Chap 1 - Indetification - NMR-2024-CLC

Polymer analysis
Chap 1- Identification
Nuclear Magnetic Resonance- NMR
Nuclear Magnetic Resonance Spectroscopy
• Nuclei are positively charged and interact with an external magnetic
field denoted by B0
• Magnetic rotation of nuclei is random in the absence of a magnetic
field
• In the presence of a strong magnet, nuclei adopt specific orientations
• When exposed to a certain frequency of electromagnetic radiation,
oriented nuclei absorb energy and causes a spinflip from a state of
lower energy to higher energy
• Nuclear magnetic resonance - Nuclei are in resonance with applied radiation
• Frequency that causes resonance depends on:
• Strength of external magnetic field
• Identity of the nucleus
• Electronic environment of the nucleus
• Larmor equation
• Relation between
• Resonance frequency of a nucleus
• Magnetic field and the magnetogyric ratio of the nucleus
 γ 
ν =   B0
 2π 
Working of an NMR Spectrometer
• Organic sample dissolved in a suitable solvent is placed in a thin glass
tube between the poles of a magnet
• 1H and 13C nuclei respond to the magnetic field by aligning themselves
to one of the two possible orientations followed by rf irradiation
• Constant and varied strength of the applied field causes each nucleus
to resonate at a slightly varied field strength
• Absorption of rf energy is monitored by a sensitive detector that
displays signals as a peak
Chuẩn bị mẫu
• The sample must be sufficiently soluble
to yield an NMR spectrum. D2O and
CDCl3 are the most commonly used
solvents. deuterated solvents). Ví dụ:
CDCl3, DMSO-d6,….
• Tetramethylsilane (TMS) as internal
standard (1 % (v/v))
• Solution depth 4.5 - 5 cm .
• Concentration: (0.01 mol/l cho phổ 1H,
0.1 mol/l cho phổ 13C).
• Tube Labeling/marking
1H NMR and 13C NMR
X-axis: The Chemical Shift (ppm)
• Chemical shift is the position on the chart at which a nucleus absorbs
• The delta (δ) scale is used in calibration of the NMR chart
• 1 δ = 1 part-per-million of the spectrometer operating frequency
Observed chemical shift (number of Hz away from TMS)

δ=
Spectrometer frequency in MHz
• The delta scale is used as the units of measurement can be used to compare
values across other instruments
1H NMR for CDCl3:
~7.265 ppm
(source: SDBS)
Chemical Shifts in 1H NMR Spectroscopy
• Protons which are equivalent in a chemical structure have identical
resonance frequencies (chemical shift values).
• Protons bonded to saturated, sp3-hybridized carbons absorb at higher
fields
• Protons bonded to sp2-hybridized carbons absorb at lower fields
• Protons bonded to electronegative atoms absorb at lower fields
Các vùng của phổ 1H NMR
Y-axis: intensity – NO!!!!
Integration of 1H NMR Absorptions: Proton
Counting
• In the figure, the peak caused by (CH3)3C–protons is larger than the

peak caused by –OCH protons
• Integration of the area under the peak can be used to quantify the
different kinds of protons in a molecule
?
?
Spin-Spin Splitting in 1H NMR Spectra
• Multiplet: Absorption of a proton that splits into multiple peaks
• The phenomenon is called spin-spin splitting
• Caused by coupling of neighboring spins
Spin-Spin Splitting in 1H NMR Spectra
• n + 1 rule: Protons that exhibit n + 1 peaks in the NMR spectrum
possess
• n = number of equivalent neighboring protons
• Coupling constant (J) is the distance between peaks in a multiplet
Rules of Spin-Spin Splitting
• Chemically equivalent protons do not show spin-spin splitting
• The signal of a proton with n equivalent neighboring protons is split into
a multiplet of n + 1 peaks with a coupling constant
• Two groups of photons coupled together have the same coupling constant,
J
• It is possible to identify multiplets in a complex NMR that are related
• Multiplets that have the same coupling constant can be related
• Multiplet-causing protons are situated adjacent to each other in the molecule
Example
• The integrated 1H NMR spectrum of a compound of formula C4H10O
is shown below
• Propose a structure
More Complex Spin-Spin Splitting Patterns
• Some hydrogens in a molecule possess accidentally overlapping
signals
• In the spectrum of toluene (methylbenzene), the five aromatic ring protons
produce a complex, overlapping pattern though they are not equivalent
More Complex Spin-Spin Splitting Patterns
• Splitting of a signal by two or more nonequivalent kinds of protons
causes a complication in 1H NMR spectroscopy
Typical correlation table 1H NMR chemical
shifts of polymer
13C NMR Spectroscopy.
• Spin-spin splitting is observed only in 1H NMR
• 13C NMR provides a count of the different carbon atoms in a molecule
• 13C resonances are 0 to 220 ppm downfield from TMS
Carbon-13 Spectra of 2-butanone and para-bromoacetophenone
Example
• Classify the resonances in the 13C spectrum of methyl propanoate,
CH3CH2CO2CH3
c d
b
a
• Methyl propanoate has four unique carbons that individually absorb in specific
regions of the 13C spectrum
DEPT 13C NMR Spectroscopy
• DEPT-NMR (distortionless enhancement by polarization transfer)
• Stages of a DEPT experiment
• Run a broadband-decoupled spectrum
• Run a DEPT-90 : only CH
• Run a DEPT-135 : CH: positive signal, CH2: negative signal, C (no H): not
appear
• The DEPT experiment manipulates the nuclear spins of carbon nuclei
DEPT-NMR for 6- DEPT-90
methyl-5-hepten-2-ol
DEPT-135
Typical 13C NMR chemical shifts of polymers
• NMR technique has been used to identify copolymers.
• For examples: 1H NMR for copolymer methyl methacrylate
(MMA) và hexyl methacrylate (HMA)
• Peaks from 0.5-2.5 ppm were assigned for protons of alkyl
methylene in copolymer
• Peaks at 3.6 và 3.9 ppm were assigned for 3 protons of-
OCH3 belonged to MMA and 2 protons of -OCH2 belonged
to HMA
• %MMA in copolymer could be calculated by
• A: peak’s integration

Chap 1 - Indetification - NMR-2024-CLC

Uploaded by

Copyright:

Available Formats

Chap 1 - Indetification - NMR-2024-CLC

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Chap 1 - Indetification - NMR-2024-CLC

Uploaded by

Copyright:

Available Formats

Polymer analysis

Observed chemical shift (number of Hz away from TMS)

• In the figure, the peak caused by (CH3)3C–protons is larger than the

You might also like