![The number of orientations of the spin state is given by
(2I+1) where I is the spin quantum no. We know that proton
(H) has I=1/2 and it has only two orientations.
Page 4
No. of orientations for H =(2I+1)
=[2*1/2+1]
=2
Transition from one possible orientation to another may be
achieved by absorption or emission of electromagnetic
radiation.
The energy required for flipping depends upon strength
of applied magnetic field.
Processional motion of nucleus in applied magnetic
field.
Processional motion of nucleus in applied
magnetic field](https://image.slidesharecdn.com/nmrtheory-140929000832-phpapp01/85/Nmr-theory-4-320.jpg)
Nmr theory
- 1. NUCLEAR MAGNETIC RESONANCE Page 1 SPECRTOSCOPY INTRODUCTION The phenomenon of nuclear magnetic resonance (NMR) was first observed in 1946 and it has been routinely applied in organic chemistry since about 1960.NMR spectroscopy is one of the most useful technique for structural elucidation available to organic chemist. In NMR we are going to study the interaction of the magnetic component with the certain nuclei hence the name NMR spectroscopy is given. Princple The NMR spectroscopy deals with nucleus of an atom that possesses magnetic moment. The nucleus of an atom is positively charged. Like electron the nuclei of certain atom also spin about their axis . The spinning of these charged particle generate a magnetic moment along the axis of the spin, so that these nuclei act like tiny bar magnet. Individual protons & neutrons have spin quantum no. +1/2 & -1/2 . Therefore depending on number of nucleons (protons+ neutrons) certain nuclei also possesses spin. The total spin quantum no. ‘I’ is a characteristic of nucleus. The nuclei that have spin no. greater than zero possesses spin.
- 2. Page 2 Magnetic and Nonmagnetic Nuclei To find out nuclear spin quantum no. I following rules are generally applied. a) Nucleus with I>0 when spins about its own axis generates a magnetic moment and are known as magnetic nuclei. b) The Nucleus with I=0 does not produce magnetic moment and are known as nonmagnetic nuclei . The nuclei which have even mass number and even atomic number have zero spin quantum no. are nonmagnetic c) The nuclei with I>0 possesses spin angular momentum and produce magnetic field are known as magnetic nuclei. 1) The nuclei which have odd mass no. and odd or even atomic no. have half integral spin like ½, 3/2, 5/2, and possesses spin quantum no. I=1/2. These are magnetic nuclei. 2) The nuclei having even mass no. and odd atomic no. have integral spin quantum no. such as 1, 2, 3 etc. possesses spin quantum no. I=1. These are also magnetic nuclei
- 3. Page 3 Nuclear Resonance
- 4. The number of orientations of the spin state is given by (2I+1) where I is the spin quantum no. We know that proton (H) has I=1/2 and it has only two orientations. Page 4 No. of orientations for H =(2I+1) =[2*1/2+1] =2 Transition from one possible orientation to another may be achieved by absorption or emission of electromagnetic radiation. The energy required for flipping depends upon strength of applied magnetic field. Processional motion of nucleus in applied magnetic field. Processional motion of nucleus in applied magnetic field
- 5. Page 5 NMR spectrometer
- 6. Page 6 NMR Graph
- 7. Page 7 Shielding and Deshielding
- 8. The induced magnetic field tries to protection the nucleus from applied magnetic field H0 . This type of protection of nuclei from H0 is called as diamagnetic shielding . When nuclei is not protected by induced magnetic field then Deshielding takes place .Thus the shielding and Deshielding depends upon the electron density around the proton. Page 8 a) More the electron density around the proton more is induced magnetic field and therefore more shielding of proton from applied magnetic field.
