CHEM 2404 Forensic and Environmental Chemistry

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In the following choose the one option which best answers the question.
1. The operation of an ionization detector can best be described as:
A. The measurement of the light emitted when ions or excited atoms or
molecules return to their ground state after excitation by incident
radiation in a crystal.
An ionization detector measures current, not light.
B. Incident radiation causes gas molecules at low pressure to migrate
under the influence of an electric field.
The molecules must be ionised to migrate under the influence of an
electric field in an ionization detector (migration of dipolar molecules
under the influence of an electric field is something completely unrelated
to ionization detectors can be important in electrophoresis).
C. Measurement of the current which results when ion pairs, generated in
a gas by incident radiation, migrate to charged electrodes.
Correct
D. A current is generated when Li+ ions and electrons doped in an
ultrapure silicon or germanium crystal, are separated by the interaction
with a -ray and move through the donor and acceptor levels of the
crystal.
Neither lithium nor lithium ions are involved in an ionization detector
they are found in lithium-drifted detectors (in which they are in silicon- or
germanium- semiconductors)
2.

Which application of Neutron Activation Analysis would be most likely to

enable an analyst to determine the relative amounts of As2O3 and As2O5 in a
sample?

A. Instrumental Neutron Activation Analysis.

B. Chemical Neutron Activation Analysis.
C. Radiochemical Neutron Activation Analysis.
Instrumental neutron activation analysis provides no speciation
information, so is inappropriate. Since the question doesnt state the
nucleide to which As is converted, it is not possible to decide whether that
nucleide has more than one oxidation state, nor, if it does, how those
oxidation states are to be separated, so theres insufficient information to
choose Radiochemical Neutron Activation Analysis. However, separation
processes for arsenic oxidation states are well known (or the existence of
two oxidation states would not have been established), so, on the
information given, Chemical Neutron Activation Analysis is the only
suitable answer.
3. Which statement best describes Neutron Activation Analysis?
A. A neutron collides with an atom producing a -ray and the change in
neutron flux before and after the collision is measured.
Incorrect the energy of the delayed -ray is measured.
B. A neutron collides with an atom producing a -ray which is measured.
Incorrect this would describe Prompt -ray Neutron Activation Analysis.
Neutron Activation Analysis normally measures the delayed -ray from the
daughter nucleus, formed by decay of the compound nucleus, itself formed
by the interaction of the neutrons with the target nucleus.
C. A neutron collides with an atom producing an excited nucleus which
decays to a daughter nucleus, which, in turn, decays emitting a -ray,
the energy of which is measured.
Correct.
D. A neutron collides with an atom producing an electron which is
measured.
-rays, not electrons, are measured (electrons are measured in Auger
spectroscopy, but this is an entirely different technique).
4. The Lithium-drifted Germanium {Ge(Li)} detector is maintained at low
temperature because:
A. Better resolution is obtained at low temperature.

Possibly true, but not the reason, since theres no suggestion it couldnt be
used at, e.g., room temperature)
.
B. Higher sensitivity is obtained at lower temperature.
Also possibly true, but, similarly not the reason.
C. Photons pass further through a crystal if the atoms of the crystal are
moving slowly.
Not true and in any case, depends on the energy of the photons,
unspecified in this answer. These devices measure specific photons.
D. So as to stop recombination of Li+ ions and electrons and loss of
lithium.
Correct.
E. Photogenerated Li+ ions will move faster to an electrode if the motions
of the atoms of the crystal host are slowed.
Again, even if true, there is nothing to suggest here that the measurement
couldnt be made at, e.g., room temperature.

