波谱分析课件 Chapter 4 Nuclear Magnetic Resonance Spectroscopy.ppt

Chapter 3 Nuclear Magnetic Resonance Spectroscopy Many atomic nuclei have the property of nuclear spin. When placed between the poles of a magnet, the axis of rotation of the spinning nuclei precess around the axis of the field. This precession can be detected by irradiation with energy in the radiofrequency region of the spectrum. When the precession and irradiation frequencies are equal the system is said to be in resonance. Nuclear Spin Do all nuclei have spin movement? Nuclear spin depends on its spin angular momentum number I If the protons and neutrons comprising these nuclei are not paired(one is odd number, the other even number), the overall spin of the charged nucleus generates a magnetic dipole along the spin axis. I=1/2, 3/2, 5/2 … Example: 1H, 13C, 15N, 19F, 31P Nuclear Spin (cont.) If both the protons and neutrons are even numbers, I=0, there is no nuclear spin movement. Example: 12C, 16O, 32S If both the protons and neutrons are odd number, I=1, 2, 3… , the nucleus will spin. Example: 2H, 14N The variations in frequency (w) is depended on the externally applied magnetic field of strength Bo CH3Br 60MHz(Bo=14100) w =162 Hz 100MHz(Bo=23500) w =270 Hz To correct the effect of Bo, Chemical shift of sample was compared with a standard TMS (tetramethyl silane) Chemical Shift δ on the left side of TMS + δ on the right side of TMS - TMS Only one peak on NMR spectrum High electronic density of H in TMS. Almost all the H peaks of organic compounds appear on the left of the TMS peak TMS is volatile compound(bp 26.5oC), very easy to remove. It dissolves in most organic solvents δ of TMS is set as 0 Calculation of chemical shift1,1,2-trichloropropane 3.3 Factors affecting chemical shift Depends on adjacent group For protons on carbon attached to an electronegative atom or group X, the chemical shift increases with the electronegativity of X. This is due to the inductive effect on the shielding of the prot