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Nuclear Magnetic Resonance spectroscopy (NMR)

Laboratory 4

Exam notes
Determine your testing location, posted on Compass Arrive 10 minutes early to get checked-in and situated Bring your U of I Student ID You may use a calculator but NOT a programmable calculator Bring a #2 pencil to fill in scantron forms You will NOT need molecular models for this exam There will be a review session Monday October 4 th at 5 pm in 1404 Siebel Center

What to bring for lab 4


There is no notebook pre-lab for lab 4 Bring the answer packet printed off of Compass for full pre-lab points There is no online quiz for lab 4, Page 29 of lab manual completed Turn in to TA at beginning of class p 29 serves as your online quiz points Remember you will be in a classroom look on Compass!

Spectroscopy
A group of analytical techniques used to determine molecular structures Typically involve irradiating sample with part of the electromagnetic spectrum NMR nuclear magnetic resonance spectroscopy Utilizes radiowaves, 106 Hz

The physics of the nucleus


Nuclei with an even atomic mass, spin quantum number I = 0 or 1 Nuclei with an odd atomic mass have a spin quantum number I = Only nuclei with I = can be observed by NMR

Nuclei are charged and spin Spinning charges create magnetic fields therefore nuclei have magnetic moments

+
nucleus

S
bar magnet

=
magnetic moment

Magnetic moments in a magnetic field

Bo

No applied magnetic field Random orientation of magnetic moments

Bo applied magnetic field Magnetic moments oriented with Bo

Orientation of spins in a magnetic field


Bo

Energy

-spin: lower energy -spin: higher energy

Bo (Tesla)

The stronger the magnetic field, the larger the energy difference

Pulsing spins with electromagnetic radiation

Bo

B1

Bo

B1 is another electromagnetic frequency Nuclei absorb B1 causing spins to flip to higher energy states B1 has a wide bandwidth of radio-frequency energy

Spins relax back to equilibrium

Bo

Time

Bo

As spins relax to a lower energy state, they emit energy, which we can measure

FT NMR

FT

FID- free induction decay

Spectrum

Fourier transform a mathematical operation that transforms one complex function into another.

http://www.chemie.uni-erlangen.de/oc/research/NMR/music3.html

What does 1HNMR do for us?


Gives information on: 1. Number of unique sets of hydrogens (number of signals) 2. Number of hydrogens in each unique set (integration of signals) 3. Number of adjacent hydrogens to each set (peak splitting) 4. Presence of functional groups (chemical shift)

1HNMR

spectrum of ethanol

Equivalent hydrogens
Hydrogens in the same chemical environment are equivalent Equivalent hydrogens give rise to one signal in a NMR spectrum If the connectivity is the same, the environment will be the same
General rules: Hydrogens on the same carbon are equivalent If the molecule is symmetrical, mirror image sets will be equivalent

1 set

2 sets

3 sets

3 sets

4 sets

3 sets

Integration of signals
The area under the signal (integration) is equal to the ratio of hydrogens giving rise to that signal A computer calculates integration and draws lines on the spectrum in those ratios

If the numerical value isnt given, we can measure the height of the vertical line

This compound has a ratio of 1:1:6

Chemical shift
X-axis of a NMR spectrum is the chemical shift, , is given in ppm Reporting chemical shift in ppm accounts for different strength NMR instruments

downfield

upfield

The origin of shielding


+

Bo

The electrons surrounding the nucleus create a magnetic field The induced magnetic field opposes the applied magnetic field Bo

Shielding and chemical shift


A nucleus with more electron density is shielded, signal appears upfield A nucleus with less electron density is deshielded, signal appears downfield

Tetramethylsilane (TMS) universal NMR standard Hydrogens are very shielded, most hydrogens appear downfield from TMS signal TMS signal is normalized to = 0

Chemical shift of functional groups

Spin-spin splitting
Some signals in spectra appear as multiplets - multiple peaks corresponding to one signal Indicates number of neighboring equivalent hydrogens
# peaks 1 2 3 name singlet doublet triplet # peaks 6 7 8 name sextet septet octet

4 5

quartet quintet

9 No clear pattern

nonet multiplet

The origin of peak splitting


For proton Ha: Hbs magnetic field can be aligned with or against Has field Depending on the alignment, Ha is either more shielded or deshielded, small difference This is reciprocal- Hb splits Ha and Ha splits Hb
Signal without Hb influence
Signal with Hb influence

With one neighboring proton there are 2 permutations- with or against Has field

This gives a doublet Signal splits into 2 smaller peaks

Peak splitting cont.


For proton Ha: With two equivalent Hb protons, there are more permutations All equivalent protons will split Ha

Signal without Hb influence

Signal with Hb influence


Gives a triplet

Typically only vicinal protons (3 bonds away from each other, i.e. protons on adjacent carbons) will split each other

The n+1 rule


If hydrogen A has n neighboring equivalent hydrogens, the number of peaks in As signal is n + 1
# of neighboring equivalent hydrogens 0 1 2 3 4 5

The ratios of area under the peaks of splitting patterns are described by Pascals triangle
# of peaks in signal 1 2 3 4 5 6

Area ratios of peaks 1 1 1 1 2 1 1 3 3 1 1 4 6 4 1 1 5 10 10 5 1

Coupling constants J
Coupling constant - The distance between peaks in a multiplet in Hz, quantitative measurement of the magnetic influence of neighboring hydrogens The distance between these peaks in Hz is the coupling constant J If Hb splits Ha then the J value for the Ha multiplet is the same as the Hb multiplet

Practice 1

Ha
triplet

Hb
How many signals will we see? What are the multiplicities of these signals? quartet

H
singlet

Practice 2
singlet

triplet

How many signals expected? Where do you expect to see signals? What is the multiplicity of each signal?

quartet

Practice 3
How many different Hs? What is the multiplicity of each signal? What is the chemical shift of each signal? What are the coupling constants? What is the ratio of H in the molecule?

Practice 3 cont.
Integration? Coupling constants? Chemical shift?
d

sept

Practice 3 cont.

Practice 3 cont.

Degrees of unsaturation
When given a molecular formula in a spectroscopy problem, the first thing you should do is determine the degrees of unsaturation
Degrees of unsaturation indicates the number of rings or double bonds

C = # of carbons H = # of hydrogens N = # of nitrogens X = # of F, Cl, Br

Tips
There are 2 peaks to watch out for: Chloroform at 7.2 ppm TMS at 0 ppm