ST.

JOSEPH COLLEGE OF ENGINEERING

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OBT751 - ANALYTICAL METHODS AND
INSTRUMENTATION

UNIT - 3
LECTURE - 4

Presented by
J.Jayashree AP/EEE
SJCE
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 UNIT – 3 NMR AND MASS SPECTROMETRY
3.3 NMR Spectrometers
• Two general types of NMR spectrometers are available:
 Wide-line spectrometers and
 High-resolution spectrometers.
• Wide-line instruments have magnets with strengths of a few tenths
of a tesla and are considerably simpler and less expensive than are
high-resolution instruments.
• High-resolution instruments are equipped with magnets with
strengths that range from 1.4 to 23.5 T, which correspond to proton
frequencies of 60 to 1000 MHz (1 GHz).
• Before about 1970, high-resolution NMR spectrometers were all of
the CW type that used permanent magnets or electromagnets to
supply the magnetic field.
• This type of instrument has been largely replaced by Fourier transform
spectrometers equipped with superconducting magnets to provide3 the
magnetic field.
 UNIT – 3 NMR AND MASS SPECTROMETRY
3.3 NMR Spectrometers
• Computers are an integral part of modern NMR instruments; they
digitize and store the signal, perform Fourier transformation of the
FID to provide the frequency-domain signal, and deliver many other
data-treatment and instrument-control functions.
• A major reason why Fourier transform instruments have become so
popular is that they permit efficient signal averaging and thus yield
greatly enhanced sensitivity.
• High-resolution NMR spectrometers are quite expensive, costing
several hundred thousand dollars and more.
• Almost all commercial NMR spectrometers today operate in the
pulsed, or FT, mode.

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 UNIT – 3 NMR AND MASS SPECTROMETRY
3.3 NMR Spectrometers
Components of Fourier Transform Spectrometers :
Figure below is a simplified block diagram showing the instrument
components of a typical FT-NMR spectrometer.
• The central component of the instrument is a highly stable magnet in
which the sample is placed.
• The sample is surrounded by a transmitter-receiver coil.
• RF radiation is produced by a crystal-controlled frequency synthesizer
having an output carrier frequency of ‫ט‬c.
• This signal passes into a pulse switch and power amplifier, which
creates an intense and reproducible pulse of RF current in the
transmitter coil.
• The resulting RF radiation impinges on the sample, contained inside
the coil.
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FIGURE :Block diagram of an FT-NMR
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spectrometer.
 UNIT – 3 NMR AND MASS SPECTROMETRY
3.3 NMR Spectrometers
• The length, amplitude, shape, and phase of the pulse are selected by
the operator; entered into the console; and controlled by the
computer.
• In the Figure, a 5-μs pulse is shown.
• The resulting FID signal is picked up by the same coil, which now
serves as a receiver.
• The signal is then amplified and transmitted to a phase-sensitive
detector.
• The detector circuitry produces the difference between the nuclear
signals ‫ט‬n and the crystal oscillator output ‫ ט‬c, which leads to the
low-frequency, time-domain signal shown on the right of the figure.
• This signal is digitized and collected in the memory of the computer
for analysis by a Fourier transform program and other data-analysis
software. The output from this program is plotted on a display device,
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 UNIT – 3 NMR AND MASS SPECTROMETRY
3.3 NMR Spectrometers
Magnets :
• The heart of all NMR instruments is the magnet.
• The sensitivity and resolution of spectrometers are both critically
dependent on the strength and quality of their magnets.
• Because both sensitivity and resolution increase with increasing field
strength, it is advantageous to operate at the highest possible field
strength.
• Spectrometer magnets of three types have been used in NMR
spectrometers:
 Permanent magnets,
 Conventional electromagnets, and
 Superconducting solenoids.

