NUCLEAR

MAGNETIC RESONANCE SPECTROSCOPY

CONTENTS
Introduction Principles of NMR Relaxation process Shielding Deshielding Chemical shift Factors affecting chemical shift Reference standards Conclusion Reference

 RADIOFREQUENCY WAVES
Lowest energy form of electromagnetic radiation(frequency-107 to109 CPS ) Energy can be calculated by planks constant Energy of radiowaves E=h =6.610-27107 =6.610-20erg Energy involved in radio frequency is very small

 These waves are not energetic enough to effect the electronic; vibrational;rotational levels of molecule
These will interact with nuclei of certain atoms that are exposed to a strong magnetic field The nuclei of atoms in a molecule on absorbing radiofrequency radiation may change their direction of spin

 PRINCIPLES OF NMR
All nuclei carry a charge Atomic nuclei contains nucleonic particle like protons &neutrons

Nuclei are positively charge due to presence of protons& they spin their axis
Charged nuclei generate a small magnetic field The circulation of nuclear charge generates a magnetic dipole along the axis

Spinning nuclei behave as they are tiny barmagnet with North pole&South pole

=>

 QUANTUM DESCRIPTION OF NMR

Spinning nucleus can only have spin angular momentum

Spin angular momentum= I(I+1)1/2 h/2 (p) I=Spin quantum number of nucleus h=planks constant
= I(I+1)1/2 h/2

=gyromagnetic ratio =magnetic moment of the nucleus

 If a nucleus having a magnetic moment is introduced in to magnetic field B0,the two energy levels are seperated
m= -1/2(anti parallel to the direction of magnetic field)

m=+1/2(parallel to the direction of magnetic field)

E2

E1

 Potential energy E of a nucleus of these orientation given by

E = -mh/2 B0
The energy for the lower energy m = +1/2 E+1/2 = -h/4 The energy for the higher energy state E - 1/2 = h/4B0

E = h/ 4 B0 - ( - h/4 B0)

E = h/2 BO
(Larmor equation)

E = h 0
Planks relation

Transition between energy states are occur due to absorption &emission of electro magnetic radiation of frequency v0 that corresponds to energy E

0 =Frequency of radiation require for the

0 = / 2 B

transition

 When the nucleus absorb energy,the nucleus will be promoted from lower energy levels E1 to the higher energy level E2 by absorption of energy (flipping of proton)

E=E2-E1(Absorption of energy E changes the magnetic moment from the parallel state m+1/2 to the antiparallel state m 1/2

If the nucleus lies in the upper energy state,E2 and radiation of energy E is incident up on the system,the nucleus will come to lower energy levelE1, emitting energy corresponds to E

 Cont. The frequency absorbed or emitted by a nucleus in moving from one energy levels to another is directly propotional to applied magnetic field RESONANCE When a nucleus is placed in a system where it absorb energy,it becomes excited. It then loses energy to return to the unexcited state It absorbs energy&again enters an excited state & process is going on Nucleus which alternately becomes excited & unexcited-Resonance

 All nuclei possess nuclear spin numbers (I)

I may be zero, half integral/integral Only nuclei with non-zero value for I will give NMR spectrum Spinning nuclei possess magnetic moment & angular momentum p.

 THE RULES FOR DETERMINIG THE NET SPIN OF A NUCLEUS

If the number of neutrons plus the number of protons is odd, then the nucleus has a halfinteger spin (i.e. 1/2, 3/2, 5/2)

If the number of neutrons and the number of protons are both even, then the nucleus has NO spin.
If the number of neutrons and the number of protons are both odd, then the nucleus has an integer spin (i.e. 1, 2, 3)

Proton no (Z) even Even/ odd

Neutron Nuclear Examples no (A-Z) spin no AXZ (I) even 0

4He 16O 1H 12C 2 6

Odd/ 3/2 even 5/2

15N

13C 0 6 7

odd

odd

123 etc

2H

14N

 A Nucleus of spin I will have 2I + 1 possible orientations. A nucleus with spin 1/2 will have 2 possible orientations.(2*1/2+1)=2 In the absence of an external magnetic field, these orientations are of equal energy. If a magnetic field is applied, then the energy levels split. - Nuclear Zeeman splitting Each level is given a magnetic quantum number, m