- 9. Page 9 Shielding For example:-Acetylene molecule Deshielding Example:-Benzene molecule
- 10. Page 10 CHEMICAL SHIFT Each nucleus (proton) in different environment requires a slightly different applied magnetic field H0 for resonance and peaks occur in different regions of the spectrum . For proton NMR spectra of organic compound the single resonance peak if the methyl groups in ‘Tetra methyl silane’ (TMS) is taken as a internal reference standard. The distance in ‘d’ values from TMS to each signal (absorption or peak ) in the spectrum is called the chemical shift for the proton or proton giving that signal.
- 11. Page 11 Advantages of TMS 1. It is chemically inert. 2. It gives unique line position. 3. It is symmetrical molecule and gives single and strong , sharp absorption peak as all 12 protons are equivalent. 4. Methyl protons of TMS are strongly shielded and hence absorption occurs at high field . It is taken as zero ppm. 5. It is soluble in most of organic solvents. 6. It is volatile(b.p.270c)and hence the recovery of sample is possible.
- 12. Measurement of Chemical shift. chemical shift is measured in frequency unit ‘Hertz’. Most of routine instruments operate at 60, 90, 100 MHz. More sophisticated instruments operate as high as 600MHz. The chemical shift recorded in Hz may vary with the spectrometer. To avoid this complication the chemical shift values are expressed in terms of delta or tau scale. Which are independent of field strength. Chemical shift in delta scale are expressed in parts per million (ppm). Page 12
- 13. Page 13 Delta Scale
- 14. Page 14
- 15. Page 15 Typical Values Functional Group Chemical Shift Alkane 0.8-1.2 1.6 Benzyl 2.3 Carbonyl 2.2 Amine 2.3 Alcohol 3.3 Alkyl Halide 3.6 Alkene 4.5-6.0 Benzene 6.0-9.0 Alcohol 0.5-4.5 Very Broad Carbox. acid 9.0-15.0 R CH3 C HC CH3 CH3 R C CH3 O R N CH3 HO CH3 H3C Cl H2C CH2 H R OH R O OH
- 16. Page 16 Spin-SSppiinn CCoouupplliinngg((SSpplliittttiinngg)) The NMR spectrum at low resolution shows a no. of broad absorption peaks (signals) corresponding to the protons in different chemical environment. Area under each peak is proportional to the no. of protons. However at high resolution these NMR signal shows multiplicity. That is they get split into several signals. It must be noted that area under signals remain the same. This multiplicity of lines is due to spin-spin coupling, which arise from small magnetic interactions that occur between the nuclei of neighboring atoms. The nuclei are said to be coupled and resulting NMR spectral pattern is known as spin-spin splitting.
- 17. Page 17 The N+1 Rule If the signal is spit by N equivalent protons, it is spit into N+1 peaks. n n + 1 Pascal pattern: 0 singlet 1 1 doublet 2 2 triplet 3 3 quartet 4 4 quintet 5
- 18. Page 18 Range of magnetic coupling Equivalent protons do not split each other. Protons bonded to the same carbon will split each other only if they are not equivalent. Protons on adjacent carbons normally will couple. Protons separated by four or more bonds will not couple. Coupling Constant The distance in Hz between adjacent peaks of a multiplet . It is measured in Hz. Range o-8 Hz. Independent of magnetic field strength. Where as the chemical shift in Hz is directly proportional to the field strength.
- 19. Page 19 Other Techniques for NMR Property Value Spin ½ Natural abundance 100% Chemical shift range 700 ppm, from -300 to 400 Frequency ratio (Ξ) 94.094011% Reference compound CFCl3 = 0 ppm Linewidth of reference T1 of reference Receptivity rel. to 1H at natural abundance 0.83 Receptivity rel. to 1H when enriched 0.83 Receptivity rel. to 13C at natural abundance 4716 Receptivity rel. to 13C when enriched 4716 19F NMR 19Fluorine is a sensitive nucleus which yields sharp signals and has a wide chemical shift range. A typical analysis of a 19F NMR spectrum may proceed similarly to that of Proton (1H). Our NMR service provides 19F NMR along with many other NMR techniques. The number of fluorines of each type in the spectrum of a pure sample can be obtained directly from the integrals of each multiplet provided that the multiplets are well separated which is very likely to the large chemical shift range. A routine NMR spectrum yields integrals with an accuracy of ±10%. Accuracies of ±1% can be achieved by increasing the relaxation delay to five times the longitudinal relaxation times (T1) of the signals of interest.
