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SPECTROSCOPY By Dr. S. R. Mane

SPECTROSCOPY By Dr. S. R. Mane M.Sc. B.Ed. Ph.D. Associate Prof. and Head, Department of Chemistry, Smt. Kusumtai Rajarambapu Patil Kanya Mahavidyalaya , Islampur . Dist.- Sangli . Email – sambhaji_mane@rediffmail.com.

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SPECTROSCOPY By Dr. S. R. Mane

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  1. SPECTROSCOPY By Dr. S. R. Mane M.Sc. B.Ed. Ph.D. Associate Prof. and Head, Department of Chemistry, Smt. KusumtaiRajarambapuPatilKanyaMahavidyalaya, Islampur. Dist.- Sangli. Email – sambhaji_mane@rediffmail.com

  2. NUCLEAR MAGNETIC RESONANCE (NMR) SPECTROSCOPY

  3. NUCLEAR SPIN The nuclei of some atoms have a property called “SPIN”. These nuclei behave as if they were spinning. ….. we don’t know if they actually do spin! This is like the spin property of an electron, which can have two spins: +1/2 and -1/2 . Each spin-active nucleus has a number of spins defined by its spin quantum number, I. The spin quantum numbers of some common nuclei follow …..

  4. Spin Quantum Numbers of Some Common Nuclei The most abundant isotopes of C and O do not have spin. Element1H 2H 12C 13C 14N 16O 17O 19F Nuclear Spin Quantum No1/2 1 0 1/2 1 0 5/21/2 ( I ) No. of Spin 2 3 0 2 3 0 6 2 States Elements with either odd mass or odd atomic number have the property of nuclear “spin”. The number of spin states is 2I + 1, whereI is the spin quantum number.

  5. THE PROTON Although interest is increasing in other nuclei, particulary C-13, the hydrogen nucleus (proton) is studied most frequently, and we will devote our attention to it first.

  6. NUCLEAR SPIN STATES - HYDROGEN NUCLEUS The spin of the positively charged nucleus generates a magnetic moment vector, m. m + + The two states are equivalent in energy in the absence of a magnetic or an electric field. m + 1/2 - 1/2 TWO SPIN STATES

  7. THE “RESONANCE” PHENOMENON absorption of energy by the spinning nucleus

  8. Nuclear Spin Energy Levels N -1/2 unaligned In a strong magnetic field (Ho) the two spin states differ in energy. +1/2 aligned Ho S

  9. Absorption of Energy quantized Opposed -1/2 -1/2 DE DE = hn Radiofrequency +1/2 +1/2 Applied Field H0 Aligned

  10. THE ENERGY SEPARATION DEPENDS ON Bo - 1/2 = kBo = hn DE Degenerate at H0 = 0 + 1/2 H0 Increasing magnetic field strength

  11. The Larmor Equation!!! DE = kBo = hncan be transformed into Gyromagnetic ratio g Frequency of the incoming radiation that will cause a transition g H0 n = 2p Strength of the magnetic field g is a constant which is different for each atomic nucleus (H, C, N, etc)

  12. A SECOND EFFECT OF A STRONG MAGNETIC FIELD WHEN A SPIN-ACTIVE HYDROGEN ATOM IS PLACED IN A STRONG MAGNETIC FIELD ….. IT BEGINS TO PRECESS OPERATION OF AN NMR SPECTROMETER DEPENDS ON THIS RESULT

  13. N w Nuclei precess at frequency w when placed in a strong magnetic field. RADIOFREQUENCY 40 - 600 MHz hn NUCLEAR MAGNETIC RESONANCE If n = w then energy will be absorbed and the spin will invert. NMR S

  14. Resonance Frequencies of Selected Nuclei Isotope Abundance Ho (Tesla) Frequency(MHz) g(radians/Tesla) 1H 99.98% 1.00 42.6 267.53 1.41 60.0 2.35 100.0 7.05 300.0 2H 0.0156% 1.00 6.5 41.1 7.05 45.8 13C 1.108% 1.00 10.7 67.28 2.35 25.0 7.05 75.0 19F 100.0% 1.00 40.0 251.7 4:1

  15. POPULATION AND SIGNAL STRENGTH The strength of the NMR signal depends on the Population Difference of the two spin states Radiation induces both upward and downward transitions. induced emission resonance For a net positive signal there must be an excess of spins in the lower state. excess population Saturation = equal populations = no signal

  16. CLASSICAL INSTRUMENTATION typical before 1960 field is scanned

  17. A Simplified 60 MHz NMR Spectrometer hn RF (60 MHz) Oscillator RF Detector Absorption signal Recorder Transmitter Receiver MAGNET MAGNET S N Probe

  18. hn Fortunately, different types of protons precess at different rates in the same magnetic field. Ho = 1.41 Tesla N EXAMPLE: 59.999995 MHz 59.999700 MHz To cause absorption of the incoming 60 MHz the magnetic field strength, Bo , must be increased to a different value for each type of proton. 59.999820 MHz 60 MHz S Differences are very small, in the parts per million range.

  19. IN THE CLASSICAL NMR EXPERIMENT THE INSTRUMENT SCANS FROM “LOW FIELD” TO “HIGH FIELD” LOW FIELD HIGH FIELD NMR CHART increasing Ho DOWNFIELD UPFIELD scan

  20. NMR Spectrum of Phenylacetone NOTICE THAT EACH DIFFERENT TYPE OF PROTON COMES AT A DIFFERENT PLACE - YOU CAN TELL HOW MANY DIFFERENT TYPES OF HYDROGEN THERE ARE

  21. MODERN INSTRUMENTATION PULSED FOURIER TRANSFORM TECHNOLOGY FT-NMR requires a computer

  22. PULSED EXCITATION N n2 n1 BROADBAND RF PULSE contains a range of frequencies n3 (n1 ..... nn) S All types of hydrogen are excited simultaneously with the single RF pulse.

