oc 2/e 12 - university of texas at austinwillson.cm.utexas.edu/teaching/chem328n/files/lecture...

36
Chemistry 328N Lecture 3 NMR Spectroscopy January 26, 2016

Upload: others

Post on 31-Mar-2021

1 views

Category:

Documents


0 download

TRANSCRIPT

Page 1: OC 2/e 12 - University of Texas at Austinwillson.cm.utexas.edu/Teaching/Chem328N/Files/Lecture 03... · 2016. 1. 29. · Born, 1856 in Smiljan, Lika (Austria-Hungary) Died 1943 in

Chemistry 328N

Lecture 3

NMR Spectroscopy

January 26 2016

Chemistry 328N

Please see me after classEnrollment issue

Hugo Nicolas Eichner

Nurbol Kaliyev

Chemistry 328N

Energy per photon

Frequency

Wave Length

nhE =

Chemistry 328N

Electromagnetic Radiation

c=nl Where C = 300 x 108 ms

ln

hchE == Where h = 9537 x 10-14 kcal secmol

See examples of calculations in sections 121 amp122

Important relationships

Chemistry 328N

Absorbance promotes atom or molecule to higher energy state

Chemistry 328N

Molecular Spectroscopy

We study three types of molecular spectroscopy

nuclear spin energy levels

vibrational energy levels

electronic energy levels

radio frequency

infrared

ultraviolet-visible

Absorption of Radiation Results

in Transition Between

Region of the

Spectrum

Chemistry 328N

Absorption of electromagnetic radiation

Described by quantum mechanical theories

Only discrete (unique) energy states are

allowed (accessible)

Therefore only discrete (unique) amounts of

radiation can be absorbed (or emitted)

How many potential energy states are

available to the ball

Chemistry 328N

Summarybull Molecular Spectroscopy Concept

ndash Discrete transitions in energy levels

ndash Transitions with varying energy (areas of spectrum)bull Nmr nuclear spin radio frequency region

bull IR vibration infrared region

bull UV-Vis electronic transitions UV to visible

bull Please know relationships between frequency wave

length and energy

bull Know length scale conversionshellipmicron

millimeter nanometer angstrom

Chemistry 328N

NMR Spectroscopy

Chemistry 328N

Spin States

Electrons have a spin quantum number of 12

with allowed values of +12 and -12

ndash One can consider this as spinning charge that

creates an associated magnetic field

ndash Electrons therefore behave like tiny bar magnets

ndash Remember the Pauli exclusion principle

Spin ldquouprdquo and spin ldquodownrdquo

Chemistry 328N

Nuclear Spin States Nuclei with an odd mass an odd atomic number

or both also have a net spin and a resulting nuclear

magnetic moment

The allowed nuclear spin states are determined by

the spin quantum number I of the nucleus

For each I there are 2I + 1 spin states

If I = 12 there are two allowed spin states

Chemistry 328N

Nuclear Spins The shell model for the nucleus tells us that

nucleons just like electrons fill orbitals

When the number of protons or neutrons

equals 2 8 20 28 50 82 and 126 orbitals

are filled Because nucleons have spin just

like electrons do their spin can pair up

when the orbitals are being filled and cancel

out

Chemistry 328N

Nuclear Spins1 If the number of neutrons and the number

of protons are both even then the nucleus

has NO spin He for example has no spin

2 If the number of neutrons plus the number

of protons is odd then the nucleus has a

half-integer spin (ie 12 32 52) (H and 13C for example are both 12)

3 If the number of neutrons and the number

of protons are both odd then the nucleus

has an integer spin (ie 1 2 3) (Deuterium

or N for example)

Chemistry 328N

Nuclear Spins in a Magnetic Field

Within a collection of 1H or 13C atoms nuclear spins are random in orientation

When placed in a strong external magneticfield the interaction between nuclear spinsand the applied magnetic field is quantizedwith the result that only certain orientationsof the nuclear magnetic moments areallowed

Chemistry 328N

Nuclear Spins in a Magnetic Field

E=hn or n =Eh

Chemistry 328N

Nuclear Magnetic Resonance

If the nucleus is irradiated with radiation

having energy (E=h) that is exactly the

same as the difference between the nuclear

spin states

ndash energy is absorbed and

ndash the nuclear spin is flipped from spin state +12

(with the applied field) to -12 (against the

applied field)

