NMR SPECTROSCOPY

Comprehensive Study Notes

Nuclear Magnetic Resonance • Theory • Interpretation • Applications

Table of Contents
1. Introduction to NMR 2. Principle Behind NMR

3. Types of NMR 4. Interpretation of ¹H NMR

5. Chemical Shift & Shielding 6. Factors Affecting Chemical Shift

7. Spin-Spin Splitting (n+1 Rule) 8. Coupling Constant

9. Interpretation of ¹³C NMR 10. Decoupling Techniques

11. Sample Spectra 12. Conclusion

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 1. Introduction to NMR Spectroscopy
Nuclear Magnetic Resonance (NMR) spectroscopy is one of the most powerful and widely used analytical
techniques in modern chemistry. It allows chemists to determine the structure of organic molecules by
probing the magnetic properties of atomic nuclei — primarily hydrogen (¹H) and carbon-13 (¹³C) — and
thereby identify the carbon–hydrogen framework within molecules.

What NMR tells us:

• Changes occur at the nuclear level of atoms.

• A magnetic field is applied along with electromagnetic radiation (EMR).

• When the correct combination of B0 and EMR is applied, resonance (flipping of the
nucleus/proton) occurs — this gives the NMR signal.

Key Concept
NMR exploits the fact that certain atomic nuclei possess spin angular momentum. When placed in an
external magnetic field (B0), these nuclei align either with or against the field, producing two distinct energy
states. Absorption of radiofrequency (RF) radiation equal to the energy difference between these states
causes the nucleus to 'flip' — the resonance event that is detected and recorded as an NMR spectrum.

■ Note: NMR is non-destructive: samples can often be recovered after measurement. It is used extensively in
pharmaceutical, biochemical, and materials research.

2. Principle Behind NMR

2.1 Nuclear Spin

• Any charged particle (such as a proton) has a tendency to spin.
• A spinning charged particle develops a magnetic field around it — it behaves like a tiny bar magnet.
• In the absence of an external field the spin states have equal energy (degenerate).

2.2 Effect of External Magnetic Field (B■)

When placed in an external magnetic field B0, the spinning nucleus can adopt two orientations:

Spin +½ (α state) Spin −½ (β state)

Aligned with B0 Aligned against B0

Lower energy — Ground State (G.S.) Higher energy — Excited State (E.S.)

Slightly more populated Slightly less populated

2.3 Resonance Condition

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Resonance occurs when the nuclei absorb radiofrequency (RF) radiation whose energy exactly matches
the energy gap ∆E between the two spin states:

∆E = h·ν = µ·B0 / I

where: h = Planck's constant | ν = resonance frequency | µ = nuclear magnetic moment | B0 =

external field strength | I = spin quantum number

For ¹H and ¹³C: I = ½ → two spin states only.

At resonance the proton 'flips' from the lower energy α-state to the higher energy β-state. The RF
frequency required is proportional to B0. Modern NMR instruments use superconducting magnets
operating at fields corresponding to ¹H frequencies of 100 – 900 MHz.

■ Note: Higher field strength (B0) → larger ∆E → better sensitivity and resolution. Common laboratory
spectrometers operate at 300, 400, 500, or 600 MHz.

B■ Field (Tesla) ¹H Frequency (MHz)

2.34 100

4.73 200

6.35 270

8.46 360

11.75 500

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 3. Types of NMR Spectroscopy
Two types of NMR spectroscopy are routinely employed to study the structure of organic molecules:

Detects hydrogen atoms (protons). Determines the type and

¹H NMR (Proton NMR) number of H atoms in a molecule. Most sensitive and most
commonly used NMR technique.

Detects carbon-13 nuclei (I = ½). Determines the carbon

¹³C NMR (Carbon-13
skeleton of the molecule. Less sensitive than ¹H NMR but
NMR)
reveals the carbon framework.

