TUTORIAL CHM261

CHAPTER 1

1. Arrange the regions in the spectrum of radiation below in the order of decreasing
energy:

Infrared, X-ray, Ultraviolet, Visible and Microwave

2. Magnetic resonance imaging (MRI) is a powerful diagnostic tool used in medicine. The
images used in hospitals operate at frequency of 4.00 x 102 MHz. Calculate:

a) the wavelength in nm
b) the energy in Joules per photon

3. Carbon dioxide absorbs energy at a wavelength of 1498 nm.

a) In what spectral range does the absorption occur?

b) Calculate the frequency of this absorption.

4. Calculate the frequency in Hz and the energy in joules of an X-ray photon with a
wavelength of 2.35 Å.

5. Determine the percent transmittance (%T), if A = 0.310.

6. If T = 0.567, what is the absorbance?

7. The molar absorptivity of MnO4- is 2.3 x 103 M-1cm-1. A spectroscopy experiment was
conducted using a 1.0-cm cuvette.

a) Calculate the concentration of permanganate solution which would give an

absorbance of 0.80.
b) Calculate the percent transmittance of solution (a).
c) Solution (a) is diluted to half its original concentration. Calculate the
transmittance of the diluted solution.

8. At 540 nm the red colored complex of iron (III) thiocyanate, FeSCN 2+ has a molar
absorptivity of 7.00 x 103 Lcm-1mol-1. A cuvette with a diameter of 1.00 cm was used in
the analysis.

a) Calculate the absorbance of a 3.75 x 10-5 M of the complex at 540 nm.

b) Calculate the absorbance of the complex solution if its concentration is twice that
in (a).
c) If a more concentrated solution is used, will the absorbance in (a) increase,
decrease or remain unchanged? Explain your answer.
d) Why is the experiment run at 540 nm?
e) Sketch and correctly label the ideal Beer's Law plot.

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 f) State one factor which causes the Beer's Law relationship to deviate from
linearity.
g) If this analysis was run using Spectronic 20, name two suitable cell materials that
can be used.

9. A 31.5 mg sample of compound Y (molecular weight = 317.17 g/mol) was dissolved

with solvent in a 250 mL volumetric flask. The absorbance of this solution at 238 nm
was 0.624 in a 1.00 cm cuvette. Calculate the molar absorptivity of compound Y
(using appropriate units).

10. Beryllium (II) forms a complex with acetylacetone (MW complex = 166.2 g/mole).
Calculate the molar absorptivity of the complex, given that a 1.34 ppm solution has a
transmittance of 55.7 % when measured in a 1.00 cm cell at 295 nm.

11. A 0.0045 M solution analyzed using the Spectronic 20 instrument has 37.0%
transmission at 470 nm in a 1.00cm cell. Using Beer's law, find the concentration of
the solution if it gives 85.2% transmission under the same conditions.

12. Calculate the missing quantities in the accompanying table. Where needed, use 200
g/mole for the molar mass of the analyte. Show all work for credit.

Parameter Values
A 0.179
%T
Є (Lmol-1cm-1)
a (cm-1ppm-1)
b 1.00 cm
Concentration 7.19 x 10-5 M
Concentration (ppm)

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 TUTORIAL CHM261

CHAPTER 2 (Part 1)

1. Name the suitable cell materials for use in the following electromagnetic region:
a) UV
b) Visible

2. Define the term 'continuum source' and give one (1) example of this source.

3. Name the type of detector commonly used in UV-Visible spectroscopy.

4. Define the term 'charge transfer complex.'

5. Draw the block diagram of a double-beam spectrophotometer and label each

component.

6. In spectroscopic analysis:
a) name one (1) suitable cell material for use in UV spectroscopy.
b) give an example of a continuum source for infrared (IR) spectroscopy.
c) state the principle of use for a quantum detector.
d) what is the function of a monochromator or a filter?

7. State one (1) advantage of a double-beam instrument compared to a single-beam

instrument.