Chemistry 328N

Nuclear Spin States

Spin quantum numbers and allowed nuclear

spin states for selected isotopes of elements

common to organic compounds

Element 1H 2H 12C 13C 14N 16O 31P

number of

spin states

12 1 0 0 0

32S

12 1

2 3 1 2 3 1

12

2 1

nuclear spin

quantum

number ( I )

Chemistry 328N

Serbian-American inventor electrical engineer and scientist

Born 1856 in Smiljan Lika (Austria-Hungary)

Died 1943 in New York City New York (USA)

Inventions a telephone repeater rotating magnetic field principle polyphase

alternating-current system induction motor alternating-current power

transmission Tesla coil transformer wireless communication radio

fluorescent lights and more than 700 other patents

Nikola Tesla

T (Tesla) = W (Weber)

m2

Chemistry 328N

Famous and Controversial picture of Tesla

httpwwwteslasocietycomindexhtml

Chemistry 328N

ldquoThe ray was described as the most important of all Teslarsquos inventions so far It was

said that IT COULD SEND CONSECRATED BEAMS OF PARTICLES THROUGH

FREE AIR and could cause armies of millions to drop dead in their tracks

Wardenclyffe Tower

if constructed would result in

An inexpensive instrument not

bigger than a watch will enable its

bearer to hear anywhere on sea or

land music or song the speech of a

political leader the address of an

eminent man of science or the

sermon of an eloquent clergyman

delivered in some other place

however distant In the same

manner any picture character

drawing or print can be transferred

from one to another place

Tesla ray gun

Chemistry 328N

)( 0BfhE == n

42

At B=10T

E = 4258MHz

Chemistry 328N

Nuclear Spins in B0

In an applied field strength of 705T (BIG)

E between nuclear spin states for

ndash 1H is approximately 00286 calmol which

corresponds to electromagnetic radiation of 300

MHz (300000000 Hz)

ndash 13C is approximately 000715 calmol which

corresponds to electromagnetic radiation of

75MHz (75000000 Hz)

ndash This E is quite smallhelliplow frequency

radiation induces ldquofliprdquo (resonance)

Chemistry 328N

ldquoResonancerdquo The transition from the lower state to the higher

occurs at unique combinations of magnetic field and frequency of electromagnetic radiation

When placed in a magnetic field of strength B a particle with a net spin can absorb a photon of frequency n The frequency n depends on the gyromagnetic ratio of the particle

n = B

For hydrogen = 4258 MHz Tesla

Allows you to calculate ldquospectrometer frequencyrdquo for 1H

This is the frequency at which ldquonakedrdquo 1H resonates in that machine

Chemistry 328N

Some Proportionality Constants

Gyromagnetic Ratio n = B

ndash For 1H = 4258 MHzT

Planckrsquos Constant E = h n

Speed of light n = c l or c = n l

Chemical Shift 119889(119901119901119898) =∆n

119878119901119890119888119905119903119900119898119890119905119890119903 119891119903119890119902119906119890119899119888119910

Chemistry 328N

NMR Spectrometer

Chemistry 328N

In principle we could hold field constant and scan frequency looking

for resonance but it is equally effective to scan field strength and hold

frequency constant

Chemistry 328N

500MHz 1H-nmr Spectrometer

Magnet

Chemistry 328N

httpwwwjeolusacomRESOURCESAnalyticalInstrumentsNMRMagnetDestructiontabid390Defaultaspx

Chemistry 328N

800 MHz machine at UH

Highest Frequency in 2013

The first Avance 1000 system was

delivered to the new lsquoCentre de RMN agrave

Tregraves Hauts Champsrsquo in Lyon France

1020 MHz nmr

June 2015

Weight 15 tons

Chemistry 328N

The 100MHz nmr Chart

1000 900 800 700 600 500 400 300 200 100 00

10

20

30

40

50

60

70

80

90

000

Si CH3

CH3

CH3

CH3

Frequency

field

The TMS resonance is defined as having ldquo0rdquo frequency

Chemistry 328N

100MHz Spectrum

450 400 350 300 250 200 150 100 50 00

5

10

15

20

Hz

CH3 Cl

325 320 315 310 305 300 295 290 285 2800

5

10

15

2030400

304 Hz

Chemistry 328N

100MHz nmr Spectrum

450 400 350 300 250 200 150 100 50 00

5

10

15

20

CH3 Br

275 270 265 260 2550

5

10

15

20

26850

Hz2685Hz

Chemistry 328N

Nuclear Magnetic Resonance

If we were dealing with 1H nuclei isolatedfrom all other atoms and electrons anycombination of applied field and radiation thatproduces a signal for one 1H would produce asignal for all 1H The same for 13C nuclei