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 4. Interpretation of ¹H NMR Spectrum
A ¹H NMR spectrum is interpreted using five key parameters. Each parameter reveals specific structural
information:

Number of Peaks Indicates the number of different types of protons in the

molecule. Chemically equivalent protons give a single signal.
Example: Ethanol (CH3CH2OH) shows 3 peaks — CH3, CH2,
OH.

Intensity of Peaks The relative area under each peak is proportional to the
number of protons of that type. Integration curves are used to
measure areas. Example: Ethanol — peaks in ratio 3:2:1
(CH3:CH2:OH).

Chemical Shift (δ) Reflects the electronic environment of the proton. Measured
in ppm relative to TMS (δ = 0). Shielded protons appear upfield
(low δ); deshielded protons appear downfield (high δ).

Splitting/Multiplicity Reveals the number of protons on adjacent carbons via the

n+1 rule. A proton with n neighbours splits into n+1 lines.

Coupling Constant (J) The distance between adjacent peaks in a multiplet,

measured in Hz. Independent of field strength; characteristic of
the proton type and geometry.

4.1 Number of Peaks — Examples

The number of peaks equals the number of chemically distinct proton environments.

Molecule No. of Peaks Peak Ratio

Ethane (CH3CH3) 1 — (all H equivalent)

Ethanol (CH3CH2OH) 3 3:2:1

Methoxyethane (CH3OCH2CH3) 3 3:2:3

Propan-1-ol (HOCH2CH2CH3) 4 1:2:2:3

Propan-2-ol ((CH3)2CHOH) 3 6:1:1

Benzyl acetate (C6H5CH2OCOCH3) 3 5:2:3

■ Note: Equivalent protons: Two protons are chemically equivalent if they are in the same chemical
environment (e.g., they can be interchanged by a symmetry operation). They give a single NMR signal.

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 5. Chemical Shift (δ)
The chemical shift is the position of an NMR signal on the frequency axis, expressed in parts per million
(ppm) relative to the internal standard TMS (tetramethylsilane). It arises because electrons surrounding a
nucleus shield it from the full applied field.

Definition: δ (ppm) = (νsample − νTMS) / νspectrometer × 106

Typical range for ¹H NMR: 0 – 12 ppm | Typical range for ¹³C NMR: 0 – 220 ppm

5.1 TMS — The Internal Standard

• TMS = Tetramethylsilane, Si(CH3)4
• Has 12 equivalent hydrogen atoms → produces a single, intense peak.
• Protons are highly shielded (Si is less electronegative than C) → NMR peak is at δ = 0, upfield of
almost all organic protons.
• Chemically inert, low boiling point, easily removed.
• Assigned δ = 0.00 ppm by convention.

5.2 Shielding and Deshielding

The electron cloud surrounding a nucleus generates a small induced magnetic field that opposes the
applied field B0. The nucleus therefore 'feels' a slightly reduced effective field (Beff = B0 − σ·B0).

Shielded Proton Deshielded Proton

High electron density around H Low electron density around H

Induced field opposes B0 Effective field closer to B0

Needs higher B0 to resonate Resonates at lower external field

Resonates at lower δ (upfield) Resonates at higher δ (downfield)

Example: CH3 groups (δ ≈ 0.9 ppm) Example: –OH, –CHO (δ > 9 ppm)

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 6. Factors Affecting Chemical Shift

6.1 Electronegativity
Electronegative substituents (F, O, N, Cl, Br, I) withdraw electron density from the nearby C–H bonds
through the σ-bond framework (inductive effect). This deshields the adjacent proton, increasing its
chemical shift.

Compound CH3I CH3Br CH3Cl CH3F

δ (ppm) 2.16 2.65 3.10 4.26

• Key rules:
– Greater electronegativity → more deshielding → higher δ.
– Multiple electronegative substituents have a cumulative effect: CHCl3 δ 7.27 > CH2Cl2 δ 5.30 >
CH3Cl δ 3.05
– More substituted carbons are more deshielded: 3° > 2° > 1°

6.2 Hybridization
The type of hybridization of the carbon bearing the proton determines the chemical shift because s-orbitals
hold electrons closer to the nucleus than p-orbitals.