 ORIENTATIONS IN NO FIELD AND IN MAGNETIC FIELD

Random arrangement

Align with/against the field

 By the external magnetic field(B0), the nuclei spins on its axis,and a magnetic moment is created,resulting in a precessional frequency

In this state the magnetic field aligned with the externally applied magnetic field

 When energy in the form of radiofrequency applied applied frequency=precessional frequency Absorption of energy takeplace&NMR signal is recorded After absorption,the nucleus moves from ground state to excited state Magnetic field caused by spin of nucleus opposes(aligned against)the externally applied magnetic field (spin reversal/antiparellel orientation)

 Classical description of NMR

PRECESSION rotation of the spinning nucleus around the magnetic field is called precession Larmor precessional frequency number of revolutions per sec made by the magnetic vector component of the nucleus around the external field B0

In the presence of a magnetic field the axis of rotating nucleus will precess around the magnetic field

Precession of a rotating particle in a magnetic field

RELAXATION PROCESS
Relaxation process: deactivation of nuclei or return from the higher energy nuclear spin state to equilibrium or steady state. 2 types: spin-lattice relaxation & spin-spin relaxation

SPIN-LATTICE RELAXATION

(longitudinal relaxation or spin cooling.) Transfer of energy from an excited nucleus to molecular lattice. Lattice-entire framework/aggregate of neighbouring atom(These may be either in the same molecule/in solvent molecule) Lattice field The magnetic field caused by motion of nuclei within the lattice

Efficiency of spin lattice relaxation(T1) half life required for the system to establish the equilibrium state.
Factors affecting T1
Gyromagnetic ratio of nucleus Mobility of lattice

Pure solids have large T1 so narrow absorption bands. Short relaxation time-----broad resonance bands. Oxygen impurity produce broad bands(very rapid spin relaxation time). Nuclei with I>1/2--mag field fluctuations occur- short relaxation time & line broadening occur

SPINSPIN RELAXATION

. ( transverse relaxation) Mutual exchange of spins between an excited nucleus & neighbour,without altering the overall spin state of the system Excited nucleus relaxes to the lower energy states No net change in the relative spin state Average lifetime of a particular excited nucleus is shortened,line broadening occurs

CHEMICAL SHIFT

Different isotopes will absorb radiofrequency energy at different frequencies for transitions to a higher energy levels Nuclei of same isotope also absorb energy at different frequencies Nucleus is surrounded by electrons ,circulation of electrons create a magnetic field Protons can be present with in or outside the circulating magnetic field

Contnd The magnetic field at the nucleus is not equal to the applied magnetic field Electrons around the nucleus shield it from the applied field Nuclear shielding The difference between the applied magnetic field and field at the nucleus A magnetic field B0 applied ,electron create a small local magnetic field of its own,which opposes B0

 SHIELDING Nucleus is surrounded by electrons Protons can be present within or outside the circulating magnetic field (circulation of electrons in double bond,triple bond,aromatic/other ring system Shielded protons When a proton is present inside the magnetic field/closer to an electropositive atom,more applied magnetic field is required to cause excitation

 diamagnetic shift Electrons in the s- orbitals (spherical symmetry) circulate in the applied field,producing a magnetic field which opposes the applied field
Proton needs strong applied field to produce the absorption signal NMR signal generation to occur at higher external magnetic field setting

NMR signal shifted upfield

Deshielding effect When a proton is present outside the magnetic field/when it is attached to an electronegative atom ,less applied magnetic field is sufficint for excitation

Low field shift-paramagnetic shift

Paramagnetic shift Electrons in p-orbitals have no spherical symmetry

They produce comparitavely large magnetic fields at the nucleus,which give a low field shift