5. A standard containing 15.9 g of antimony (Sb) and a bullet sample weighing

325 mg were irradiated simultaneously in a nuclear reactor. The standard and
sample were removed from the irradiation source. The standard was counted
4.30 minutes after the end of the irradiation and the 124Sb counting rate was
determined to be 7.31 x 103 cpm. Then the sample was counted 5.15 minutes
after the end of the irradiation and had a 124Sb counting rate of 2.13 x 103
cpm. What is the concentration (in parts per million) of Sb in the sample? For
124Sb, the half life is 1.54 minutes.
Rstd
Wstd (e - T )std
=
Rsam
Wsam (e - T )sam
where:
R = counting rates of standard (Rstd) and sample (Rsam)
W = mass of the element in the standard(Wstd) and in the sample(Wstd)
T = elapsed time since irradiation
= 0.693/1/2

here:

= 0.693/1/2 = 0.693/1.54 = 0.45

Rstd
Wstd (e - T )std
=
Rsam Wsam ( e - T )sam
7.31x 10 3 15.9 x 10-6 ( e -0.45x 4.30 )std
=
2.13 x 10 3
x ( e -0.45x5.15 )sam
3.4319
x

15.9 x 10-6 (0.1444) 2.3309 x 10-5

x (0.0985)
x

2.3309 x 10-5
6.7919 x 10 -6
3.4319

i.e., in the 333 x 10-3 g bullet sample, there were 6.7919 x 10-6 g Sb,
i.e., [Sb] = 2.0396 x 10-5 g/g = 20.396 = 20.4ppm
6.

Fluorescence techniques are of value in forensic chemistry primarily

because:
A. There are no interferences from other molecules.
There is nothing in the theory of fluorescence to suggest other molecules
will nor fluoresce in the presence of a target molecule, so this (desirable as
it may be) is incorrect.
B. The wavelengths of the incident and observed radiation are different.
Correct a characteristic of fluorescence techniques is that the energies of
the incident and exiting photons are different.
C. Beers Law is obeyed under all circumstances.
Incorrect. Nothing in the derivation of Beers Law makes this exception for
fluorescence techniques.
D. The fluorescence of rhodamine 6G is solvent dependent.
Although this is true, it is a specific example, not necessarily of relevance
to forensic chemistry in general, and so, not an advantage specific to
fluorescence techniques.

7.

It is suspected that a person has been poisoned by thallium acetate. Thallium

in the blood serum was determined by atomic absorption spectroscopy, as
follows:

Two separate two hundred microlitre (200 L) aliquots of serum (1 L = 10-6

L) were prepared. To only ONE of them was added ten microlitres (10 L) of
a 0.020 M solution of TlNO3. Each of the two solutions was then diluted to
1.00 mL and assayed by AAS. The two solutions gave signals of 41.8 and
55.9 arbitrary units.
Which of the following best corresponds to the concentration of thallium (as
M) in the serum.
A flow diagram for the analysis is reproduced below:

y mole Tl in
200 L

y mole Tl in
200 L

10 L
spike

210 L of sample
with
+

x + y mole of Tl

200 L of sample
with
+

y mole Tl

dilute to 1 ml
which then
contains
+

x + y mole Tl

Gives a reading of
55.9 units

dilute to 1mL
which then
contains
y mole Tl+

Gives a reading of
41.8 units

FIRST: calculate the number of moles of Tl+ in the spike

The spike is 10 L of a 0.020 M solution of TlNO3.
Since 1 L = 106 L, the spike is 10 x 106 L of a 0.02 M solution of TlNO3.
If there are 0.020 mole of Tl+ in 1L
There will be x mole of Tl+ in 10 x 106 L
And so
x = (10 x 106/1)(0.020) = 2 x 107 mole of Tl+.
This 2 x 10 mole of Tl+ is responsible for the increase in the signal of the
spiked sample.
The increase in the signal is 55.9 41.8 = 14.1 units
So
2 x 107 mole of Tl+ gives 14.1 units
7

SECOND: use this value to calculate the number of moles of Tl+ in the sample
y mole of Tl+ in the sample gave a response of 41.8 units
2 x 107 mole of Tl+ gives 14.1 units
So,
y = (41.8/14.1)( 2 x 107) = 5.929 x 107 mole Tl+.
This is the number of mole of Tl+ in 1 mL
The 1 mL was a dilution of 200 L, i.e., of 200 x 107 L
So the 5.929 x 107 mole Tl+ came from the 200 x 107 L
THIRD: calculate the [Tl+] in M
If there are 5.929 x 107 mole Tl+ in 200 x 107 L
There will be z mole Tl+ in 1 L
So,
Z = (1/200 x 107)(5.929 x 107) = 2.9645 x 103 mole Tl+ per L
And,
[Tl+] = 2.9645 x 103 M = 2964.5 M.
8.