But helliphydrogens in organic molecules are notisolated from all other atoms they aresurrounded by electrons which are caused tocirculate by the presence of the applied field

Chemistry 328N

Nuclear Magnetic Resonance

The circulation of electrons around anucleus in an applied field is calleddiamagnetic current

This current generates a field that opposesthe applied field diamagnetic nuclearshielding results Lenzrsquos Law

The difference in resonance frequenciesbetween the various hydrogen nuclei withina molecule is due to shieldingdeshielding isvery small but very important

Chemistry 328N

Lenzrsquos Law

Heinrich Lenz

1804-1865

Chemistry 328N

Conditions for Resonance

It is the frequency of the radiation and the

NET field at the nucleus that matters

The NET field is the sum of all incident

magnetic fields including those from

ndash The Giant Magnet (applied field)

ndash Diamagnetic Shielding field (electrons)

ndash Coupling (spin fields of adjacent nuclei)

ndash credit card strips earthrsquos field etchellip

Page 2: OC 2/e 12 - University of Texas at Austinwillson.cm.utexas.edu/Teaching/Chem328N/Files/Lecture 03... · 2016. 1. 29. · Born, 1856 in Smiljan, Lika (Austria-Hungary) Died 1943 in

Chemistry 328N

Please see me after classEnrollment issue

Hugo Nicolas Eichner

Nurbol Kaliyev

Chemistry 328N

Energy per photon

Frequency

Wave Length

nhE =

Chemistry 328N

Electromagnetic Radiation

c=nl Where C = 300 x 108 ms

ln

hchE == Where h = 9537 x 10-14 kcal secmol

See examples of calculations in sections 121 amp122

Important relationships

Chemistry 328N

Absorbance promotes atom or molecule to higher energy state

Chemistry 328N

Molecular Spectroscopy

We study three types of molecular spectroscopy

nuclear spin energy levels

vibrational energy levels

electronic energy levels

radio frequency

infrared

ultraviolet-visible

Absorption of Radiation Results

in Transition Between

Region of the

Spectrum

Chemistry 328N

Absorption of electromagnetic radiation

Described by quantum mechanical theories

Only discrete (unique) energy states are

allowed (accessible)

Therefore only discrete (unique) amounts of

radiation can be absorbed (or emitted)

How many potential energy states are

available to the ball

Chemistry 328N

Summarybull Molecular Spectroscopy Concept

ndash Discrete transitions in energy levels

ndash Transitions with varying energy (areas of spectrum)bull Nmr nuclear spin radio frequency region

bull IR vibration infrared region

bull UV-Vis electronic transitions UV to visible

bull Please know relationships between frequency wave

length and energy

bull Know length scale conversionshellipmicron

millimeter nanometer angstrom

Chemistry 328N

NMR Spectroscopy

Chemistry 328N

Spin States

Electrons have a spin quantum number of 12

with allowed values of +12 and -12

ndash One can consider this as spinning charge that

creates an associated magnetic field

ndash Electrons therefore behave like tiny bar magnets

ndash Remember the Pauli exclusion principle

Spin ldquouprdquo and spin ldquodownrdquo

Chemistry 328N

Nuclear Spin States Nuclei with an odd mass an odd atomic number

or both also have a net spin and a resulting nuclear

magnetic moment

The allowed nuclear spin states are determined by

the spin quantum number I of the nucleus

For each I there are 2I + 1 spin states

If I = 12 there are two allowed spin states

Chemistry 328N

Nuclear Spins The shell model for the nucleus tells us that

nucleons just like electrons fill orbitals

When the number of protons or neutrons

equals 2 8 20 28 50 82 and 126 orbitals

are filled Because nucleons have spin just

like electrons do their spin can pair up

when the orbitals are being filled and cancel

out

Chemistry 328N

Nuclear Spins1 If the number of neutrons and the number

of protons are both even then the nucleus

has NO spin He for example has no spin

2 If the number of neutrons plus the number

of protons is odd then the nucleus has a

half-integer spin (ie 12 32 52) (H and 13C for example are both 12)