Hybridization % s-character Chemical Shift (δ, ppm) Example

sp3 25% 0.1 – 4.0 Alkanes, CH3

sp2 33.3% 4.5 – 7.0 Alkenes, Aromatics

Alkynes (due to
sp 50% 2.0 – 3.0 (anomalous)
anisotropy)

■ Note: Vinyl protons (sp2, alkenes) resonate at higher δ than aliphatic (sp3) protons because the s-orbital
holds electrons closer to carbon, leaving protons more deshielded. The anomalously low shift of alkyne
protons (sp) is due to magnetic anisotropy (shielding along the molecular axis).

6.3 Magnetic Anisotropy

Magnetic anisotropy refers to the non-uniform magnetic field created by π-electrons (in aromatics,
alkenes, alkynes, carbonyls) when they interact with B0. This induced field causes both shielding and
deshielding depending on the spatial position of the proton relative to the π-system.

Observe
System Proton Position Effect dδ
(ppm)

Deshielded (induced field

Benzene (aromatic) In ring plane (equatorial) ≈ 7.27
adds to B0)

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 Shielded (field opposes
Benzene (aromatic) Above/below ring —
B0)

Alkene (C=C) Vinyl protons Deshielded 4.5 – 6.5

Alkyne (C≡C) Terminal ≡C–H Shielded (along axis) 2.0 – 3.0

Carbonyl (C=O) Aldehyde H Strongly deshielded 9 – 10

Benzene ring current: Delocalized π-electrons circulate in the aromatic ring under B0, creating a ring
current. The induced field reinforces B0 at the equatorial positions (where H atoms lie) → strong
deshielding → δ ≈ 7–8 ppm. Above and below the ring plane the induced field opposes B0 → shielding.

Acetylene (sp carbons): The cylindrical π-electron cloud circulates in a way that the induced field
opposes B0 along the molecular axis where the terminal H sits → shielding → anomalously low δ (2–3
ppm) despite high s-character.

6.4 Hydrogen Bonding

• Protons involved in hydrogen bonding (–OH, –NH, –COOH) are deshielded.
• Stronger H-bonding → greater deshielding → higher δ.
• These signals are often broad and their position varies with concentration, temperature, and solvent.
• Carboxylic acid –COOH protons: δ ≈ 10–12 ppm (very strong H-bonding).
• Alcohol –OH: δ ≈ 0.5–5 ppm (variable).

6.5 Typical ¹H Chemical Shift Reference Table

Proton Environment δ (ppm)

TMS (reference) 0.00

R–CH3 (primary alkyl) 0.9 – 1.0

R2–CH2 (secondary alkyl) 1.2 – 1.4

R3–CH (tertiary alkyl) 1.4 – 1.7

C≡C–H (terminal alkyne) 2.0 – 3.0

C–CH2–C=O (next to carbonyl) 2.0 – 2.7

R–O–CH3 (methoxy) 3.3 – 3.5

R–Cl, R–Br (next to halogen) 3.0 – 4.5

C=C–H (vinyl) 4.5 – 6.5

ArH (aromatic) 6.5 – 8.5

R–CHO (aldehyde) 9.0 – 10.0

R–COOH (carboxylic acid) 10.0 – 12.0

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7. Spin-Spin Splitting / Multiplicity — The n+1 Rule
Spin-spin splitting (also called scalar coupling) arises because protons on adjacent carbons sense each
other's magnetic spin states. This interaction is transmitted through bonds (not through space) and splits a
single NMR peak into a multiplet.

The n+1 Rule: If a proton has n equivalent neighbouring protons (on adjacent carbons), its signal
is split into n+1 lines (a multiplet).

The relative intensities of the lines in the multiplet follow Pascal's Triangle.

