高分子材料研究方法-核磁共振与电子顺磁共振波谱法课件.pptxVIP

Chap 3 NMR Spectroscopy and EPR SpectroscopyIntroduction1H NMR Spectroscopy13C NMR SpectroscopyEPR SpectroscopyApplications on Polymers1 3.1 IntroductionMagnetism and SpinMagnetic ResonanceNMR SpectroscopyEPR Spectroscopy2 3.1.1 Magnetism and SpinMagnetismMoving charges generate magnetic fieldsThe magnetism of materials are related with the spin of microparticles3 3.1.1 Magnetism and Spin4 3.1.2 Magnetic ResonanceMagnetic Resonance5 3.1.3 NMR Spectroscopy6 3.1.3 NMR Spectroscopy7 3.1.3 NMR SpectroscopyRelaxation: excited nuclei return to the lower energy levels without radiationSpin-crystal relaxation: energy exchanged to surrounding particles/ T1 (half life)Spin-spin relaxation: energy exchanged with adjacent nucleus/ T2 (half life)8 3.1.4 EPR SpectroscopyUnpaired electrons9 3.2 1H NMR SpectroscopyChemical ShiftsSpin-Spin CouplingIntegral of Absorption PeakElucidation of 1H NMR Spectra10 3.2.1 Chemical Shifts11 3.2.1 Chemical ShiftsThe Shielding EffectHeff = H0(1-σ)ν=γHeff /2πHeff: the field experienced by the nucleus;H0: the external field (of the spectrometer);σ: the nondimensional shielding constant; ν: the frequency at which NMR transitionoccurs; γ: the magnetogyric ratio.12 3.2.1 Chemical ShiftsThe Shielding EffectShielding：H attached to an electron-donating substituent → a decrease in HeffDeshielding:H attached to an electron-withdrawing group → an increase in Heff13 3.2.1 Chemical ShiftsChemical Shifts?δ=(νsample-νreference)/νspectrometer ×106 (ppm)Normally, tetramethylsilane (TMS) is chosen as the reference in non-aqueous media. In TMS, 12 protons are all chemically equivalent and give a single peak at an H0 higher than most otherproton resonances.14 15 3.2.1 Chemical ShiftsChemical ShiftsThe range of the 1H chemical shifts:rather small, 0-15.H0 will not influence the 1H chemical shifts16 3.2.1 Chemical ShiftsChemical ShiftsFactors influencing chemical shifts:① The electronegtivity:The more electronegtive the atom which the carbon bearing the proton is atta