3 If the number of neutrons and the number

of protons are both odd then the nucleus

has an integer spin (ie 1 2 3) (Deuterium

or N for example)

Chemistry 328N

Nuclear Spins in a Magnetic Field

Within a collection of 1H or 13C atoms nuclear spins are random in orientation

When placed in a strong external magneticfield the interaction between nuclear spinsand the applied magnetic field is quantizedwith the result that only certain orientationsof the nuclear magnetic moments areallowed

Chemistry 328N

Nuclear Spins in a Magnetic Field

E=hn or n =Eh

Chemistry 328N

Nuclear Magnetic Resonance

If the nucleus is irradiated with radiation

having energy (E=h) that is exactly the

same as the difference between the nuclear

spin states

ndash energy is absorbed and

ndash the nuclear spin is flipped from spin state +12

(with the applied field) to -12 (against the

applied field)

Chemistry 328N

Nuclear Spin States

Spin quantum numbers and allowed nuclear

spin states for selected isotopes of elements

common to organic compounds

Element 1H 2H 12C 13C 14N 16O 31P

number of

spin states

12 1 0 0 0

32S

12 1

2 3 1 2 3 1

12

2 1

nuclear spin

quantum

number ( I )

Chemistry 328N

Serbian-American inventor electrical engineer and scientist

Born 1856 in Smiljan Lika (Austria-Hungary)

Died 1943 in New York City New York (USA)

Inventions a telephone repeater rotating magnetic field principle polyphase

alternating-current system induction motor alternating-current power

transmission Tesla coil transformer wireless communication radio

fluorescent lights and more than 700 other patents

Nikola Tesla

T (Tesla) = W (Weber)

m2

Chemistry 328N

Famous and Controversial picture of Tesla

httpwwwteslasocietycomindexhtml

Chemistry 328N

ldquoThe ray was described as the most important of all Teslarsquos inventions so far It was

said that IT COULD SEND CONSECRATED BEAMS OF PARTICLES THROUGH

FREE AIR and could cause armies of millions to drop dead in their tracks

Wardenclyffe Tower

if constructed would result in

An inexpensive instrument not

bigger than a watch will enable its

bearer to hear anywhere on sea or

land music or song the speech of a

political leader the address of an

eminent man of science or the

sermon of an eloquent clergyman

delivered in some other place

however distant In the same

manner any picture character

drawing or print can be transferred

from one to another place

Tesla ray gun

Chemistry 328N

)( 0BfhE == n

42

At B=10T

E = 4258MHz

Chemistry 328N

Nuclear Spins in B0

In an applied field strength of 705T (BIG)

E between nuclear spin states for

ndash 1H is approximately 00286 calmol which

corresponds to electromagnetic radiation of 300

MHz (300000000 Hz)

ndash 13C is approximately 000715 calmol which

corresponds to electromagnetic radiation of

75MHz (75000000 Hz)

ndash This E is quite smallhelliplow frequency

radiation induces ldquofliprdquo (resonance)

Chemistry 328N

ldquoResonancerdquo The transition from the lower state to the higher

occurs at unique combinations of magnetic field and frequency of electromagnetic radiation

When placed in a magnetic field of strength B a particle with a net spin can absorb a photon of frequency n The frequency n depends on the gyromagnetic ratio of the particle

n = B

For hydrogen = 4258 MHz Tesla

Allows you to calculate ldquospectrometer frequencyrdquo for 1H

This is the frequency at which ldquonakedrdquo 1H resonates in that machine

Chemistry 328N

Some Proportionality Constants

Gyromagnetic Ratio n = B

ndash For 1H = 4258 MHzT

Planckrsquos Constant E = h n

Speed of light n = c l or c = n l

Chemical Shift 119889(119901119901119898) =∆n

119878119901119890119888119905119903119900119898119890119905119890119903 119891119903119890119902119906119890119899119888119910

