Chapter 1

The Analyst’s Toolbox

Problem 1.1: Absorption of UV-vis photons usually is associated with electronic transitions—that is, such
absorptions cause electrons to move from one energy level to another. In your course on general
chemistry, you learned that energy levels are quantized. Based only on that information, what types of
peaks (broad or narrow) would you expect to see in a UV-vis spectrum? Explain your answer. Propose
some ideas for why we usually observe smooth, broad peaks in UV-vis spectroscopy?

This is an open-ended question, so graders will need to adjust based on how students explain their
answers.
Initially, we would expect a peak associated with the transition between two quantized energy levels to
be narrow, since if there is only one possible energy for each state (the fundamental meaning of
quantized), there can be only one value for a difference in energy. However, we are aware that atoms in
molecules are in constant motion, moving (vibrating) with respect to one another. For every quantized
electronic energy level, there might be multiple vibrational states. This could lead to a broadening of
peaks related to the electronic transition. Further, interactions between molecules in solution cause
changes in electronic energy levels, and the interactions between solutes and solvent molecules are not
the same from one solute molecule to the next.

Problem 1.2: Beer’s law states that absorbance = εbc. In this equation, ε is the molar absorptivity (in units
of cm-1∙M-1), b is the absorbent path length in cm, and c is the concentration in molarity. Estimate ε for the
DPK peak seen at 272 nm in Figure 1.2, assuming a standard cell path length of 1.0 cm.

From the figure, we know that c =0.0828 mM DPK, and we can estimate the absorbance for the 272 peak
as about 0.66 AU. We know that A = εbc, so
A 0.66
ε= = 3 -1 -1
bc ( 1.0 cm)(0.0828 x 1 0−3 M ) = 7971 = 8.0 x 10 cm M

Problem 1.3: Using the molar absorptivity calculated in Problem 1.2, what would be the concentration of
DPK required to produce an absorbance of 0.433 at 272 nm?

Estimated ε from Problem 1.2 was 7971 cm-1M-1.

A=εbc
0.433 = (7971 cm-1M-1)(1.0 cm)(C)
C = 5.432 x 10-5M = 5.5 x 10-5 M DPK

Problem 1.4: A 13.50 mg sample of impure DPK was dissolved in 50.00 mL acetonitrile and placed in a
sample cell with a path length of 0.05 cm. The absorbance was found to be 0.513 at a wavelength of 272
nm. What was the percent purity of the DPK sample? Hint: Use the molar absorptivity calculated in
Problem 1.2.

We know from Problem 1.2 that the molar absorptivity is 7971 cm-1M-1, so we can estimate the
concentration as
A=εbc
0.513 = (7971 cm-1M-1)(0.05 cm)(C)
C = 1.287 x 10-3 M DPK
mg DPK
For percent purity, we need % purity= x 100%
mg sample
We can get the mg DPK from the concentration as:
−3
1.287 x 10 mol Dpk 184.19 g DPK 1000 mg
mg DPK= x 0.05000 L soln x x = 11.85 mg DPK
L soln mol DPK g

mg DPK 11.85 mg DPK

% purity= x 100= x 100 = 87.81% = 88% pure
mg sample 13.5 mg Sample

Problem 1.5: What is the underlying basis for the relationship between the absorptivity (strength or
height) of the peak and quantitative sensitivity?

In a calibration plot (such as students will have done in Quantitative Analysis and perhaps in Gen. Chem.)
we plot absorbance vs. concentration. This means that our slope is proportional to absorptivity. A large
absorptivity yields a large calibration slope – meaning a small change in concentration yields a large
change in absorbance, which is our measured signal. That is the essence of sensitivity – a signal that is
sensitive to small changes in the independent variable (concentration in this case).

Problem 1.6: Estimate ε for the peak seen at 1690 cm-1 in Figure 1.4. (See Problem 1.2.)

In the figure caption we are given the concentration as 0.058 M DPK and the path length as 0.2 mm,
which is 0.02 cm. We can estimate the absorbance of the 1690 cm -1 peak as about 0.44 AU. We know
that A = εbc, so
A 0.44
ε= = = 379 = 400 cm-1M-1
bc ( 0.02 cm)(0.058 M )

Problem 1.7: This is an open-ended question, so you will need to defend your answer. You are setting up
a new analytical laboratory. Which do you purchase first: a UV-vis or an FTIR instrument? In every such
instance, a chemist must take into account cost and benefit and also must consider what is needed in his
or her analyses. Be sure to explain your answer.

No specific correct answer – graders will need to adjust based on student explanation.

Problem 1.8: In a standard 1H NMR spectrum, what type of splitting pattern would you expect for each
unique proton in 1-chloropropane? 2-chloropropane?

1-chloropropane triplet, sextet (or quartet of triplets), triplet

2 chloropropane septet, doublet

Problem 1.9: The spectra of 2-butanone, methylethylether, and 1-butyne will each exhibit a triplet, a
quartet, and a singlet similar to the spectrum seen for diethylmalonate (Figure 1.9). For each of those
compounds, explain how you would distinguish it from diethylmalonate using the NMR spectra. Hint:
Consider the shielding effects of nearby nuclei.

diethylmalonate

2-butanone methylethylether 1-butyne

We would expect the order of the triplet, singlet and quartet to be the same for all 4 compounds (from
right to left in the spectrum, the triplet would come first, the singlet next and the quartet last). However,
in 2-butanone, none of the proton-bearing carbons are directly bonded to an electronegative element
(oxygen), so all of the peaks should be positioned below 4 ppm (note that only the CH 2 bonded to the
oxygen… that is, the quartet… is shifted above 4 ppm). Also the integration of the peak (c) would indicate
it has the same number of protons as (a) in 2-butanone, and it has half of the number of protons to (b) in
diethylmalonate.
In methylethylether, we would expect the quartet and singlet to both be shifted above 4 ppm. The
integration would be similar to 2-butanone.
In 1-butyne, no electronegative elements are present; while the triple bond will affect shielding, it will not
be to the extent that oxygen would. All peaks would probably fall below 3 ppm. The integration of the
peaks would be unique among all the compounds considered.