8. Define the term 'chromophores'.

True / False

No Statement True/False
The n ----> pi* and pi ----> pi* transitions are the most observed and useful
1
transition in organic molecules.
The absorption of UV-Vis radiation corresponds to the excitation of outer electrons
2
of a molecule
Sigma ----> sigma* and n ----> sigma* transitions require low energy radiation for
3
the transition to occur.
Solvents such as ethanol can be used for UV analysis since it does not absorb in
4
the UV region.
Most organic compounds require chromophores to supply the pi* orbitals for
5
absorption in the UV region.
Conjugated compounds which contain alternating multiple bonds show absorption
6
peaks in the UV region.
The molar absorptivity of absorbing species in the UV region is usually lower than
7
10 L/[Link]

8 Two examples of chromophores are carbonyl and carboxyl functional groups

9 In the iron(III) thiocyanate complex , the metal ion is the electron acceptor

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 TUTORIAL CHM261

CHAPTER 2 (Part 2)

1. State the purpose of running samples using infrared spectroscopy.

2. Briefly describe a method of preparing pure liquid samples for infrared (IR)
spectroscopy.

3. State why an IR spectrometer is often purged with dry nitrogen.

4. Based on their IR spectrum, how can you differentiate between a ketone and an
aldehyde?

5. Propanone and 2-propen-1-ol are constitutional isomers. In order to distinguish

between them using IR spectroscopy, provide one (1) absorption peak for each
functional group and its corresponding wavenumber.

6. What are the strong absorptions from 3100-3000 cm-1 in the IR spectrum of toluene
due to?

7. The IR C=C stretching absorption in symmetrical alkenes are usually absent. Explain
why this is so.

8. Without doing any calculations, which member of each pair do you expect to occur at
the higher frequency?
a) C=C or C=O
b) C=O or C-O

9. Briefly describe one (1) method of preparing a solid sample for infrared (IR)
spectroscopy if the solid sample is insoluble in CCI4 or other common IR solvents.

10. In an experiment, a student obtained the IR spectrum of 1-hexanol using a 'neat' liquid.
Explain what a 'neat' liquid means.

11. Identify two peaks which can be found on the IR spectrum of toluene. Based on
Appendix 1, state the bonds and the approximate wavenumber associated with each
peak.

12. State the requirement for a molecule to be IR active.

13. Which of the following compounds would be expected to show peaks in the IR
region?

CO, CO2, HF, H2, KCI, N2

14. State the necessary criteria for absorption to occur in the IR region.

15. Name two (2) common solvents used in IR spectroscopy.

16. State three (3) advantages of using the FT-IR.

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17. Describe the sample preparation of a solid compound using the Mull method.

18. The following is an IR spectrum of (CH3)2CHCH2CH(OH)CH3. Select two absorption

bands on the spectrum and indicate the bond and wavenumber associated with each
peak.

19. At what approximate wavenumber might the following compounds show one (1) most
obvious IR absorption? Also state the type of bonds which correspond to the
wavenumber you give.

a) CH3COCH3
b) (CH3)2CHCH2CH=CH2

20. The following is the IR spectrum of alcohol, which has the molecular formula C2H6O.
Select three (3) significant peaks associated with alcohol from the given spectrum.
State the wavenumber and the bond associated with each peak you selected.

21. Assume that you have a compound with molecular formula C3H6O. If the compound has
an IR absorption at 1715 cm-1, what can you conclude?

22. Cyclohexene and 2-hexyn both have the molecular formula C6H10. By referring to
Appendix 1, how would you use IR spectroscopy to distinguish between these two
compounds?

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23. A compound shows strong, very broad IR absorption in the region 3300-3600 cm-1
and strong, sharp absorption at 1715 cm-1. Name one (1) functional group which
accounts for both of these absorptions.

24. What is the significance of the fingerprint region in the interpretation of an IR

spectrum?

25. Molecules such as O2 and N2 do not absorb infrared radiation. Explain why.

26. Briefly explain the purpose of running a ‘background’ spectrum at the beginning of an
IR analysis.

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 TUTORIAL CHM261

CHAPTER 3

1. Explain the following terms associated with atomic spectroscopy:

a) Atomization
b) Nebulization

2. Using a simple phrase, state the function of the following devices found in an atomic
absorption spectrophotometer (AAS).

a) Hollow Cathode Lamp

b) Chopper
c) Burner

3. List two (2) methods to overcome chemical interferences in atomic spectroscopy.

4. Ionization interference is one type of interference in AAS.

a) Explain what is meant by 'ionization interference'.

b) State one (1) method to cure this type of interference.