7.1 Multiplicity Nomenclature

n (neighbours) Multiplicity Pattern Intensity Ratio

0 Singlet (s) 1 line 1

1 Doublet (d) 2 lines 1:1

2 Triplet (t) 3 lines 1:2:1

3 Quartet (q) 4 lines 1:3:3:1

4 Quintet 5 lines 1:4:6:4:1

5 Sextet 6 lines 1 : 5 : 10 : 10 : 5 : 1

6 Septet 7 lines 1 : 6 : 15 : 20 : 15 : 6 : 1

8 Nonet 9 lines Pascal row 9

7.2 Theory Behind Spin-Spin Splitting

Though the applied magnetic field B0 is constant, each proton experiences a slightly different local field
because its neighbouring protons can be aligned with or against B0. These different local fields cause the
resonance frequency of the observed proton to shift slightly — giving rise to the observed multiplet pattern.

• A proton with 2 equivalent neighbours (e.g., CH2) splits into a triplet (net spin combinations: +1, 0,
−1 with intensities 1:2:1).
• A proton with 3 equivalent neighbours (e.g., CH3) splits into a quartet (net spins: +3/2, +1/2, −1/2,
−3/2 with intensities 1:3:3:1).

7.3 Pascal's Triangle

Pascal's Triangle gives the relative peak intensities within each multiplet. The difference in peak areas is
due to the different statistical probabilities of the various spin arrangements of adjacent protons.

Multiplet Pascal's Triangle Row

Singlet 1

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 Doublet 11

Triplet 121

Quartet 1331

Quintet 14641

Sextet 1 5 10 10 5 1

Septet 1 6 15 20 15 6 1

7.4 Common Splitting Pattern Examples

• No neighbours: Singlet (n+1 = 1) | area = relative count
• One neighbour: Doublet (n+1 = 2)
• Two neighbours: Triplet (n+1 = 3)
• Six neighbours: Septet (n+1 = 7)
• Ethyl iodide (CH3CH2I): CH2I quartet (n=3), CH3 triplet (n=2) | Integral 2:3
• 2-Nitropropane (CH3CHCH3, NO2): CH septet (6 neighbours), 2×CH3 doublet | Integral 1:6
• Ethyl ethanoate (CH3COOCH2CH3): OCOCH3 singlet (n=0), OCH2 quartet (n=3), CH3 triplet (n=2)

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 8. Coupling Constant (J)
The coupling constant J is the distance (in Hz) between adjacent peaks of a multiplet. It measures the
strength of spin-spin coupling between two nuclei.

• J is independent of the external field B0 (unlike chemical shift in Hz).

• J is specific to each type of proton pair and depends on the number of bonds, bond angles, and
dihedral angles.

• Measured in Hertz (Hz) or cycles per second (cps).

• For a doublet: J = separation between the two lines.

• For a triplet: J = separation between adjacent lines (all equal).

Coupling Type Typical J (Hz)

3
J vicinal (H–C–C–H, free rotation) 6–8 Hz
3
J vicinal (cis alkene) 6–12 Hz
3
J vicinal (trans alkene) 12–18 Hz
2
J geminal (H–C–H) 10–15 Hz
4
J long-range (allylic) 0–3 Hz

Aromatic (ortho) 6–9 Hz

Aromatic (meta) 1–3 Hz

Aromatic (para) 0–1 Hz

■ Note: Because J is field-independent, it is the same in a 300 MHz or 600 MHz instrument. This makes J a
reliable diagnostic parameter for structure elucidation.

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 9. Interpretation of ¹³C NMR Spectrum

9.1 Why ¹³C NMR?

• Carbon NMR provides information about the carbon skeleton of a molecule.
• ¹²C (most abundant, 98.9%) has I = 0 → NMR inactive.
• ¹³C has I = ½ and is NMR active, but its natural abundance is only 1.08%.
• The resonance signals of ¹³C are about 6000 times weaker than ¹H signals.
• Because only ~1% of carbons are ¹³C, the chance of two adjacent ¹³C atoms in the same molecule is
very low (~0.01%). Most spectra arise from a combination of many individual scans (FT-NMR).