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 UNIT – 3 NMR AND MASS SPECTROMETRY
3.3 NMR Spectrometers
• These magnets attain fields as large as 23.5 T, corresponding to a
proton frequency of 1 GHz.
• To superconduct, the solenoid, wound from superconducting
niobium- tin or niobium-titanium wire, is bathed in liquid helium at a
temperature of 4 K.
• The advantages of superconducting solenoids, are
 high field strengths,
 high stability,
 low operating cost, and
 simplicity and small size
Locking the Magnetic Field :
• A field-frequency lock system is used in commercial NMR
instruments.
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 UNIT – 3 NMR AND MASS SPECTROMETRY
3.3 NMR Spectrometers
• In these systems, a reference nucleus is continuously irradiated and
monitored at a frequency corresponding to its resonance maximum
at the rated field strength of the magnet.
• Changes in the intensity of the reference signal control a feedback
circuit, whose output is fed into coils in the magnetic gap in such a
way as to correct for the drift.
• For a given type of nucleus, the ratio between the field strength and
resonance frequencies is a constant regardless of the nucleus.
• Thus, the drift correction for the reference signal is applicable to the
signals for all nuclei in the sample area.
• In modern spectrometers, the reference signal is provided by the
deuterium in the solvent, and a second transmitter coil tuned to the
frequency for deuterium monitors the reference.
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 UNIT – 3 NMR AND MASS SPECTROMETRY
3.3 NMR Spectrometers
Shimming :
• Shim coils are pairs of wire loops through which carefully controlled currents
are passed, producing small magnetic fields that compensate for
inhomogeneities in the primary magnetic field.
• Ordinarily, shimming must be carried out each time a new sample is
introduced into the spectrometer.
Sample Spinning :
• The effects of field inhomogeneities are also counteracted by spinning the
sample along its longitudinal axis.
• Spinning is accomplished by means of a small plastic turbine that slips over
the sample tube.
• A stream of air drives the turbine at a rate of 20 to 50 revolutions per second.
• If this frequency is much greater than the frequency spread caused by
magnetic inhomogeneities, the nuclei experience an averaged environment
that causes apparent frequency dispersions to collapse toward zero. 11
 UNIT – 3 NMR AND MASS SPECTROMETRY
3.3 NMR Spectrometers
The Sample Probe :
• A key component of an NMR spectrometer is the sample probe, which
serves multiple functions.
• It holds the sample in a fixed position in the magnetic field, contains an
air turbine to spin the sample, and houses the coil or coils that permit
excitation and detection of the NMR signal.
• In addition, the probe ordinarily contains two other transmitter coils, one
for locking and the other for decoupling.
• The usual NMR sample cell consists of a 5-mm (outside diameter) glass
tube containing 500–650 μL of liquid.
• Microtubes for smaller sample volumes and larger tubes for special
needs are also available.
Transmitter-Receiver Coils :
• The adjustable probes in modern NMR spectrometers contain transmitter
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and receiver coils.
 UNIT – 3 NMR AND MASS SPECTROMETRY
3.3 NMR Spectrometers
• The receiver coils are arranged according to the experiment purpose.
• For observing protons, the probe usually has an inner coil for 1H
detection and an outer coil, called the X-nucleus coil, for detecting
nuclei such as 13C or 15N.
• The inner coil is generally the closest to the sample to maximize
sensitivity.
• For experiments to detect nuclei other than protons, the X-nucleus
coil is placed on the inside and the 1H coil on the outside.
The Pulse Generator :
• RF generators and frequency synthesizers produce a signal of
essentially a single frequency.
• To generate Fourier transform spectra, however, the sample must be
irradiated with a range of frequencies sufficiently great to excite
nuclei with different resonance frequencies 13
 UNIT – 3 NMR AND MASS SPECTROMETRY
3.3 NMR Spectrometers
• Fortunately, a sufficiently short pulse of radiation, provides a
relatively broad band of frequencies centered on the frequency of
the oscillator.
• The frequency range of this band is about 1/(4) Hz, where  is the
length in seconds of each pulse.
• The narrower the square wave, the broader the range of component
frequencies.
• Thus, a narrow pulse generated by rapidly switching an RF oscillator
consists of a band of frequencies capable of exciting all nuclei whose
resonances occur in the vicinity of the frequency of the oscillator.
• The typical pulse generator consists of three parts:
 a frequency synthesizer,
 a gate to switch the pulse on and off at appropriate times, and
 a power amplifier to amplify the pulse to about 50 to 100 W. 14
 UNIT – 3 NMR AND MASS SPECTROMETRY
3.3 NMR Spectrometers
The Receiver System:
• Voltages generated by the current in the detector coil are in the
nanovolt-to-microvolt range and thus must be amplified to a range of
about 0 to 10 V before the signal can be further processed and
digitized.
• The first stage of amplification generally takes place in a preamplifier,
which is mounted in the probe so that it is as close to the receiver coil
as possible to minimize the effects of noise from other parts of the
instrument.
• Further amplification then is carried out in an external RF amplifier.
The Detector and Data-Processing System :
• The high-frequency radio signal is first converted to an audio-
frequency signal, which is much easier to digitize.
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 UNIT – 3 NMR AND MASS SPECTROMETRY
3.3 NMR Spectrometers
• The signal from the RF amplifier can be thought of as being made up
of two components:
 a carrier signal, which has the frequency of the oscillator
producing it, and
 a superimposed NMR signal from the analyte.
• The analyte signal differs in frequency from that of the carrier by a
few parts per million.
• The proton NMR data generated by a 500-MHz spectrometer would
lie in the frequency range of 500,000,000 to 500,005,000 Hz.
• To digitize such high-frequency signals and extract the small
differences attributed to the sample in the digital domain is not
practical;
• Therefore, the carrier frequency c is subtracted electronically from
the analyte signal frequency s in the analog domain. 16
 UNIT – 3 NMR AND MASS SPECTROMETRY
3.3 NMR Spectrometers
Sampling the Audio Signal :
• The sinusoidal audio signal obtained after subtracting the carrier
frequency is then digitized by sampling the signal voltage, periodically
converting it to a digital form with an analog-to-digital converter.
• To accurately represent a sine or a cosine wave digitally, it is
necessary, according to the Nyquist sampling theorem, to sample the
signal at least twice during each cycle.
• If sampling is done at a frequency that is less than twice the signal
frequency, folding, or aliasing, of the signal occurs.
• In modern NMR spectrometers, quadrature phase-sensitive detectors
make possible the determination of positive and negative differences
between the carrier frequency and NMR frequencies.