5. State the differences between flame atomic emission spectroscopy (FAES) and flame AAS
(FAAS), in terms of principle and instrumentation.

6. The determination of sodium and potassium in blood was done by flame emission
spectroscopy. The accuracy of this analysis depends on flame stability. Explain.

7. Explain why source modulation is employed in flame AAS.

8. What is the purpose of adding 1000 ppm of CsCI solution when conducting an atomic
spectroscopy experiment?

9. Why releasing agent such as La3+ is added during the analysis of calcium using flame
absorption or emission methods?

10. SO42- and PO43- hinder the atomization of Ca2+ by forming non volatile salts.

a) Name the type of interference described above.

b) State two methods which can be used to prevent this type of interference.

11. In flame atomic absorption spectroscopy, briefly describe the processes involved in
atomization of sample.

a) Volatilization
b) Aspiration

12. Explain the spectral interference that occurs in AAS. Suggest one (1) method to
overcome this problem.

13. State two disadvantages of AAS when used for elemental analysis.
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14. Explain why flame atomic emission analysis is sensitive to flame temperature.

15. A standard addition method was used in the determination of chromium in an aqueous
sample using atomic absorption spectroscopy. 10 mL of the unknown were pipette into
each of five 50.0-mL volumetric flasks. Various volumes of a standard containing 12.2 ppm
chromium were added to the flasks, following which the solutions were diluted to volume.

Plot the appropriate graph and determine the amount of chromium in an aqueous
sample. Clearly show all the calculation steps.
(Ans : 15.23 ppm)

16. A standard addition method was used in the determination of Cu(ll) in a wastewater
sample using atomic absorption spectroscopy. 5.00 mL aliquots of the wastewater sample
were pipetted into each of five 50.0-mL volumetric flasks. Different volumes of a 2.5 ppm
Cu(ll) standard solution were added into the volumetric flasks as shown below. All the
resultant solutions were diluted to the mark and absorbance measured at the maximum
wavelength gave the following readings.

Plot the appropriate graph and determine the amount of Cu(ll) in the wastewater sample.
Clearly show all the calculation steps.
(Ans : 1.55 ppm)

17. An analysis was done on an unknown sample to determine the metal ion concentration
using the standard addition method. 10 mL aliquots of the unknown metal solution were
each added into 50.0 mL volumetric flasks. The response of the instrument was measured
for each solution and the results of the experiment are summarized below. Determine the
concentration of the metal ion in the sample.

Conc of added standard (ppm) Response

0 3.06
15 4.56
30 6.06
45 7.56

(Ans : 150 ppm)

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18. A sample was analyzed for a metal ion by adding 10 mL aliquots of the unknown into
five 50.0 mL volumetric flasks. To each flask was added a various volume (0, 10, 20,30
and 40 mL) of 12.2 ppm standard solution of this metal ion. Each flask was then diluted
to 50.0 mL. AAS analysis was conducted. When a graph of Absorbance (y axis) was
plotted against volume of standard, a linear regression with y= 8.81 x 10-3 x + 0.202 is
obtained. Calculate the concentration of the metal ion in the sample.

(Ans: 28 ppm)

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 TUTORIAL CHM261

CHAPTER 4

1. The following data was obtained when a sample mixture was analyzed by GC on a
column 1.1 m long.

a) Calculate the retention factor, k', for hexanol. Ans: 25.67

b) Calculate the resolution, Rs, between propanol and butanol peaks. Are the peaks
completely resolved? Ans: 7.33
c) Calculate N and H using data from the propanol peak. Ans: N=1600, H=0.069 cm
d) State the probable reason why a fronting peak appears in a chromatogram.