  23. FREE INDUCTION DECAY ( relaxation ) n1 n2 n3 n1, n2, n3 have different half lifes

  24. COMPOSITE FID “time domain“ spectrum n1 + n2 + n3 + ...... time

  25. FOURIER TRANSFORM A mathematical technique that resolves a complex FID signal into the individual frequencies that add together to make it. ( Details not given here. ) DOMAINS ARE MATHEMATICAL TERMS converted to TIME DOMAIN FREQUENCY DOMAIN FID NMR SPECTRUM FT-NMR computer n1 + n2 + n3 + ...... COMPLEX SIGNAL Fourier Transform individual frequencies a mixture of frequencies decaying (with time) converted to a spectrum

  26. The Composite FID is Transformed into a classical NMR Spectrum “Frequency domain” spectrum

  27. COMPARISON OF CW AND FT TECHNIQUES

  28. CONTINUOUS WAVE (CW) METHOD THE OLDER, CLASSICAL METHOD The magnetic field is “scanned” from a low field strength to a higher field strength while a constant beam of radiofrequency (continuous wave) is supplied at a fixed frequency (say 100 MHz). Using this method, it requires several minutes to plot an NMR spectrum. SLOW, HIGH NOISE LEVEL

  29. PULSED FOURIER TRANSFORM (FT) METHOD FAST LOW NOISE THE NEWER COMPUTER-BASED METHOD Most protons relax (decay) from their excited states very quickly (within a second). The excitation pulse, the data collection (FID), and the computer-driven Fourier Transform (FT) take only a few seconds. The pulse and data collection cycles may be repeated every few seconds. Many repetitions can be performed in a very short time, leading to improved signal …..

  30. IMPROVED SIGNAL-TO-NOISE RATIO By adding the signals from many pulses together, the signal strength may be increased above the noise level. signal enhanced signal noise 1st pulse 2nd pulse add many pulses noise is random and cancels out nth pulse etc.

  31. SPIN-SPIN SPLITTING

  32. SPIN-SPIN SPLITTING Often a group of hydrogens will appear as a multiplet rather than as a single peak. Multiplets are named as follows: Singlet Quintet Doublet Septet Triplet Octet Quartet Nonet This happens because of interaction with neighboring hydrogens and is called SPIN-SPIN SPLITTING.

  33. 1,1,2-Trichloroethane The two kinds of hydrogens do not appear as single peaks, rather there is a “triplet” and a “doublet”. integral = 2 integral = 1 The subpeaks are due to spin-spin splitting and are predicted by the n+1 rule. triplet doublet

  34. n + 1 RULE

  35. 1,1,2-Trichloroethane integral = 2 integral = 1 Where do these multiplets come from ? ….. interaction with neighbors

  36. this hydrogen’s peak is split by its two neighbors these hydrogens are split by their single neighbor MULTIPLETS singlet doublet triplet quartet quintet sextet septet two neighbors n+1 = 3 triplet one neighbor n+1 = 2 doublet

  37. EXCEPTIONS TO THE N+1 RULE IMPORTANT ! Protons that are equivalent by symmetry usually do not split one another 1) no splitting if x=y no splitting if x=y Protons in the same group usually do not split one another 2) more detail later or

  38. EXCEPTIONS TO THE N+1 RULE The n+1 rule applies principally to protons in aliphatic (saturated) chains or on saturated rings. 3) or YES YES but does not apply (in the simple way shown here) to protons on double bonds or on benzene rings. NO NO

  39. SOME COMMON PATTERNS

  40. SOME COMMON SPLITTING PATTERNS ( x = y ) ( x = y )

  41. SOME EXAMPLE SPECTRA WITH SPLITTING

  42. NMR Spectrum of Bromoethane

  43. in higher multiplets the outer peaks are often nearly lost in the baseline 1:6:15:20:16:6:1 NMR Spectrum of 2-Nitropropane

  44. NMR Spectrum of Acetaldehyde offset = 2.0 ppm

  45. INTENSITIES OF MULTIPLET PEAKS PASCAL’S TRIANGLE

  46. The interior entries are the sums of the two numbers immediately above. PASCAL’S TRIANGLE Intensities of multiplet peaks 1 singlet 1 1 doublet 1 2 1 triplet 1 3 3 1 quartet 1 4 6 4 1 quintet 1 5 10 10 5 1 sextet 1 6 15 20 15 6 1 septet 1 7 21 35 35 21 7 1 octet

  47. THE ORIGIN OF SPIN-SPIN SPLITTING HOW IT HAPPENS

  48. THE CHEMICAL SHIFT OF PROTON HA IS AFFECTED BY THE SPIN OF ITS NEIGHBORS aligned with Bo opposed to Bo +1/2 -1/2 50 % of molecules 50 % of molecules H H H H A A C C C C Bo downfield upfield neighbor aligned neighbor opposed At any given time about half of the molecules in solution will have spin +1/2 and the other half will have spin -1/2.

  49. SPIN ARRANGEMENTS one neighbor n+1 = 2 doublet one neighbor n+1 = 2 doublet H H H H C C C C yellow spins blue spins The resonance positions (splitting) of a given hydrogen is affected by the possible spins of its neighbor.

  50. SPIN ARRANGEMENTS two neighbors n+1 = 3 triplet one neighbor n+1 = 2 doublet methine spins methylene spins

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