements in the sample.
 Interferences - Spectral

➢ Light scatter or absorption by solid particles, unvaporized solvent droplets or molecular

species in the flame will cause a positive interference in atomic absorption spectrophotometry.
A problem for wavelengths less than 300 nm. Also known as background absorption.
➢ This can happen when solutions of high concentration are aspirated as the salts may not be
completely desolvated or dissociated into its atoms.

➢ Can be minimized by using a line source (HCT), but not eliminated completely.

➢ This issue is minimized by measuring absorbance of a line that is close to the absorption line of
the test element and not absorbed by the elements itself or by background correction.
➢ In background correction, a mirror alternately passes through the hollow cathode lamp’s
radiation (resonance line) and the continuum radiation. The absorption of each is measured
and the continuum source absorption is automatically subtracted from the hollow-cathode
absorbance. Since finally its the difference in absorbance, so only one measurement is required.
 Interferences – Non spectral

➢ Ionization: Most common in hot flames. Caused by the presence of other easily ionized elements
(alkali and alkaline earth elements) in the sample. This results in decrease of signal. (Not that serious,
however effects the sensitivity and linearity)
➢ This can be overcome by adding large amounts of element that is easily oxidized, to the sample and
add to more free electrons to the flame to suppress ionization of the test element.
K, Rb and Cs are commonly used as ionization suppressants.

Chemical Interferences: Refractory element Formation

➢ Caused by refractory ( Refractory metals are a class of metals that are extraordinarily resistant
to heat and wear) elements such as Al, Ti, Mo and V due to their reaction with O and OH species
in the flame to produce thermally stable metal oxides and hydroxides

❖ This can be minimized using a releasing agent or complexation agent. Usage of high temperature
and/or reducing flames is another option.
SrCl2 Lanthanum (III) nitrate
La(NO3)3. 6 H2O
 Interferences - Physical

➢ The rate of sample uptake in the burner and the atomization efficiency
(includes gas flow rates, sample viscosity due to temperature or solvent
variation etc.), high solids content and variation in the flame temperature.
➢ This can be overcome by frequent calibration and use of internal standards.

➢ Internal standard addition: e.g. Li for K and Na. Usually used for fluctuations
in gas flow and aspiration rates.

➢ Standard addition calibration: Signal suppression (or enhancement) caused by

the sample matrix; e.g. due to high viscosity or chemical reaction with the
analyte. A varying known amount of the sample is sequentially increased and the
corresponding increase in peak area is measured.
Example: A serum sample is analyzed for K by FES using the method of std additions. Two 0.5 mL aliquots are
added to 5 mL portions of water. To one portion is added 10 μL of 0.05 M KCl solution. The net emission signals
in arbitrary units are 32.1 and 58.6. What is the concentration of K in the serum?

The amount of standard added = 0.01 mL x 0.05 M = 5 x10-4 mmol

Produced signal = 58.6-32.1 = 26.5 au

The millimoles of K in the sample = 5 x10-4 mmol x (32.1/26.5) = 6.06 x10-4 mmol

This is in 0.5 mL serum, so the concentration is

(6.06 x10-4 mmol)/0.5 mL serum = 1.21 x10-3 mmol/mL serum

 Measurement of AA
• Ideally, the amount of light reaching the detector is given by Beers Law:
I = Io×10−εcl
• Several interferences can change this to:
I = Io×10−εcl + Iemission − Ibackground − Iscattering
• Iemission is due to analyte emission in the flame
• Eliminated from the absorbance by modulation of the light source: measures only AC levels;
emission DC level.
• Ibackground, Iscattering: due to absorption by the flame or are induced by sample matrix and are
independent of the analyte.
• Broad band in nature.
• Flame interferences nulled by comparing a blank with sample
– Sample matrix is a troublesome problem. Caused by, for example, high salt content (e.g.
NaCl or KI). These have broad band absorption spectrum in flame since they are not
reduced by it. Most common approach uses secondary continuum source (e.g. D2 lamp):
– Each lamp (D2 and HCT) modulated but are 180° out of phase with each other.
– Detection system measures difference between two absorbance signals.
Advantages of emission Spectrometer over absorption
methods:
1. Lower inter element interference because of higher temperature.
2. Emission spectra are obtained under a single set of excitation conditions and several
elements can be recorded simultaneously.
3. Multi element can be analyzed from very small sample.
4. Low concentration refractory compounds can be determined
5. Nonmetals can also be determined by plasma sources.
6. Very high concentration range (linear range) for plasma sources.

•The type of power

source used to generate
the plasma—DC, AC
(typically with radio
frequency ( RF )) and
microwave
UV-Vis Spectroscopy
 Electronic Excitation by UV/Vis Spectroscopy
X-ray: core electron IR: molecular Radio waves:
excitation vibrations Nuclear spin states
(in a magnetic field)

UV-vis valence electron excitation

Absorption of UV or Visible radiations by the molecule leads to the
transitions among the electronic energy levels of the molecule hence also
well known as electronic spectroscopy

Strength: Ability to measure the extent of multiple bond or aromatic

conjugation within molecule

Mostly aromatic and hetero aromatic systems

Conjugated and non conjugated diene
Conjugated diene and conjugated triene
CHROMOPHORE:
• Originally, term chromophore was applied to the system responsible for imparting color to
a compound.
• However, many groups absorb light but do not impart color
• Chromophore, is thus defined as any functional group that absorbs electromagnetic
radiation.

Chromophore Example Excitation λmax, nm ε Solvent

C=C Ethene π __> π* 171 15,000 hexane

C≡C 1-Hexyne π __> π* 180 10,000 hexane
n __> π* 290 15 hexane
C=O Acetone
π __> π* 180 10,000
n __> π* 275 17 ethanol
N=O Nitromethane
π __> π* 200 5,000

C-X, X=Br Methyl bromide; n __> σ* 205 200 hexane

X=I Methyl Iodide n __> σ* 255 360