9.2 ¹³C Chemical Shifts

¹³C NMR has a much wider chemical shift range (0–220 ppm) compared to ¹H NMR (0–12 ppm). The
same factors that affect ¹H shifts (electronegativity, hybridization, anisotropy) also affect ¹³C shifts, but the
effect is larger because the electronegative atom is directly bonded to carbon (through one bond C–X),
whereas for protons the effect occurs through two bonds (H–C–X).

Carbon Type δ Range (ppm)

R–CH3 (primary) 8–30

R2CH2 (secondary) 15–55

R3CH (tertiary) 20–60

C–O (ether, alcohol) 40–80

C–Cl 35–80

C–Br 25–65

C–I 0–40

C–N 30–65

C≡C (alkyne) 65–90

C=C (alkene) 100–150

ArC (aromatic) 110–175

C≡N (nitrile) 110–140

R–COOR, R–COOH (ester, acid) 155–185

R–CONH2 (amide) 155–185

R–COR, R–CHO (ketone, aldehyde) 185–220

9.3 Spin-Spin Splitting in ¹³C NMR (Heteronuclear Coupling)

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 In ¹³C NMR, each carbon is split by the directly attached protons (H–¹³C coupling, 1J). The n+1 rule
applies — but here n is the number of H atoms directly bonded to that ¹³C.

Carbon Type Attached H n+1 Pattern

Methyl (–CH3) 3 4 Quartet

Methylene (–CH2–) 2 3 Triplet

Methine (–CH–) 1 2 Doublet

Quaternary (–C–) 0 1 Singlet

9.4 Proton Decoupling Techniques

Because ¹³C signals are weak and overlapping multiplets are complex, modern instruments apply
decoupling techniques:

Broad-Band Proton All ¹H–¹³C coupling is removed by irradiating all ¹H frequencies

Decoupled (BBD) simultaneously. Every ¹³C appears as a single sharp singlet. Simple
spectrum — easy to count carbons. Disadvantage: loses multiplicity
information about attached H atoms.

Off-Resonance Only long-range C–H couplings are removed; directly attached H–C
Decoupled (ORD) coupling is retained. Gives simplified multiplets indicating CH3
(quartet), CH2 (triplet), CH (doublet), and quaternary C (singlet). Helps
assign carbon types without full complexity.

DEPT (Distortionless Modern pulse sequence that differentiates CH3, CH2, CH, and C.
Enhancement by Peaks appear positive or negative depending on the number of
Polarisation attached H — most powerful method for carbon assignment.
Transfer)

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 10. Sample Spectra Analysis
Benzyl Acetate (¹H NMR)
C6H5CH2OCOCH3 — Three distinct proton environments.

Proton
δ (ppm) No. H Pattern Integral Ratio
Group

ArH (phenyl) 7.3 – 7.5 5 Multiplet 5

OCH2 5.1 2 Singlet 2

OCOCH3 2.0 3 Singlet 3

2,2-Dimethylbutane (¹³C NMR, proton-decoupled)

CH3–C(CH3)2–CH2–CH3 — Four unique carbon environments.

Carbon Label δ (ppm) Multiplicity (ORD)

CH3 terminal (×3 equivalent,

b ≈ 32 Quartet
C(CH3)3)

Quaternary C c ≈ 32 Singlet

CH2 d ≈ 36 Triplet

Terminal CH3 a ≈8 Quartet

Cyclohexanol (¹³C NMR, proton-decoupled)

C6H11OH — Four unique carbons due to symmetry (ring symmetry reduces 6C to 4 types).

Carbon Label δ (ppm)

C–OH (bearing oxygen) d ≈ 70

Adjacent CH2 a ≈ 35

Next CH2 b ≈ 26

Farthest CH2 c ≈ 24

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Cyclohexene (¹³C NMR, proton-decoupled)
C6H10 — Three unique carbons (ring symmetry).