The principle behind Marshs test for arsenic is:

A. Volatile AsH3 is formed and can be precipitated in the presence of
copper.
Recall that Marshs test involves the conversion of the arsenic
compound to As2O5, and addition of the As2O5 to a suspension of zinc.
Acid is added to this suspension, generating hydrogen. The hydrogen
reduces the As2O5 to AsH3. The AsH3 is volatile and is allowed to
escape along a glass tube. The glass tube is passed through a (e.g.,)
Bunsen flame and the heat of the flame reduced the AsH3 to elemental
As(s), which is deposited as a shiny mirror on the walls of the tube.

Zn(s) Zn2+(aq) + 2e
2H+(aq) + 2e H2(g)
Zn(s) + 2H+(aq) Zn2+(aq) + H2(g)
As2O5(s) + 8H2(g) 2AsH3(g) + 5H2O
AsH3(g) + heat As(s) + 3/2H2(g)
There is no mention of copper in this sequence of reactions. So this
answer is incorrect (however, copper will interfere with the Marsh
test).
B. Arsenic compounds are precipitated by H2S as yellow orpiment, which
can be easily detected.
This describes the test that Marsh performed at the trial of John Bogle.
It was the failure of the test, the acquittal of Bogle, and his subsequent
confession, which inspired Marsh to develop a more reliable test for
arsenic.
C. Zinc reduces arsenic compounds to AsH3.
As outlined in the chemistry above, zinc is present as a reducing agent,
and AsH3 is generated, but zinc does not directly reduce the arsenic
compounds. Rather, zinc reduces the acid to H2, which reduces the
arsenic compounds.
D. Volatile AsH3, produced from arsenic oxides, can be thermally
degraded to elemental arsenic.
Correct.
9. The amount of an element in a sample subjected to Neutron Activation
Analysis can be calculated from the expression for first order radioactive
decay, assuming:
A. nothing else
This is correct try it if youre of mathematical bent. If you dont like
maths, this answer can be determined by eliminating the others.
The mathematical solution is:
For a sample of concentration (in this case, mass, since its a solid), a,
decaying by a first-order process, with a rate constant, k,

So,
Assume the number of counts from an analyte (R) is proportional to the
mass of the analyte, i.e.,
R a,
If the proportionality constant for that element is, say, , then,
R = a
Thus, after time T,
R = a0e-kT
So, if the initial mass of standard is Wstd, and the standard has a
counting rate, Rstd, after a time, T,
Then,
Rstd = (Wstd)initial e-kT
If the initial mass of the sample is Wsample, and the standard has a
counting rate, Rsample, after a time, T,
Then
Rsample = (Wsample)initial e-kT
So,

This is the same as the equation in the notes, with k = (when

evaluated at when a = a0/2, i.e., when t = t = , k = 0.693/).
B. That the measurement is made within three half-lives of irradiating the
sample.
There is nothing in the formula for determining the amount of the
analyte element that imposes this requirement. It is perhaps a practical
point, because if too many half-lives have passed, there wont be much
radiation to measure, but its not required in the derivation.
D. That the mass of the analyte element in the standard is less than that in
the unknown sample.
There is nothing in the formula for determining the amount of the
analyte element that imposes this requirement. The formula has only
the ratio of the masses, which, unless one is zero (which would violate
a boundary condition and so cant apply), must always be finite.
E. That the mass of the analyte element in the standard is more than that
in the unknown sample.
There is nothing in the formula for determining the amount of the
analyte element that imposes this requirement. The formula has only

the ratio of the masses, which, unless one is zero (which would violate
a boundary condition and so cant apply), must always be finite.

