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NMR and ESR Spectroscopy Questions and Answers

1.

Atomic numbers of V, Cr, Fe and Zn are 23, 24, 26 and 30, respectively. Which one of the following materials does NOT show an electron spin resonance (ESR) spectra?

Exam Year(s)

GATE Physics - 2024,

Answer: D

The material that shows no ESR spectrum is Zn.

Electron spin resonance needs unpaired electron spins. Zinc (Z = 30) has the configuration [Ar]3d104s2: completely filled shells, no unpaired electrons, and it is diamagnetic, so it gives no ESR signal.

V ([Ar]3d34s2), Cr ([Ar]3d54s1) and Fe ([Ar]3d64s2) all have partly filled 3d shells and unpaired electrons, the condition for a resonance absorption between spin states in a magnetic field.

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2.

Nuclear Magnetic Resonance (NMR) spectrometer normally operates at :

Exam Year(s)

MH SET - 2019, SET Exam - 2019,

Answer: A

An NMR spectrometer operates in the Radio frequency region.

Nuclear spin energy levels split in a magnetic field by very small amounts. For protons in fields of a few tesla, the resonance frequency is tens to hundreds of megahertz, for example 400 MHz at 9.4 T, which lies in the radio frequency range.

Microwaves are used for electron spin resonance (ESR) and for rotational spectra, ultraviolet radiation excites electronic transitions, and audio frequencies are far too low for nuclear resonance in practical fields.

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3.

For NMR spectra of proton nuclei, the commonly used reference is :

Exam Year(s)

MH SET - 2020, SET Exam - 2020,

Answer: D

The usual reference is tetramethylsilane (TMS), printed 'Tetramethylsilame'.

TMS, Si(CH\(_{3}\))\(_{4}\), has twelve equivalent protons that give one sharp, strong signal. Silicon is less electronegative than carbon, so these protons are highly shielded and their signal lies upfield of almost all organic protons; it is assigned \(\delta = 0\) ppm. TMS is also chemically inert, soluble in most organic solvents and volatile, so it is easily removed.

Ethyl alcohol and methyl alcohol give several signals, including an OH peak that shifts with conditions, so they are unsuitable references. Carbon tetrachloride has no protons at all; it is used as a solvent, not a reference.

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4.

For proton (1H), placed in a magnetic field of 2.3 Tesla, the resonant frequency observed in an NMR spectrometer is (Given : \(g_{N} = 5.58\), \(\beta_{N} = 5.05 \times 10^{-27}\) JT-1 and h = 6.6 × 10-34 Js)

Exam Year(s)

MH SET - 2020, SET Exam - 2020,

Answer: D

The resonant frequency is about 100 MHz.

NMR resonance occurs when \(h\nu = g_{N}\beta_{N}B\):

\[ \begin{aligned} \nu &= \frac{g_{N}\beta_{N}B}{h} \\ &= \frac{5.58 \times 5.05 \times 10^{-27} \times 2.3}{6.6 \times 10^{-34}} \\ &= 9.8 \times 10^{7}\ \text{Hz} \approx 100\ \text{MHz} \end{aligned} \]

That matches the rule that protons resonate at about 42.6 MHz per tesla, so a 2.35 T magnet makes a '100 MHz' spectrometer. 1000 MHz would need about 23 T, and the kHz and 1 MHz options are far too low.

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