Chemistry 328N

NMR Spectrometer

Chemistry 328N

In principle we could hold field constant and scan frequency looking

for resonance but it is equally effective to scan field strength and hold

frequency constant

Chemistry 328N

500MHz 1H-nmr Spectrometer

Magnet

Chemistry 328N

httpwwwjeolusacomRESOURCESAnalyticalInstrumentsNMRMagnetDestructiontabid390Defaultaspx

Chemistry 328N

800 MHz machine at UH

Highest Frequency in 2013

The first Avance 1000 system was

delivered to the new lsquoCentre de RMN agrave

Tregraves Hauts Champsrsquo in Lyon France

1020 MHz nmr

June 2015

Weight 15 tons

Chemistry 328N

The 100MHz nmr Chart

1000 900 800 700 600 500 400 300 200 100 00

10

20

30

40

50

60

70

80

90

000

Si CH3

CH3

CH3

CH3

Frequency

field

The TMS resonance is defined as having ldquo0rdquo frequency

Chemistry 328N

100MHz Spectrum

450 400 350 300 250 200 150 100 50 00

5

10

15

20

Hz

CH3 Cl

325 320 315 310 305 300 295 290 285 2800

5

10

15

2030400

304 Hz

Chemistry 328N

100MHz nmr Spectrum

450 400 350 300 250 200 150 100 50 00

5

10

15

20

CH3 Br

275 270 265 260 2550

5

10

15

20

26850

Hz2685Hz

Chemistry 328N

Nuclear Magnetic Resonance

If we were dealing with 1H nuclei isolatedfrom all other atoms and electrons anycombination of applied field and radiation thatproduces a signal for one 1H would produce asignal for all 1H The same for 13C nuclei

But helliphydrogens in organic molecules are notisolated from all other atoms they aresurrounded by electrons which are caused tocirculate by the presence of the applied field

Chemistry 328N

Nuclear Magnetic Resonance

The circulation of electrons around anucleus in an applied field is calleddiamagnetic current

This current generates a field that opposesthe applied field diamagnetic nuclearshielding results Lenzrsquos Law

The difference in resonance frequenciesbetween the various hydrogen nuclei withina molecule is due to shieldingdeshielding isvery small but very important

Chemistry 328N

Lenzrsquos Law

Heinrich Lenz

1804-1865

Chemistry 328N

Conditions for Resonance

It is the frequency of the radiation and the

NET field at the nucleus that matters

The NET field is the sum of all incident

magnetic fields including those from

ndash The Giant Magnet (applied field)

ndash Diamagnetic Shielding field (electrons)

ndash Coupling (spin fields of adjacent nuclei)

ndash credit card strips earthrsquos field etchellip

Page 3: OC 2/e 12 - University of Texas at Austinwillson.cm.utexas.edu/Teaching/Chem328N/Files/Lecture 03... · 2016. 1. 29. · Born, 1856 in Smiljan, Lika (Austria-Hungary) Died 1943 in

Chemistry 328N

Energy per photon

Frequency

Wave Length

nhE =

Chemistry 328N

Electromagnetic Radiation

c=nl Where C = 300 x 108 ms

ln

hchE == Where h = 9537 x 10-14 kcal secmol

See examples of calculations in sections 121 amp122

Important relationships

Chemistry 328N

Absorbance promotes atom or molecule to higher energy state

Chemistry 328N

Molecular Spectroscopy

We study three types of molecular spectroscopy

nuclear spin energy levels

vibrational energy levels

electronic energy levels

radio frequency

infrared

ultraviolet-visible

Absorption of Radiation Results

in Transition Between

Region of the

Spectrum

Chemistry 328N

Absorption of electromagnetic radiation

Described by quantum mechanical theories

Only discrete (unique) energy states are

allowed (accessible)

Therefore only discrete (unique) amounts of

radiation can be absorbed (or emitted)