 Positive shielding Secondary fields produced by the circulating electrons oppose the applied field at a particular nucleus in a molecule Effective field experience by the nucleus is less than the applied field Resonance position moves upfield in NMR spectrum Value of applied field necessary to bring the nucleus in to resonance greater than where no secondary opposing field

NEGATIVE SHIELDING If the secondary field produced by the circulating electrons reinforces the applied field, the position of resonance moves downfield

CHEMICAL SHIFT
The shift in the position of NMR signal (compared with a standard reference) resulting from the shielding & deshielding by electrons are considered as chemical shift = H0 (ref)-H0 (sample)/H0 (ref) *10
dimensionless&expressed in ppm
6.ppm

Relationship between TMS signals; and scales.

MEASUREMENT OF CHEMICAL SHIFT

Chemical shift is represented by scale: 0 to -10 scale TMS as zero marker. Dimensionless expression;. scale =10 0 Greater the deshielding of protons, larger value of ./greater the shielding of protons,smaller value of

CAUSES FOR CHEMICAL SHIFT

Positive shielding :resonance position moves upfield. Negative shielding: resonance position moves downfield.

REFERENCE STANDARDS

Chemical inertness
Magnetic isotropy(magnetically neutral)

Give a single sharp peak

Easily recognizable peak

Miscibility with wide range of solvents

volatility

TYPE Organic solvents Aqueous solvents

REFERENCE Tetramethyl silane

Sodium salt of 3-trimethyl silyl propane sulphonic acid TMS

For C13 External sample of H3PO4 Water

For phosphorous NMR

For oxygen NMR

TMS AS REFERENCE STANDARDS

All the 12 atoms in identical environment. Shielding on protons is maximum.

Far volatile & is easily removed.

All 12 protons are equivalent ;so strong signal is obtained. Soluble in all organic solvents.

 FACTORS AFFECTING CHEMICAL SHIFT Inductive effect Anisotropic effect Hydrogen bonding

INDUCTIVE EFFECTS

Electronegative atoms(halogen,oxygen,nitrogen) deshield the protons Absorption occurs downfield Extend of deshielding electro negativity of X

Protons in CH3-F more deshielded than CH3Cl

Protons in CH3OCH3more deshielded than CH3-CH3

 A magnetic field is applied to a molecule having pi electrons These electrons begins to circulate at right angles to the direction of applied field induced magnetic field The effect of this field on the nearby protons depends on orientation of the proton with respect to pi bond producing the induced field Effect may be shielding/deshielding

ANISOTROPIC EFFECT(space effect)

 RING CURRENT IN AROMATICS

The plane of the ring is perpendicular to the magnetic field The field can induce a flow of the pi electrons around the ring to create a current ring current The secondary field induced act in opposition to the applied field The induced field exerts a magnetic effect on the protons attached to the ring in the direction of the field

HYDROGEN BONDING

Increased hydrogen bonding leads to greater proton deshielding. If a hydrogen atom exhibits hydrogen bonding in a compound; it will be deshielded due to strongly electronegative atom attached to it. The chemical shifts of intramolecular hydrogen bonded protons are independent of temperature and solute concentration.

 NMR is one of the most useful analytical tool yet developed for the ellucidation of structure of compounds NMR in medical diagnosis MRI/Tomograpy(possible to create two/three dimensional pictures of objects, by proper adjustment of magnetic field) The irradiation frequencies are very low in energyharmless to human tissues &organ MRI are mainly used in locating small tumours,brain disorders etc which are invisible to X-ray analysis

CONCLUSION

 REFERENCES Organic spectroscopy- William Kemp 3rd page no-104-109

edition,

Instrumental analysis-Skoog,Holler page no-551-591 Spectrometric identification of organic compoundsRobert M Silverstein page no-144 Instrumental methods of chemical analysis Gurdeep Chatwaal

Instrumental methods of analysis-Robert H Willard page no 160 http://wikipedia.org