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 UNIT – 3 NMR AND MASS SPECTROMETRY
3.3 NMR Spectrometers
• The effect of folding is illustrated in Figure below, which shows, as the
dashed curve, a 1600-Hz cosine signal that is being sampled at a rate
of 2000 data per second. FIGURE : Folding of a
spectral line brought about
by sampling at a frequency
that is less than the Nyquist
frequency of 3200 Hz and
that is sampled at a
frequency of 2000 samples
per second as shown by
dots; solid line is a cosine
wave having a frequency of
400 Hz. (b) Frequency-
domain spectrum of dashed
signal in (a) showing the
folded line at 400 Hz.
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 UNIT – 3 NMR AND MASS SPECTROMETRY
3.3 NMR Spectrometers
• The solid dots represent the times at which the computer sampled
and digitized the data.
• This sampling rate is less than the Nyquist frequency, which is 2 3
1600 Hz 5 3200 Hz.
• The effect of this inadequate sampling rate is demonstrated by the
solid curve in Figure above is a 400-Hz cosine wave.
• In modern NMR spectrometers, quadrature phase-sensitive detectors
make possible the determination of positive and negative differences
between the carrier frequency and NMR frequencies.
• Because these detectors are able to sense the sign of the frequency
difference, folding is avoided.
Signal Integration :
• The areas of proton NMR signals are almost always directly
proportional to the number of protons involved. 19
 UNIT – 3 NMR AND MASS SPECTROMETRY
3.3 NMR Spectrometers
• Hence, modern NMR spectrometers provide not only the NMR signal
itself, but for 1H spectra, the integral of the signal.
• For 13C spectra, the signals are in general not proportional to the
number of nuclei present. Usually, the integral data appear as step
functions superimposed on the NMR spectrum as illustrated in Figure
below

FIGURE Absorption and

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 UNIT – 3 NMR AND MASS SPECTROMETRY
3.3 NMR Spectrometers
Sample Handling
• High-resolution NMR studies have been restricted to samples that
could be converted to a nonviscous liquid state.
• Most often, a 2% to 15% solution of the sample is used, although
pure liquid samples can also be examined if their viscosities are
sufficiently low.
• Solvents must have no resonances of their own in the spectral region
of interest.
• Usually, NMR solvents are deuterated to provide the field-frequency
lock signal
• The most commonly used solvent for organic compounds is
deuterated chloroform (CDCl3).
• For highly polar and ionic compounds, D2O can be used along with a
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water-suppression method to remove the intense HOD solvent
 UNIT – 3 NMR AND MASS SPECTROMETRY
3.3 NMR Spectrometers
• High-quality NMR tubes are necessary with modern
highfield spectrometers.
• If tubes have been previously used, they must be
carefully cleaned and thoroughly dried prior to use.
• Sample-tube cleaners are available commercially for this
purpose.
• Cleaning solutions, such as chromic acid–sulfuric acid,
should never be used because paramagnetic chromium
ions can adsorb to the walls and broaden proton NMR
spectra.
• It is now possible to routinely collect high-resolution
spectra for solid samples. 22
THANK YOU
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