CHEM 2052 INSTRUMENTAL ANALYSIS II–MIDTERM EXAM (30%)

(TIME ALLOWED 30:00 MINUTE)

Name:............................................................ ID. No....................................................

PART 1: CHOOSE THE BEST ANSWER FROM THE OPTIONS UNDERNEATH EACH
QUESTION BELOW AND CIRCLE YOUR BEST ANSWER: (1 point each)

1. Which of the following shows the correct order of various electromagnetic waves if
arranged in increasing order of their frequencies?

A- Gamma rays, infrared waves, visible light, ultraviolet rays, x-rays and radio waves .

B- Radio waves, infrared waves, visible light, ultraviolet rays, x-rays and gamma rays .

C- Radio waves, visible light, infrared waves, x-rays, ultraviolet rays and gamma rays .

D- Gamma rays, visible light, infrared waves, x-rays, ultraviolet rays and radio waves

2. The human eye is most sensitive to light with a wavelength near 550 nm. To what photon
energy is the human eye most sensitive? E(J) = E(eV) × 1.60*10 -19 , h = 6.63 * 10-34 Js , c
= 3 * 1010 cm/s

A) 2.49 eV B) 3.61 X10 –19 eV C) 2.25 eV D) 1.83 eV

3. What is the main difference between molecular spectrum (ms) and atomic spectrum (as) ?
select the correct answer :

A- (ms) involves electronic , vibrational and rotational transitions and consists of bands
while( as) involves only electronic transitions and consists of lines .

B- (as) involves electronic , vibrational and rotational transitions and consists of bands while
(ms) involves only electronic transitions and consists of lines .
C- (as) involves electronic , vibrational and rotational transitions and consists of lines while
(ms) involves only electronic transitions and consists of bands

3. Which is the correct order of events in the process of atomization?

A. nebulization - desolvation – volatilization

B. volatilization - desolvation - nebulization

C. desolvation - volatilization - nebulization

D. nebulization - volatilization - desolvation

4. A 2.50-mL aliquot of a solution that contains 3.8 ppm iron(III) is treated with an
appropriate excess of KSCN to form the Fe(SCN) 2+ complex (molar absorptivity of
7.00x103 L cm-1 mol-1) and diluted to 50.0 mL. What is the absorbance of the resulting
solution at 580 nm in a 2.50cm cell. (Given: mmol Fe/mL =(3.8 mg Fe/1000
mL)*(mmol Fe/55.8mg Fe) = 6.81x10 -5 M)

A. 66500 B. 1.192 C. 0.06 D. None of the above

B. What are the following Abbreviations stand for : AAS , AES and ICP-AES

C. What is the difference between absorption and emission?

D. Define each of the following terms : ( a) A releasing agent ( b) A protective agent

(c) An ionization suppressor (d) Atomization (e) A hollow cathode lamp (f)
Sputtering , (g) Self-absorption ?

E. What is the main interference in arc spark emission spectrometry?

F.
G.
H.
I.
J.
K. Discuss all types of interferences that can occur in atomic spectrometry.

L. Why are atomic emission methods with an ICP source better suited for multi-element analysis
than flame absorption methods?

In AAS, an external light source, such as a hollow cathode lamp, must be used to excite the atom
of interest. Given that HC lamps provide narrow bandwidth excitation, and given that the
absorption spectra for elements vary, multielement analysis by AA requires multiple excitation
sources. In Plasma AES, the energy of the plasma is sufficient to excite the atoms in the sample,
so the requirement for a separate excitation source is removed.

M. Describe how continuum-source background correction works in atomic absorption

spectrometry.
In this method the sample is alternately excited by a narrow band hollow cathode lamp and a
continuum deuterium lamp. When the HC lamp is "on", the response at the detector is a
combination of absorbance and background effects. Since the D2 continuum is so much broader
than the absorbance band, the contribution of sample absorbance to the signal when the D2 lamp
is "on" is minimal. The majority of the response is due to background. Thus comparing the two
signals allows for compensation of background effects.

N. Why do absorbance spectra from atomic species tend to exhibit narrower bands than for
molecular species?
Molecular bands are complicated by the addition of rotational and vibrational transitions on top
of electronic energy levels. This increases the number and range of energy of the molecular
transition in comparison to atomic spectra, which are not complicated by rotations and vibrations
O. Why are detection limits for most elements lowest for electrothermal AAS and highest for flame
AES, with ICPAES in the middle?
Electrothermal methods, like GFAAS, lead to lower detection limits primarily because of the
efficiency with which the sample is used. In GFAAS, the entire sample is atomized and exposed
to the measurement stage. In flame and plasma methods, the bulk of the sample is directed to
waste and only a small fraction is actually exposed to the measurement stage.

