CONFIDENTIAL 1 AS/OCT 2023/CHM626
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UNIVERSITI TEKNOLOGI MARA
SUGGESTION ANSWERS
TEST 1
COURSE : ORGANIC SPECTROSCOPY
COURSE CODE : CHM626
EXAMINATION : OCTOBER 2023
TIME : 1.5 HOURS
INSTRUCTIONS TO CANDIDATES
1. This question paper consists of five (5) questions.
2. Do not bring any material into the examination room unless permission is given by the
invigilator.
3. Please check to make sure that this examination pack consists of
i) the Question Paper
ii) a two − pages Appendix containing NMR correlation charts
4. Answer ALL questions in YOUR OWN ANSWER SHEET. Start each answer on a new page.
5. Answer ALL questions in English.
50
DO NOT TURN THIS PAGE UNTIL YOU ARE TOLD TO DO SO
This examination paper consists of 5 printed pages
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CONFIDENTIAL 2 AS/OCT 2023/CHM626
QUESTION 1
a) A is an organic compound that only contains the atoms C, H and O.
i) Find the mass percentage of each element when combustion of 8.23 mg of a
compound A produced 9.62 mg CO2 and 3.94 mg H2O.
C; 9.62 x 10-3/44 g/mol x 12 g/mol = 2.62mg
C% = 2.62/8.23 X 100 = 31.83% (1M)
H; 3.94 x 10-3/18 g/mol x 2 g/mol = 0.44 mg
H% = 0.44/8.23 x 100 = 5.35% (1M)
O% = 100%- 31.83%-5.35%= 62.82% (1M)
ii) Determine the empirical formula of compound A.
Element C H O
No of moles 31.83/12 5.35/1 62.82/16
= 2.753 = 5.35 = 3.926
Mole ratio 2.753/2.753 5.35/2.753 3.926/2.753
=1 =2 = 1.4
Simplest ratio 2 4 3
(x2)
(2M)
Hence the empirical formula is: C2H4O3 (1M)
b) Mass spectrum is a method of analysis that ionizes chemical species and classifies
the ions according to the ratio of mass to charge.
i) Define base peak and nitrogen rule.
Base peak = The most abundant peak. Assigned an arbitrary intensity of 100. (1M)
Nitrogen rule = The nitrogen rule states that a molecule that contains nitrogen atoms
will give a molecular ion peak will be an ODD number (2M)
ii) Discuss how to differentiate the following pairs aromatic hydrocarbon isomers by
mass spectrometry.
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CONFIDENTIAL 3 AS/OCT 2023/CHM626
(B) (C)
Different fragmentation patterns (1M) and
different base peaks (1M) (B) m/z 105, (C) m/z 91 (1M)
QUESTION 2
a) The mass spectrum of 2-pentanol is shown below. Illustrate structure of the fragment
ions which appear at m/z 45.
OH OH
1M 1M
H
H 1M
H O
m/z 45
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CONFIDENTIAL 4 AS/OCT 2023/CHM626
b)
Ketone D with molecular formula of C5H10O give the following mass spectrum.
i) Indicate molecular ion peak and base peak.
Molecular ion peak: m/z 86 (1M)
Base peak: m/z 57 (1M)
ii) Propose structure of the fragment ions at m/z 57 and m/z 29.
CH3CH2C O
m/z 57 (1M) CH3CH2+ (1M)
QUESTION 3
a) Describe the structure for compound that meet the following properties.
Molecular formula; C3H7Cl
Splitting pattern in 1H NMR; one doublet and one septet.
(1M)
One doublet- CH3-CH (1M)
One septet (CH3)2-CH (1M)
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CONFIDENTIAL 5 AS/OCT 2023/CHM626
b) Sketch the 1H NMR peaks of compound E and indicate the number of its non-
equivalent protons.
CH A 3
H3C C CH3
B CH2
OH C
(E)
3 non-equivalent protons (1M)
triplet pn boleh for OH
(3M)
QUESTION 4
a) Describe how hydrogen bonding affect the 1H NMR chemical shifts.
The presence of hydrogen bonding will reduce the electron density (1M) around the
protons attached to the electronegative atom and deshield the proton (1M). Thus, the
value of chemical shift of those protons will increase (1M).
b) Compute the chemical shift in part per million for proton that has resonance 150Hz
downfield from TMS on spectrometer that operates at 60MHz.
δ = (150 Hz/60 MHz) x (1 MHz/1 x106 Hz)(1M)
= 2.5 ppm (1M)
c) Magnetic anisotropic field formed due to pi-bonded electrons in the molecule will affect
the nearby protons. Construct the magnetic anisotropic field diagrams that occur in
alkene and alkyne.
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CONFIDENTIAL 6 AS/OCT 2023/CHM626
(2M) (2M)
QUESTION 5
The mass spectrum of compound G is shown below. Given compound G contains one
oxygen with 1H NMR chemical shifts (ppm) of 3.7 (singlet), 6.8 (multiplet), and 7.2
(multiplet). Answer the following questions.
a) Determine the molecular using Rule of Thirteen and index of hydrogen deficiency.
108/13= 8; r= 4 (1M) → CnHn+r → C8H12 (1M) (+O- CH4) (1M) → C7H8O (1M)
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CONFIDENTIAL 7 AS/OCT 2023/CHM626
b) Elucidate the possible structure of compound G based on the above information and
with the aids of Hydrogen Deficiency Index.
IHD = n-r+2/2 = 8-4+2/2 = 3+1 = 4 (2M) (probably contain benzene) (1M)
3.7 ppm; singlet ; CH3-O (1M) 6.8 &7.2; multiplet; CH-aromatic (1M)
OCH3
(1M)
c) Examine why the methyl proton peak appears at 3.7 ppm at the downfield region.
The presence of electronegative atom ie oxygen (1M) and anisotropic of the
benzene ring (1M), reduces the electron density around the methyl group (1M) and deshield
the protons (1M) causing it to appear at lower field region compared to the ordinary methyl
protons (1M).
END OF QUESTION PAPER
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