2. State two (2) methods which can improve the efficiency of a chromatographic column.

3. Consider a chromatography experiment in which a mixture of two components, P (k' =

4.00) and Q (k' = 5.00) are injected into a column with N = 1.00 x 103 theoretical plates.
The retention time for the less retained component, P is 10.0 min. Calculate:

a) tM Ans: 2 min
b) retention time for component Q Ans: 12 min
c) peak width (at base), Wb for component P Ans: 1.26 min
d) selectivity factor, α of the column Ans: 1.25

4. Describe the following terms used in chromatography:

a) Mobile phase
b) Retention time
c) Stationary phase
d) Resolution

5. State whether plate height H, will increase or decrease and also whether the
chromatographic column will be more or less efficient if the following changes were
made during a chromatographic analysis.

a) Increasing the flow rate of the mobile phase,

b) Reducing the particle size of a packed column,
c) Increasing the diameter of a capillary column in GC.
d) Increasing the length of column L, in GC.

6. List two ways to increase the number of theoretical plates in a GC experiment.

7. Explain why a chromatogram shows unsymmetrical peak shapes such as 'fronting' or

'tailing.'

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8. The following data was obtained from the chromatogram of species A, B, C and D run
on a GC which used a 30 m column:

a) the number of plates for compounds B and C on this column Ans: B = 2473.98, C
= 2334.82
b) the retention factor, k' for peaks B and C. Ans: B = 3.206, C = 3.441
c) the resolution of peaks B and C. Ans: 0.667

9. A mixture of organic acids was separated by reversed-phase liquid chromatography.

The data obtained from the chart recorder were as follows:

For acid A, the retention time was 4.4 min with the width at baseline of 1.6 min. For
acid B, the retention time was 6.8 min with the width at baseline of 1.2 min. A non-
retained compound generated a peak that appeared 0.8 min after injection. The mobile
phase flow rate in the column was 20 mL/min. The column was 1.0 m in length.

Calculate:

a) The capacity factor (k') for acid A. Ans: 4.5

b) The resolution achieved of compounds A and B. Ans: 1.743
c) The average number of theoretical plates in the column. Ans: 317.39
d) The average plate height. Ans: 3.15 x 10-3 m

10. What observation on a chromatogram would lead you to conclude that sample injected
into a GC column are overloaded/too much.

11. Heptane and toluene were separated with retention times of 15.4 min and 16.5 min,
respectively on a 1.0-meter packed column. An unretained species passed through the
column in 1.8 min. The peak widths measured at the base were 1.15 min for heptane
and 1.20 min for toluene. Calculate:

a) The resolution achieved between the peaks Ans: 0.9362

b) The average number of plates for the column Ans: 2947.12
c) The average plate height Ans: 3.39 x 10-4 m
d) Capacity factor, k' for toluene Ans: 8.167

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12. The following data were obtained in a GC analysis of a sample mixture. The
chromatogram of 200 ppm butyl acetate showed a retention time of 4.4 min and
produced a peak area of 20360.

a) What is species A?
b) Calculate the concentration of A. Ans: 240.67 ppm, Response factor: 101.8 ppm-1
c) Determine the selectivity and resolution factors for peaks A and B. Ans: α = 1.67,
Rs = 1.60
d) Are peaks A and B well separated? Justify your answer. Ans: Yes. Rs = 1.6 > 1.5

13. Trace amounts of phenol can be detected by HPLC. A 20-uL of 25 mg/L of a phenol
standard gives a peak of 140 cm2 and a 20-uL water sample gives a peak of 26 cm2
due to phenol. Using the 'response factor' method, calculate the phenol content in
water, in units of parts per million (ppm). (Refer Laboratory Manual, pg 59)

14. Based on the following chromatogram, name the liquid chromatography technique
which was probably used to separate the mixture.

15. Chromatograms of compounds A and B were obtained at the same flow rate with two
columns at equal length.

a) Which column has more theoretical plates?

b) Which column has a higher plate height?
c) Which column gives higher resolution?

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16. Name the specific type of liquid chromatography in which:

a) Different sized solutes penetrate voids in the stationary phase to different extents
and largest solutes are eluted first
b) Ions in mobile phase are attracted to counterions covalently attached to the
stationary phase.

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 TUTORIAL CHM261

CHAPTER 5

1. In gas chromatography (GC), what is the recommended sample injection port

temperature?

2. Name the GC detector which is most suitable for analysis of environmental samples
such as pesticides and polychlorinated biphenyls.