Plasma emission methods tend to produce lower detection limits than flame methods because the
increased temperature of the plasma leads to more efficient atomization and an increased
population of the excited state. An increase number of excited state atoms leads to greater
emission signals and ultimately lower detection limits.

P. Briefly describe the process involved in flame atomization for atomic absorption spectroscopy
equipment
Q. Why is flame emission in a relatively cool flame actually preferred for the measurement of
sodium when compared to that of a hot flame or plasma, even though the hotter source will
give a higher excited state population?
In this case, the concern is with the ionization of Na to Na +. At higher temperature, the easily
ionized sodium atoms will be converted to ions, decreasing the number of sodium atoms in the
gas phase, therefore decreasing the number of excited state atoms and the atomic emission.
 https://www.chem.uci.edu/~jsnowick/organicspectroscopy/index.html

R. We discussed three general limitations to Beer’s law. Explain the source of each limitation and its effect
on a calibration curve using the instrument described and the information presented in the BKH paper
as an illustrative example. Answer. A strong answer to this question will discuss the following points: •
fundamental limitation: the requirement that the absorbing particles act independently of each other
and that the refractive index of the sample is independent of concentration; at high concentrations,
neither condition remains true and ¤ becomes concentration-dependent, giving positive or negative
deviations from Beer’s law • instrumental limitations, which takes two forms: – non-monochromatic
radiation: Beer’s law requires that ¤ is constant for all wavelengths of light that pass through the
sample; when this is not true, there is a negative deviation from Beer’s law – stray light: when light—
either from the instrument’s light source or from another source—reaches the detector without
passing through the sample, then it is not accounted for in either PT or P0, which means that the
transmittance becomes T = (PT + Pstray)/(P0 + Pstray); at high concentrations of the analyte, Pstray
becomes sufficiently large relative to PT, resulting in negative deviations from Beer’s law • chemical
limitations: if the analyte’s concentration depends on the position of an equilibrium, then changes in
the equilibrium’s position will result in a change in absorbance even though there is no change in the
analyte’s total analytical concentration; the result is a negative or a positive deviation from Beer’s law

Which of the following is the principle of Atomic Absorption Spectroscopy?

a) Radiation is absorbed by non-excited atoms in vapour state and are excited to higher states
b) Medium absorbs radiation and transmitted radiation is measured
c) Colour is measured
d) Colour is simply observed

Answer: a

Explanation: Atoms in gaseous state absorb the radiation and are excited to higher state. Since, the
higher state is unstable the atom returns the ground state with the emission of radiation which is
measured.

2. In Atomic Absorption Spectroscopy, which of the following is the generally used radiation
source?

a) Tungsten lamp
b) Xenon mercury arc lamp
c) Hydrogen or deuterium discharge lamp
d) Hollow cathode lamp

Answer: d

Explanation: Hollow cathode lamp is the source used in Atomic Absorption Spectroscopy. It emits stable
and intense radiation.

3. In Atomic Absorption Spectroscopy, with what material is the cathode in Hollow cathode lamp
constructed?

a) Tungsten
b) Quartz
c) Element to be investigated
d) Aluminium

Answer: c

Explanation: The cathode in Hollow cathode lamp is constructed of the element to be investigated. The
anode is made of tungsten.
4. How can the intensity of radiation be increased in Hollow cathode lamp?

a) Addition of non-conductive protective shield of mica

b) Addition of nitrogen to neon or argon in the lamp
c) Increasing the pressure of the filling gas
d) Changing the metal of the anode

Answer: a

Explanation: The intensity of radiation is increased in Hollow cathode lamp by the addition of non-
conductive protective shield of mica. The protective shield can be made of glass too.

5. Which of the following is the function of the chopper in Atomic Absorption Spectroscopy?

a) To split the beam into two

b) To break the steady light into pulsating light
c) To filter unwanted components
d) To reduce the sample into atomic state

Answer: b

Explanation: The function of the chopper in Atomic Absorption Spectroscopy is to break the steady light
into pulsating light. It is a rotating wheel placed between the flame and the source.

