Quiz #1 Due June 16, 2014 10:00AM

25 points total SHOW YOUR WORK

Name __________________________________

1. Short answer question.

(a) Absorption spectroscopy ________ is the measurement of the amount of light absorbed
by a compound as a function of the wavelength of light.
(b) The energy of a photon is inversely ________ proportional to its wavelength.

(c) The energy of a photon is directly ________ proportional to its frequency.

(d) An infrared wavelength of 4.48m is equivalent to a wavenumber of 2230_____ cm-1.

(e) What wavelength in mm is equivalent to a wavenumber of 1750 cm-1? 5.71 x 10-3 mm

(f) The region of the IR spectrum which contains the most complex vibrations (600-1400
cm-1) is called the fingerprint ________ region of the spectrum.
(g) In order for a vibration mode to be observable in the IR, the vibration must change the
___dipole moment _____ of the molecule.

(h) An _____odd___ molecular ion peak usually indicates the presence of an odd number of
nitrogen atoms in the molecule.
(i) The mass spectrum of alcohols often fail to exhibit detectable M peaks but instead show
relatively large __M-18______ peaks.

(j) In a mass spectrum, the peak of greatest abundance is referred to as the base peak ___.
(k) In the presence of an external magnetic field the approximate ratio of 1H nuclei with
spins compared to spins is respectively: __50:50______.
(l) __tetramethylsilane ______ is commonly used as an internal reference in NMR
spectroscopy; its signal is assigned d = 0 in 1H and 13C NMR spectroscopy.
(m) On a 90 MHz spectrometer, calculate the frequency at which a proton absorbs if it
appears at 4.20 ppm. 378 Hz
(n) What is the relative area of each peak in a quartet spin-spin splitting pattern?
1:3:3:1

(o) Give two reason why 13C NMR is less sensitive than 1H NMR.
Natural isotopic abundance of 13C is about 100 times less than that of 1H or gyromagnetic
ratio of 13C is much smaller.
(p) Why is carbon-carbon splitting typically not seen in 13C NMR spectra?
Only 1% of the carbon atoms are 13C so the probability of two 13C nuclei being adjacent is
very small.

2. Rank the following bonds in order of increasing stretching frequency (cm-1) in IR

spectroscopy:
C-O < C=O < CC < C-H
3. Rank the following bonds in order of increasing stretching frequency (cm-1) in IR
spectroscopy:
C-N < C=O < CN < O-H
4. If the mass spectrum of chlorobenzene shows a peak with an m/z value of 114, having an
abundance of 15%, calculate the m/z value and approximate abundance of the molecular ion
peak.
m/z = 112, approximate abundance = 45%
5. For the following compounds, give approximate frequencies for distinctive peaks in the IR
spectrum.
(a)

(b)

(c)

6. The following is the mass spectrum of an unknown liquid with bp 100-105 C.

(a) What compound is this? 1-bromobutane
(b) Suggest structures for the fragments at 136, 107, and 93.
(c) Why is the peat at m/z 57 so strong?

7. For the following compound shown below,

(a) Sketch 1H spectrum, showing approximate chemical shifts
1
H NMR (d): 1.0 (3H, t), 2.0 (3H, s), 2.1 (2H, q)
(b) Sketch 13C spectrum (totally decoupled, with a singlet for each type of carbon), showing
approximate chemical shifts
(c) Sketch 13C spectrum in the off-resonance-decoupled spectrum
(d) Sketch 13C spectra expected using the DEPT-90 and DEPT-135 techniques.

8. Predict the multiplicity and the chemical shift for each shaded proton in the following
compounds.

9. Deduce the identity of the following compounds from the spectral data given.
(a) C5H10O:
1
H NMR (ppm): 1.2 (6H, doublet), 2.1 (3H, singlet), 2.8 (1H, septet)
-1
IR (cm ): 2980, 1710
MS: m/z 71, 43
(CH3)2CHCOCH3

(b) C9H7Cl
-1
IR (cm ): 3050, 2950, 2220, 1620
1
H NMR (d): 7.8 (2H, d), 7.2 (2H, d), 2.1 (3H, s)
13
C NMR (d): 140 (s), 132, (s), 125 (d), 122 (d), 88 (s), 83 (s), 18 (q)

(c) C3H6Br2: 2.4 (2H, quintet), 3.5 (4H, triplet) (ppm)

Answer: BrCH2CH2CH2Br