3. In a GC analysis:

a) name two (2) common carrier gases.

b) state one (1) characteristic of a carrier gas.
c) state the effect of injecting too much sample into the column.
d) explain why it may be necessary to do temperature programming.
e) state one (1) advantage of using a capillary column.

4. Name two (2) detectors used in GC and indicate the types of compounds suitable for
each detector.

5. Describe what is temperature programming in a GC analysis. Explain why it may be

necessary to run temperature programming in GC.

6. Between a capillary column and a packed column, name the column which:

a) requires the use of lower sample volumes,

b) have a smaller internal diameter.

7. In a GC analysis, a mixture of compounds was found to have a wide range of boiling

points between 80 °C to 200 °C. When analyzed using an isothermal run, the peaks
were not well separated. Briefly explain how this problem could be solved in order to
produce well-separated peaks.

8. For each of the following descriptions, select a suitable GC detector (thermal

conductivity, flame ionization, electron capture) which:
9.
a) can only be used for samples that are able to be burned,
b) is well suited for pesticide residue analysis,
c) is universally applicable but not very sensitive,
d) uses a radioactive source.

10. Explain how qualitative analysis can be performed in GC with the use of retention
times.

11. State the type of samples which can be separated by gas chromatography (GC) but
not by high performance liquid chromatography (HPLC).

12. Draw the parts of a gas chromatograph in a well-labelled diagram.

13. What is meant by 'isothermal' run in GC?

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14. What is the goal of chromatography?

15. Briefly explain how qualitative analysis and quantitative analysis can be performed
using a chromatographic methods.

16. Briefly describe how flame ionization (FID) and thermal conductivity detectors
(TCD) operate, and include what types of analyte each detector is most suited for
detecting.

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 TUTORIAL CHM261

CHAPTER 6

1. Correctly label the following HPLC instrument:

2. Describe what are isocratic and gradient elution in HPLC.

3. Explain why 'sparging' is important in HPLC.

4. Briefly state the basis of separation for ion chromatography and size-exclusion
chromatography.

5. You wish to separate a mixture of water-insoluble polymers by collecting the

component with the highest molecular weight as the first fraction. Name the suitable
liquid chromatography technique you should use.

6. Distinguish between gel permeation chromatography and gel filtration

chromatography in terms of mobile phases and packing used and state the
application of each method.

7. State the type of samples that would be suitable for analysis using:

a) gas chromatography (GC)

b) high performance liquid chromatography (HPLC)

8. A reversed phase high performance liquid chromatography (HPLC) experiment was

run using the following conditions:
Column: 4.5 x 250 mm packed with 5 um, C18 bonded phase particles.
Flow rate: 2 mL/min.

a) Name one type of compound (polar/non-polar) suitable for analysis using HPLC.
b) State how particulate matter can be removed from the mobile phase solvents and
solutes.
c) How are dissolved air bubbles removed from the mobile phase solvents
d) What is the use of a guard column?

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9. A normal phase HPLC column was used to separate a sample containing a mixture of
C10 ester, a C10 alcohol and a C10 hydrocarbon.

a) Predict the elution order of the compounds.

b) Why did you choose the order in (a)?

10. Chromatogram 1 was obtained by analysis of a sample containing a mixture of two

sugars, A and B, using reversed-phase HPLC. Chromatogram 2 was obtained by
analyzing another sample of the sugar mixture using the same reversed-phase HPLC
instrument but under different experimental conditions. Suggest what experimental
condition was changed in order to obtain chromatogram 2.

11. Benzene is eluted from a reversed-phase C18 column in 9 min using a mobile phase
system consisting of 50 % acetonitrile and 50 % water. Estimate the retention time of
benzene if the mobile phase is changed to 70 % acetonitrile and 30 % water. Explain
your answer.

12. A sample containing compounds A, B and C was analyzed by HPLC using a C18
bonded phase column. A 20:80 (v/v) solution of ethanol and water was used as the
mobile phase and the following chromatogram was obtained.

Assuming the separation of compounds based on their polarity.

a) Is this a normal or reversed phase chromatography? Explain your answer.

b) Which compound is the most polar?
c) How would you change the mobile phase composition so that compound C would
elute sooner, without changing the relative positions of compound A and B?
Explain your answer.

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