A. nothing else
10. Neutron Activation Analysis relies on the detection of -rays rather than a
particles or electrons because:
A. -rays carry no charge, whereas -particles and electrons are charged.
True, but not the essential reason -rays are used.
B. The probability of absorption of a photon by a matrix decreases with
increasing energy of the photon.
Correct. This is a rather technical way of saying that -rays have more
penetrating power than do -particles or electrons.
C. -particles and electrons move too slowly for enough to be counted in
a reasonable time.
If the -particles and electrons cant escape from the sample, because
their penetrating powers are insufficient, then they wont be counted,
irrespective of how fast they move. -rays are energetic enough to
escape the matrix of the sample and so are the radiation of choice.
D. If -particles and electrons collide they can form He atoms, which
wont be detected by an ionization chamber.
True, but the technique would use one or the other, not both together.
11.

The technique of X-ray Fluorescence is best described as:

A. An incident X-ray ejects an electron from an atom and the energy of
the electron is measured.
The incident X-ray does eject an electron (from the core shell) but
what is measured is the energy of the X-ray emitted as a consequence
of an outer shell electron moving to the core.
B. An incident X-ray ejects an electron from an atom and the X-ray
produced when an outer-shell electron fills the electron hole is
measured.
Correct.

F. An incident X-ray ejects an electron from an atom and the X-ray

produced when an outer-shell electron fills the electron hole ejects
an electron, which is measured.
This is a description of Auger spectroscopy, not X-ray Fluorescence.
D. An incident X-ray ejects an electron from an atom and measurement of
the intensities of the incident and transmitted X-rays allows the
characteristic absorption co-efficient of the analyte to be determined.
This is a combination of the action of the incident X-ray in X-ray
Fluorescence and the unrelated determination of the absorption coefficient of the analyte. Moreover, the description is one of comparing
intensities of X-rays, not energies, as in X-ray Fluorescence.
12.

Atomic absorption spectroscopy relies on:

A. A molecule aspirated into a flame absorbing light at energies
characteristic of its constituent atoms.
Atomic absorption spectroscopy is, as the name suggests, the
spectroscopy of atoms, not molecules.
B. Measuring the emission of radiation as a sample, atomised in a flame
relaxes to the ground state from a thermally promoted excited state.
This is a better description of flame photometry (or flame emission
spectroscopy) than of atomic absorption spectroscopy.
C. The absorption of light by a sample atomised in a flame and in its
thermally promoted excited state.
Atomic absorption spectroscopy involves absorption of light from the
atom in its ground state, not in its excited state.
D. Detecting the absorption of energy by gas phase atoms in their ground
states.
Correct.

13.

The hollow cathode lamp widely used in atomic absorption spectrometry

operates by:
A. A pure metal cathode is heated to vaporise metal atoms in an excited
electronic state, and the atoms collide with gas in the lamp emitting
radiation characteristic of that metal.

The atoms are not vaporised from the cathode, but are sputtered off by
collisions of exited gas ions with the cathode.
B. Inert gas ions, produced by collisions with high energy electrons
emitted by a metal cathode, are accelerated to the cathode, sputtering
from its surface metal atoms which, following gas phase collisions
with electrons or ions, relax to their ground state, emitting radiation
characteristic of that metal.
Correct.
C. High energy electrons are accelerated by a high voltage between an
anode and a metal cathode, sputtering from the cathode surface metal
atoms, which, following promotion to an excited electronic state by
collisions with gas phase atoms or ions, relax to their ground state,
emitting radiation characteristic of that metal.
The atoms do not leave the cathode as a result of the impact of
electrons, but are sputtered off as a result of collisions of gas ions
accelerated towards the cathode. This is closer to a description of the
Coolidge hot cathode tube, except that electrons are generated by
heating a tungsten cathode and travel to the anode (at which X-rays are
produced), and the tube is at a reasonably high vacuum (so there arent
gas phase atoms nor ions).
D. Passing light through the flame and analyte, with a chopper
periodically blocking and unblocking the light, such that subtraction of
the signal from the flame from that of the flame and analyte allows the
concentration of the analyte to be determined.
This is a description of the means by which the radiation emitted by the
lamp can be detected in the presence of the signal from the flame,
rather than a description of the generation of radiation by the lamp.