6. Which of the following is the function of Flame or Emission system in Atomic Absorption
Spectroscopy?

a) To split the beam into two

b) To break the steady light into pulsating light
c) To filter unwanted components
d) To reduce the sample into atomic state

Answer: d

Explanation: The function of Flame or Emission system in Atomic Absorption Spectroscopy is to reduce

the sample into atomic state. In Atomic Absorption Spectroscopy, the production of atomic vapour by
flame is the most important phase.

7. Atomic absorption spectroscopy is also called as Absorption Flame Photometry.

a) True
b) False
Answer: a

Explanation: In Atomic Absorption Spectroscopy, sample is sprayed into the flame. Hence, it is called
Absorption Flame Photometry.

8. Which of the following is not a component of emission system in Flame photometer?

a) Burner
b) Atomiser
c) Fuel gases and their regulation
d) Chopper

Answer: d

Explanation: Chopper is not a component of emission system in Flame photometer. The parts of flame
photometer are burner, atomiser, fuel gases and their regulation and flame.

9. Which of the following is the function of atomiser in the emission system of Atomic Absorption
Spectroscopy?

a) To split the beam into two

b) To break the steady light into pulsating light
c) To break large mass of liquid into small drops
d) To reduce the sample into atomic state

Answer: c

Explanation: The function of atomiser in the emission system of Atomic Absorption Spectroscopy is to

break large mass of liquid into small drops. It also introduces liquid sample into the flame at a stable rate.

10. Which of the following is not a fuel used in flame photometry?

a) Acetylene
b) Propane
c) Hydrogen
d) Camphor oil

Answer: d

Explanation: The commonly used fuel gases in flame photometry are acetylene, propane and hydrogen.
Oxygen supply is given to the fuel gases.

11. Which of the following is not the requirement of a good flame in flame photometer?
a) Liquid sample must be evaporated to form solid residue
b) Solid residue must decompose to form atoms
c) Atoms must be produced such that they have the ability to get excited to higher states
d) Atoms must be produced such that they are in stable state

Answer: d

Explanation: Atoms must be produced such that they have the ability to get excited to higher states.
These atoms in higher states return to ground state with the emission of photons.

12. Atomic Absorption Spectroscopy is used for the analysis of metals.

a) True
b) False

Answer: a

Explanation: Atomic Absorption Spectroscopy is used for the analysis of metals.

13. Which of the following options explains the process of ‘sputtering’ that occurs in Hollow
Cathode Lamp?

a) Positive ions collide with cathode surface and metal atoms from cathode are ejected
b) Negative ions collide with cathode surface and metal atoms from anode are ejected
c) Positive ions collide with negative ions and metal atoms from anode are ejected
d) Positive ions collide with negative ions and photons are ejected

Answer: a

Explanation: When potential is applied across the electrode, the gas filled in tube ionises and flow of
current occurs. Positive ions collide with negatively charged cathode surface and metal atoms from
cathode are ejected.

14. At what pressure should the gases in the sealed tube be maintained in the Hollow cathode
lamp?

a) 1 to 5 torr
b) 20 to 30 torr
c) 40 to 50 torr
d) 50 to 55 torr

Answer: a
Explanation: It consists of a cylindrical cathode and an anode made of tungsten. The tube is sealed and
neon and argon are filled at a pressure of 1 to 5 torr.

15. The diagram show below is the picture of Hollow cathode lamp. Identify the unmarked
component.

a) Glass tube
b) Quartz window
c) Non- conducting glass
d) Mica shield

Answer: b

Explanation: The unmarked portion is Quartz window. The window can be made of quartz or borosilicate
glass.

(30m)-Spectral interference:oAdsorption or
emission of an interfering species overlaps or lies
close to the analyteadsorption or emission. (Less
than about 0.1Å)oResults from the presence of
combustion products that exhibit broadband
absorptionoOr particulate products that scatter
radiationoThe effect from both is reducing the
power of the transmitted beam and lead to
positiveanalytical errors.oOvercome: if the source
is known, add excess of radiation buffer to
samples and standards.oThe interfering substance
has high concentration of radiation buffer
compared to samplematrix. It will cause
contribution from sample matrix will be
insignificant.-Chemical interference: (more
common than spectral interference)oConsist of (i)
formation of low volatility compounds, (ii)
Dissociation equlibria, (iii)
Ionizationequlibria.§(i) Formation of low
volatility compounds