Carbon Label δ (ppm) Environment

sp2 C=C c ≈ 127 Alkene carbon

Allylic CH2 a ≈ 25 Adjacent to double bond

CH2 b ≈ 22 Saturated ring CH2

Cyclohexanone (¹³C NMR, proton-decoupled)

C6H10O — Four unique carbons. Carbonyl at δ 211.3 ppm.

Carbon Label δ (ppm) Environment

C=O (carbonyl) d 211.3 Ketone carbon — very downfield

α-CH2 (×2 eq.) c ≈ 41 Adjacent to C=O

β-CH2 (×2 eq.) b ≈ 27 Beta to C=O

γ-CH2 (×2 eq.) a ≈ 25 Gamma to C=O

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 11. Quick Reference Summary

11.1 Step-by-Step Guide to Reading a ¹H NMR Spectrum

• Step 1: Count the number of peaks → tells you the number of distinct proton environments.
• Step 2: Measure the integration (area under each peak) → gives the relative ratio of H atoms.
• Step 3: Read the chemical shift (δ) of each peak → identifies the type of proton (alkyl, vinyl,
aromatic, etc.).
• Step 4: Determine the multiplicity of each peak → apply n+1 rule to find the number of adjacent H.
• Step 5: Measure the coupling constant J → confirms coupling partners and geometry.
• Step 6: Combine all information to propose a molecular structure consistent with the spectrum.

11.2 Common ¹H Chemical Shifts at a Glance

δ (ppm) Proton Type

0.0 TMS (reference)

0.9 R–CH3 (primary alkyl)

1.2–1.4 R–CH2–R (secondary alkyl)

2.0–2.5 α to C=O, allylic

2.0–3.0 C≡C–H (alkyne, anisotropy)

3.3–3.5 O–CH3 (methoxy)

3.5–4.5 C–halogen, C–O

4.5–6.5 C=C–H (vinyl)

6.5–8.0 Ar–H (aromatic)

9–10 R–CHO (aldehyde)

10–12 RCOOH, strong H-bond

11.3 Common ¹³C Chemical Shifts at a Glance

δ (ppm) Carbon Type

8–30 R–CH3

15–55 R2CH2

20–60 R3CH, R4C

40–80 C–O

35–80 C–Cl

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 65–90 C≡C (alkyne)

100–150 C=C (alkene)

110–175 Aromatic C

155–185 Ester, acid, amide carbonyls

185–220 Ketone, aldehyde carbonyls

11.4 Multiplicity Summary (n+1 Rule)

Signal n neighbours n+1 lines Intensity ratio

Singlet 0 1 1

Doublet 1 2 1:1

Triplet 2 3 1:2:1

Quartet 3 4 1:3:3:1

Quintet 4 5 1:4:6:4:1

Sextet 5 6 1:5:10:10:5:1

Septet 6 7 1:6:15:20:15:6:1

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 12. Conclusion
NMR spectroscopy is an indispensable tool in the structural characterisation of organic molecules. By
analysing the four key parameters of a ¹H NMR spectrum (number of peaks, intensity, chemical shift, and
splitting pattern) and the complementary information from ¹³C NMR, chemists can determine molecular
structures with remarkable precision and confidence.

Key Takeaways:

• NMR is based on the absorption of radiofrequency radiation by nuclei with spin I = ½ placed in
an external magnetic field.

• ¹H NMR: reveals number, type, and connectivity of hydrogen atoms.

• ¹³C NMR: reveals the carbon skeleton; wide shift range (0–220 ppm).

• Chemical shift reflects electronic environment — shielding (upfield) vs. deshielding (downfield).

• The n+1 rule and Pascal's Triangle predict splitting patterns.

• Coupling constant J (Hz) is field-independent and identifies neighbouring protons.

• Used together with IR spectroscopy, the complete molecular structure can often be established
unambiguously.

• Wide applications in pharmaceutical development, metabolomics, polymer chemistry, and

quality control.

These notes were compiled from the NMR_Consolidated slide deck and expanded with additional detail to serve as a
comprehensive study reference.

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