School of Chemistry and Biochemistry, Thapar University, Patiala

UCB008Applied Chemistry
Tutorial Sheet (Atomic Spectroscopy I)

1. What is atomic spectroscopy?

Answer: Atomic absorption is the process that occurs when a ground state atom absorbs energy in the
form of light of a specific wavelength and is elevated to an excited state. The amount of light energy
absorbed at this wavelength will increase as the number of atoms of the selected element in the light
path increases. The relationship between the amount of light absorbed and the concentration of analyte
present in known standards can be used to determine unknown concentrations by measuring the amount
of light they absorb. Instrument readouts can be calibrated to display concentrations directly.

2. What is an "atomizer"?
Answer:
- It is the conversion of molecules to their component atoms in gaseous state; and it is carried out
by introduction of the molecules solution in the flame in very fine droplet.

AA spectroscopy requires that the analyte atoms be in the gas phase. Ions or atoms in a sample must
undergo desolvation and vaporization in a high temperature source such as a flame or graphite furnace.
Flame AA can only analyze solutions, while graphite furnace AA can accept solutions, slurries, or solid
samples.
Flame AA uses a slot type burner to increase the path length, and therefore to increase the total
absorbance (see Beer Lambert law). Sample solutions are usually aspirated with the gas flow into a
nebulizing/mixing chamber to form small droplets before entering the flame.
The graphite furnace has several advantages over a flame. It is a much more efficient atomizer
than a flame and it can directly accept very small absolute quantities of sample. It also provides a
reducing environment for easily oxidized elements. Samples are placed directly in the graphite furnace
and the furnace is electrically heated in several steps to dry the sample, ash organic matter, and vaporize
the analyte atoms.

3. What kind of light is detected in atomic absorption spectroscopy (AAS) and atomic emission
spectroscopy (AES)?
Answer: In case of AAS it is transmitted light whereas in AES the emitted light is detected.

4. Why is the color of a flame containing sodium atoms different from that of a flame containing potassium
atoms?

5. What is the difference between a total consumption burner and a premix burner? Which is used for
which technique?

6. List various steps involved until the detection of analyte using AES.
Answer
(i) Liquid sample containing analyte is aspirated into the flame
(ii) Formation of liquid droplets
(iii) Evaporation of solvent affording residue
(iv) Decomposition of residue into neutral atoms
(v) Excitation of atoms and emission of radiation
(vi) Wavelength and intensity of emitted radiation measure by AES

7. Name the factors that affect the intensity of emitted radiation in AES?
Answer
(i) Viscosity of solution: Increase in viscosity, decreases the intensity due to decrease in
efficiency of atomization process.
 (ii) Presence of acids: Acid usually decreases the intensity of emitted light as they can disturb
the initial dissociation equilibrium.
(iii) Presence of other metals can also affect the emitted lights intensity.

8. What are the main limitations of flame photometry (AES)?

Answer
(i) It does not provide information about the molecular form of metal present in the original
sample.
(ii) Only liquid samples may be tested.
(iii) It cant be used for the detection of all the metal atoms.

9. If E1 and E2 are the energies of ground state and excited state for a metal M, then what is the wavelength
of emitted radiation?
Answer: The wavelength of the emitted light is given by:
E2-E1=h = hc/ Or = hc/ E2-E1
Where h is Planks constant, c is the velocity of light and is the wavelength of emitted radiation.

10. What temperature can be achieved by each of the following flames?

(a) air/natural gas
(b) air/acetylene
(c) N2O/acetylene
(d) oxygen/acetylene

11. What is the purpose of the high-energy flame, discharge, or plasma source in atomic spectroscopy?

School of Chemistry and Biochemistry, Thapar University, Patiala

UCB008Applied Chemistry
Tutorial Sheet (Atomic Spectroscopy II)

1. Which analytical technique AAS or AES is more sensitive to change in temperature and Why?
Answer: The AES technique is more sensitive to change in temperature as the fraction of atoms in the
excited state predominantly depend upon the temperature employed. Higher the temperature, more
number of atoms could be excited.

2. In AAS, sometime it is imperative to use O2 or N2O oxidant for the fuel-oxidant mixture. What is that
condition when we need to use such strong oxidants?
Answer: When the analyte requires more energy for atomization, strong oxidants like O2 or N2O are
used.

3. What is the principle of atomic absorption spectrometer?

Answer: Atomic absorption (AA) spectroscopy uses the absorption of light to measure the concentration
of gas phase atoms. Since samples are usually liquids or solids, the analyte atoms or ions must be
vaporized in a flame or graphite furnace. The atoms absorb ultraviolet or visible light and make
transitions to higher electronic energy levels. The analyte concentration is determined from the amount
of absorption. Applying the Beer Lambert law directly in AA spectroscopy is difficult due to variations
in the atomization efficiency from the sample matrix, and non-uniformity of concentration and path
length of analyte atoms (in graphite furnace AA). Concentration measurements are usually determined
from a working curve after calibrating the instrument with standards of known concentration.
4. What is the role of a monochromator in the atomic absorption spectrometer?

5. Describe the process sputtering.

Answer: When the potential difference across the electrodes in hollow cathode is sufficiently large that
the gaseous cations formed acquire enough kinetic energy to dislodge metal atoms from the cathode
surface and produce an atomic cloud in a process called sputtering.

6. What is the role of inert gas (He or Ne) in the Hollow Cathode?
Answer:
(i) It is the main source of current-carrying capacity in hollow cathode.
(ii) It dislodges atoms from the surface of the cathode.
(iii) It is primarily responsible for the excitation of the ground state metal atoms.

7. For the same concentration of Nickel, the absorbance at 352.4 nm was found to be about 30% greater for
a solution that contained 50% ethanol than for an aqueous solution in AA. Explain?
Answer: Generally, organic solvents have lower surface tension than the water. Hence, such organic
solutions result in formation of small drop sizes and that in turn increases the amount of the sample that
reaches the flame. Consequently, an increase in absorbance is observed for the ethanol solution of
Nickel than the aqueous one.

8. What type of metals cant be easily detected by AAS? Give two examples.
Answer: The metals that can undergo oxidation in the flame forming corresponding oxides, are difficult
to analyze using AAS. For example: Al, W, Ti, Mo.

9. Why does Beer's law apply in the case of AA, but not in the case of flame photometry?

10. What are the essential differences between atomic absorption and flame photometry?