Problem 1.10: Consider the spectrum shown in Figure 1.11. Looking at the structure of the compound
given in the figure, what gives rise to the specific peaks we see? That is, why do you think we observe
certain fragments but not others?

The largest peak represents half of the molecule, meaning the bond between the two carbonyls is weak.
This is as expected, since the electronegativity of the oxygens in the carbonyl and the ester linkages would
cause them to withdraw electron density from that central bond. Another major peak is associated with
the central two carbonyls alone. Again, the electronegative oxygens on each side of the bonds that must
break to form that fragment weakens the bonds. A similar case can be made for the third labeled peak at
m/z=59.

Problem 1.11: Both spectra shown in Figure 1.12 exhibit a notable peak at m/z = 30 amu. Postulate at
least one fragment that could give rise to that peak in both spectra.

NO+ is the only one that could be a part of both structures.

For picric acid, also possible is C-OH2+

Problem 1.12: Consider what you know about MS and HPLC. Why is it only relatively recently that MS has
been used as a detector for HPLC?

The main consideration is that analytes must be in the gas state in the mass spectrometer. The technical
difficulties with having to vaporize solvent along with analytes had to be overcome before MS could be
used as a viable detector for HPLC.

Problem 1.13: Consider the chromatogram given in Figure 1.13, noting that peak 7, methamphetamine,
and peak 8, 4-methylenedioxymethamphetamine, are not fully separated. Why do you think the
experimenters had difficulty in that separation?

Methamphetamine MDMA
The two compounds have similar structures, particularly the polar amine group and aromatic ring. They
would have been similarly attracted to the stationary phase and so would not have fully separated.

Exercise 1.1: Given the relationship absorbance = εbc, where ε is the molar absorptivity (in units of
cm-1∙M-1) and c is the concentration in molarity, estimate ε for the peak seen at 356 nm in Figure 1.2.

Absorbance is about 0.625, concentration for that peak is 4.17 mM.

A = εbc
0.625 = (ε)(1 cm)(4.17 x 10-3 M)
ε = 149.8 = 150. cm-1M-1

Exercise 1.2: The molar absorptivities for all three peaks exhibited by DPK in Figure 1.2 have been
determined in this chapter. What conjectures can you make about the transitions that give rise to those
peaks?

The two peaks at lower wavelength (240 and 272 nm) are more intense. The concentration had to be
increased by a factor of about 50 in order to even see the peak at 356 nm. We can assume, then, that the
two higher energy peaks are more favored – they have a higher probability of occurring. This is not due to
energy, at least not directly, since they require photons of higher energy to achieve the transition. It must
be due to something else about the molecule that causes those transitions to be favored.

Exercise 1.3: Consider the peak at about 1000 cm-1 in Figure 1.4.
(a) Convert the wavenumber (cm-1) to wavelength in micrometers.
(b) Estimate the absorbance of that peak and convert it to percent transmittance.

(a) Wavelength in cm = 1/(1000 cm-1) = 0.001 cm.

Wavelength in microns = 0.001 cm x 104 μm/cm = 10 μm.
(b) A = 0.3. A = -log(T), so T = 0.523 and %T = 52%
Exercise 1.4: The Fourier transform is mentioned with respect to two instruments in this chapter. Find a
reliable website that describes the Fourier transform and summarize your findings in 250 words or less.

The Fourier transform converts a complex signal into one that can be represented by a series of sinusoidal
waves. The size of a given peak in the transformed plot is a measure of the intensity (amplitude of a given
sinusoidal wave.

Exercise 1.5: Rationalize the positions of the base peaks of the two spectra shown in Figure 1.12.

In (a), picric acid, the base peak is at about 238 amu, which would be the parent minus a proton. For (b),
TNT, the base peak is around 212, which is the parent minus 15 amu.
For picric acid, the proton on the hydroxyl group is relatively acidic, and so would be easily lost. The bond
between the ring and the oxygen in picric acid would be stronger than that between the methyl and the
ring in TNT. This is because the highly electron withdrawing nitro groups would weaken the ring-methyl
bond because the oxygen in the hydroxyl will resist that electron withdrawal, retaining a greater bond
strength.

Exercise 1.6: What region of the EMS (in Hertz) is utilized by each of the following spectroscopies?
(a) UV-vis (b) FTIR

(a) UV-Vis is 195 – 900 nm in terms of wavelength. We can convert these to frequency with c = λν, or
8
❑ c 2.998 x 10 m/ s
195 nm: ν= = = 1.54 x 1015 Hz
❑ λ −9
195 x 1 0 m
c 2.998 x 10 8 m/ s
900 nm: ν= = = 3.31 x 1014 Hz
λ −9
900 x 1 0 m

(b) FTIR (assuming mid-IR) is 2500-50000 nm

c 2.998 x 10 8 m/ s
2500 nm: ν= = = 1.20 x 1014 Hz
λ 2500 x 1 0−9 m
8
c 2.998 x 1 0 m/s
50,000 nm: ν= = = 6.0 x 1012 Hz
λ 50,000 x 10−9 m