- 20. Page 20 13C NMR The 1D 13Carbon NMR experiment is much less sensitive than Proton (1H) but has a much larger chemical shift range. Its low natural abundance (1.108%) and proton decoupling means that spin-spin couplings are seldom observed. This greatly simplifies the spectrum and makes it less crowded. 13C is a low sensitivity nucleus that yields sharp signals and has a wide chemical shift range. A typical analysis of a 13C NMR spectrum consists of matching expected chemical shifts to the expected moieties. Our NMR service provides 13C NMR along with many other NMR techniques Each type of signal has a characteristic chemical shift range that can be used for assignment Property Value Spin ½ Natural abundance 1.108% Chemical shift range 200 ppm, from 0 to 200 Frequency ratio (Ξ) 25.145020% Reference compound TMS < 1% in CDCl3 = 0 ppm Linewidth of reference 0.19 Hz T1 of reference 9 s Receptivity rel. to 1H at natural abundance 1.70×10-4 Receptivity rel. to 1H when enriched 0.0159 Receptivity rel. to 13C at natural abundance 1.00 Receptivity rel. to 13C when enriched 93.5
- 21. Page 21 Property Value Spin ½ Natural abundance 100% Chemical shift range 430 ppm, from -180 to 250 Frequency ratio (Ξ) 40.480742% Reference compound 85% H3PO4 in H2O = 0 ppm Linewidth of reference 1 Hz T1 of reference 0.5 s Receptivity rel. to 1H at natural abundance 6.63 × 10-3 Receptivity rel. to 1H when enriched 6.63 × 10-3 Receptivity rel. to 13C at natural abundance 37.7 Receptivity rel. to 13C when enriched 37.7 31P NMR The 1D 31Phosphorus NMR experiment is much less sensitive than Proton (1H) but more sensitive than 13Carbon. 31Phosphorus is a medium sensitivity nucleus that yields sharp lines (fig. 1) and has a wide chemical shift range. It is usually acquired with 1Hdecoupling (fig. 2) means that spin-spin couplings are seldom observed. This greatly simplifies the spectrum and makes it less crowded. Where there are one-bond 31P-1H couplings present then the decoupling power needs to be at lest twice that needed for 13C because of the large coupling constant.
- 22. Page 22 Conclusion • 1) To find out different kinds of protons in the molecule. • 2) The intensity of a signal that is area under the signal gives idea about the proton ratio in the compound. • 3) Position of signals tells us about the electronic environment of proton. • 4)The proton in the vicinity of aromatic ring has higher delta value (7-9) • 5)Multiplicity of signal tells us about information of neighbouring protons. • 6) Detection of hydrogen bonding. • 7) Study of geometrical isomerism as well as conformation. • 8) J helps to study the NMR spectrum of more complex compound.
- 23. Page 23 Bibliography:- NMR, NQR, EPR and Mossbauer Spectroscopy in Inorganic Chemistry, .V. Parish, Ellis Haywood. Practical NMR Spectroscopy, M.L. Martin. J.J. Deepish and G.J. Martin, Heyden. Spectrometric Identification of Organic Compounds, R.M. Silverstein, G.C. Bassler adn T.C. Morrill, John Wiley. Introduction to NMR spectroscopy, R.J. Abraham, J. Fisher and P. Loftus, Wiley. Application of Spectroscopy of Organic Compounds, J.R. Dyer Prentice Hall. Spectroscopic Methods in Organic Chemistry D.H. Williams, I. Fleming, Tata McGraw-Hill.