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A Problem-Solving Spectral and Structural Database = a Fun and Engaging Way to Teach Spectroscopy Assoc. Prof. Richard Morrison School of Chemistry Monash University (Richard.Morrison@sci.monash.edu.au)
Microanalysis
Percentage by mass of each atom in molecule C
% mass Atom ratio 54.5 54.5/12.01 = 4.54 4.54/2.27 = 1.98 C2H4O C2H4O C4H8O2 C6H12O3
H
9.2 9.2/1.008 = 9.13 9.13/2.27 = 4.02
O
36.3 36.3/16.00 = 2.27 2.27/2.27 = 1.00
Mass Spectrometry
Electron-impact (EI) mass spectrum Positive ions are separated based on their mass-tocharge (m/z) ratio One electron is removed as a result of impact Molecular ion (M.+) an odd-electron ion at an even m/z if an even # of nitrogens Fragment ions are indicative of structure, isotope peaks can also be very useful (think halogens !) Double bond equivalents : CxHyNzOn = x-y/2+z/2+1 (rings + double bonds)
STAV VCE Chemistry Conference
Methyl bromide - MS
-cleavage
-cleavage
Infrared Spectroscopy
Reveals presence of molecular functional groups by the vibrations of their bonds Peaks beyond fingerprint region important (> 1500 cm-1) Presence/absence of peaks can both be useful !! O-H bond: 3200 3500 cm-1 Strong and broad N-H bond: 3100 3500 cm-1 Medium C-H bond: 2850 3100 cm-1 Medium to strong C=O bond: 1630 1800 cm-1 Strong C=C bond: 1600 1680 cm-1 Weak
STAV VCE Chemistry Conference
IR Spectroscopy
Aniline
STAV VCE Chemistry Conference
NMR Spectroscopy
Nucleii : resonance frequencies, isotope abundances
Not all nucleii are NMR active Not all nucleii are NMR active
NMR Spectroscopy
Absorption of radio-frequency radiation of the appropriate energy flips the nuclear spin
STAV VCE Chemistry Conference
E=h
Bapp
STAV VCE Chemistry Conference
aligned with B
E=h
Blocal
STAV VCE Chemistry Conference
aligned with B
1H
NMR Spectroscopy
1H
Chemical Environments
1H
OH and NH2 protons can give broad OH and NH2 protons can give broad signals due to exchange processes signals due to exchange processes
1H
Integration : the area under an NMR peak is proportional to the number of equivalent hydrogens in an environment.
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B- B+
STAV VCE Chemistry Conference
aligned with B
Singlet n=0
Doublet n=1
Triplet n=2
Quartet n=3
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Spin-spin coupling
12
1H
NMR Spectroscopy
1
2 1 3
1H
NMR Spectroscopy
2 1 1
13
1H
NMR Spectroscopy
1H
NMR Spectroscopy
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1H
NMR Spectroscopy
1
2 1 3
3 2
1H
NMR Spectroscopy
2-4
3 4
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13C
NMR Spectroscopy
Distinct peak for each C environment (13C =1.1%) Chemical shifts:0-200 ppm vs 0-12 ppm for 1H depends on hybridization of C and electronegativity of attached groups Peak areas are not indicative (a quirk of the instrumentation in pulsed FT-NMR) Spin-spin coupling is not important : 13C-13C is unlikely due to low 13C abundance and 13C-1H coupling is removed by a technique known as broadband decoupling
13C
H
H
X C H C C C H
Vinylic
Ester/Amide/ Aldehyde/ Ketone/ Carboxylic Acid
Aromatic 120
Saturated C-H
240
200
160
Chemical shift () Chemical shift related to the BL which is determined by the Chemical shift related to the BL which is determined by the hybridization of the carbon centre and the groups attached. hybridization of the carbon centre and the groups attached.
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13C
NMR Spectroscopy
Aromatic C - H
13C
NMR Spectroscopy
1
3 2 1
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13C
NMR Spectroscopy
1
1
2 3
Aldehyde C Aliphatic C
13C
NMR Spectroscopy
1 2
3 4
Aliphatic C
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13C
NMR Spectroscopy
1 2 4 3
4 5 13
13C
NMR Spectroscopy
2
1
Alkene C Alkane C
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Packages / Applications
Use
NIST WebBook ChemDraw Microsoft Word, Notebook IGOR Spartan Adobe Photoshop LabVIEW
Source of IR & MS spectra Computing NMR, 2D structures Reformatting data JCAMP: Reformatting files 3D Structures Image processing Building and presenting Chemical Detectives
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