Name __________________

Chemistry 471/526
Instrumental Methods of Analysis/Advanced Analytical Chemistry
Exam III, October 23-30, 2015
1.(5) A Raman shifter with H2 gas was used to produce new wavelengths from a fixed
wavelength KrF laser. The output wavelength of the excimer laser is 249 nm and the
fundamental vibrational frequency of H2 is 4400 cm-1. Find the wavelengths of the first
three of the five Stokes and each of the two anti-Stokes lines produced at the output of
the Raman shifter from harmonics of this vibrational mode.
2.(5) A 31P NMR spectrum was obtained for the following compound, adenosine
triphosphate (ATP).
What would the spectrum be expected to look like? (Assume no spin-spin coupling. Do
not give exact shifts, only relative positions of the expected peaks.)
3.(7) The NMR spectrum of a polyester dissolved in trifluoroacetic acid gave multiplets
centered around 2.0 (45), 4.75 (114), and 8.0 (133). The integrator readings for the
peaks are given in parentheses. The peaks at 4.75 include all protons immediately
adjacent to oxygen atoms. (a) Determine the mole percent of the three following
components in the polymer. (b) Determine the weight percent of each component.

1.

CH2
3.

CH 2

CH2

CH2

CH

CH
CH2

2.

CH2

Page Score _____ / _____

1

Name __________________

4(5) Methylene bromide was chosen as the internal standard for the quantitative
analysis of propionaldehyde in a solution. A series of standard solutions were prepared by
using pipettes to successively add 0.5, 1.0, 1.5, 2.0, and 2.5 mL of propionaldehyde to
each of five labeled 10 mL volumetric flasks. A pipette was used to add 1 mL of
methylene bromide to each flask and the flasks were filled to the mark with solvent. An 8
mL portion of the analyte was added by pipette to each of three 10 mL volumetric flasks.
A 1 mL portion of methylene bromide was added to each flask and the solutions were
filled to the mark with solvent. The integrated peak areas corresponding to the methylene
bromide protons and the aldehydic proton of propionaldehyde were measured for each
solution. Determine the percentage (v/v) of propionaldehyde in each sample solution, the
mean percentage, and the standard deviation of the results.
_________________________________________________________
Volume of
Relative aldehydic
aldehyde, mL peak area
0.5
1.0
1.5
2.0
2.5
Sample 1
Sample 2
Sample 3

Relative CH2Br2
peak area

5.0
8.7
18.6
19.5
26.8
19.4
18.5
19.5

12.0
10.0
14.0
11.0
12.0
12.1
11.2
12.4

5(8). An experiment was run .to determine percent recoveries. The peak heights were
used for the assay. After the standards were run and then the samples, all the recoveries
were found .to be significantly greater than 100%. The operator decided that there was
some change in the experimental condition between the time the standards were run and
the time the samples were run.
a. Could the results occur if all the k values were constant?
b. Could the results occur if all the t R values were constant?
c. Would there be a simple way .to change the assay .to avoid the problem in the
future?

Page Score _____ / _____

2

Name __________________

6.(10) A chromatographic column was operated under the following conditions:

Column: 1.2 m .d. 2.0 m packed with Chromosorb P weight of paraffin stationary
liquid, 2.43 g; density, 0.796 g/mL
Pressures: inlet, 18.3 psi above room; room, 768 Torr
Outlet flow rate: 31.3 mL/min
Temperatures: room, 19.6C; column, 90.3C
Retention time: air, 0.395 min
Retention times and peak widths i-propylamine, 4.51 and 0.36 min; n-propylamine, 4.91
and 0.382 min
Calculate the following
a. the average flow rate in the column.
b. the corrected retention volumes for air and the two amines.
c. the specific retention volumes for the two amines.
d. partition coefficients for the two amines.

.
5.(5) Gaseous HCl exhibits an infrared peak at 2890 cm-1 due to the hydrogen/cholorine
stritching vibration.
(a)
(b)

Calculate the force constant for the bond.

Calculate the wavenumber of the absorption peak for DCl assuming the force
constant is the same as that calculated in part (a).

Page Score _____ / _____

3

Name __________________

7.(10) Calculate the retention index for each of the following compounds:
____________________________________________________

Compound
(tR - t M)
____________________________________________________
(a)
(b)
c)
(d)
(e)
(f)

(g)
(h)
(i)

Propane
n-Butane
n-Pentane
n-Heptane
Toluene
n-Propanol
n-Octane
n -Butanol
Methylethyl ketone

1.29
2.21
4.10
14.08
16.32

8.(10) The following data were obtained by gas-liquid chromatography on a 40 cm

packed column:
Compound

tR /min

W /min

Air
Methylcyclohexene
Toluene

1. 9
10.9
13.4

0 .76
0.82
1.06

Calculate
(a) an average number of plates from the data.
(b) the standard deviation for the average in (a).
(c) an average plate height for the column.
(d) the capacity factor for each of the three species.

Page Score _____ / _____

4

Name __________________

9.(5) (a) A chromatography column with a length of 50.6 cm and inner diameter of 19.2
mm is packed with a stationary phase that occupies of the volume. Fine the linear flow
rate (cm/min) if the volume flow rate is 2.22 mL/min.
(b) Find the retention time for a solute with a capacity factor 8.04.
10.(5) Two compounds with capacity factors of 5.00 and 5.10 are separated on a column
with a plate height of 155 m. What length of column is required to give a resolution of
1.00? Of 2.00?
11.(5) (a) How many theoretical plates produce a chromatography peak eluting at 12.83
min with a width at the base of 18.4 s?
(b) If the length of the column is 15.8 cm, fine the plate height.
12.(5) Retention times in a gas chromatogram are 1.21 min for CH 4, 7.33 min for hexane,
7.66 min for unknown, and 8.41 min for heptane. Fine the Kovats retention index for the
unknown.
13.(5) Compounds C and D gave the following HPLC results:

Compound
C
D

Concentration
(g/mL) in
mixture
2.36
3.37

Peak area (cm2)

4.41
5.52

A solution was prepared by mixing 1.23 mg of D in 5.00 mL with 10.00 mL of unknown

containing just C, and diluting to 25.00 mL. Peak areas of 3.33 and 2.22 cm2 were
observed for C and D, respectively. Find the concentration of C (g/mL) in the unknown.
14.(5) Polar solutes were separated by HPLC using a bonded phase containing polar
diol substituents [-CH(OH)CH2OH]. How would the retention times be affected if the
eluent were changed from 40 vol% to 60 vol % acetonitrile in water?
15.(5) Toluene exhibited a capacity factor of 3.50 and a plate height of 10.6 m on a
14.0-cm HPLC column. If unretained solute is eluted in 1.33 min, find the retention time
and width (w1/2) at half-height for toluene. If you want to use a faster linear flow rate, but
get the same separation efficiency, should you raise or lower the column temperature?

Page Score _____ / _____

5