How many potential energy states are

available to the ball

Chemistry 328N

Summarybull Molecular Spectroscopy Concept

ndash Discrete transitions in energy levels

ndash Transitions with varying energy (areas of spectrum)bull Nmr nuclear spin radio frequency region

bull IR vibration infrared region

bull UV-Vis electronic transitions UV to visible

bull Please know relationships between frequency wave

length and energy

bull Know length scale conversionshellipmicron

millimeter nanometer angstrom

Chemistry 328N

NMR Spectroscopy

Chemistry 328N

Spin States

Electrons have a spin quantum number of 12

with allowed values of +12 and -12

ndash One can consider this as spinning charge that

creates an associated magnetic field

ndash Electrons therefore behave like tiny bar magnets

ndash Remember the Pauli exclusion principle

Spin ldquouprdquo and spin ldquodownrdquo

Chemistry 328N

Nuclear Spin States Nuclei with an odd mass an odd atomic number

or both also have a net spin and a resulting nuclear

magnetic moment

The allowed nuclear spin states are determined by

the spin quantum number I of the nucleus

For each I there are 2I + 1 spin states

If I = 12 there are two allowed spin states

Chemistry 328N

Nuclear Spins The shell model for the nucleus tells us that

nucleons just like electrons fill orbitals

When the number of protons or neutrons

equals 2 8 20 28 50 82 and 126 orbitals

are filled Because nucleons have spin just

like electrons do their spin can pair up

when the orbitals are being filled and cancel

out

Chemistry 328N

Nuclear Spins1 If the number of neutrons and the number

of protons are both even then the nucleus

has NO spin He for example has no spin

2 If the number of neutrons plus the number

of protons is odd then the nucleus has a

half-integer spin (ie 12 32 52) (H and 13C for example are both 12)

3 If the number of neutrons and the number

of protons are both odd then the nucleus

has an integer spin (ie 1 2 3) (Deuterium

or N for example)

Chemistry 328N

Nuclear Spins in a Magnetic Field

Within a collection of 1H or 13C atoms nuclear spins are random in orientation

When placed in a strong external magneticfield the interaction between nuclear spinsand the applied magnetic field is quantizedwith the result that only certain orientationsof the nuclear magnetic moments areallowed

Chemistry 328N

Nuclear Spins in a Magnetic Field

E=hn or n =Eh

Chemistry 328N

Nuclear Magnetic Resonance

If the nucleus is irradiated with radiation

having energy (E=h) that is exactly the

same as the difference between the nuclear

spin states

ndash energy is absorbed and

ndash the nuclear spin is flipped from spin state +12

(with the applied field) to -12 (against the

applied field)

Chemistry 328N

Nuclear Spin States

Spin quantum numbers and allowed nuclear

spin states for selected isotopes of elements

common to organic compounds

Element 1H 2H 12C 13C 14N 16O 31P

number of

spin states

12 1 0 0 0

32S

12 1

2 3 1 2 3 1

12

2 1

nuclear spin

quantum

number ( I )

Chemistry 328N

Serbian-American inventor electrical engineer and scientist

Born 1856 in Smiljan Lika (Austria-Hungary)

Died 1943 in New York City New York (USA)

Inventions a telephone repeater rotating magnetic field principle polyphase

alternating-current system induction motor alternating-current power

transmission Tesla coil transformer wireless communication radio

fluorescent lights and more than 700 other patents

Nikola Tesla

T (Tesla) = W (Weber)

m2

Chemistry 328N

Famous and Controversial picture of Tesla

httpwwwteslasocietycomindexhtml

Chemistry 328N

ldquoThe ray was described as the most important of all Teslarsquos inventions so far It was

said that IT COULD SEND CONSECRATED BEAMS OF PARTICLES THROUGH

FREE AIR and could cause armies of millions to drop dead in their tracks

Wardenclyffe Tower

if constructed would result in

An inexpensive instrument not

bigger than a watch will enable its

bearer to hear anywhere on sea or

land music or song the speech of a

political leader the address of an

eminent man of science or the

sermon of an eloquent clergyman

delivered in some other place

however distant In the same

manner any picture character

drawing or print can be transferred

from one to another place

Tesla ray gun

Chemistry 328N

)( 0BfhE == n

42

At B=10T

E = 4258MHz

Chemistry 328N

Nuclear Spins in B0

In an applied field strength of 705T (BIG)

E between nuclear spin states for

ndash 1H is approximately 00286 calmol which

corresponds to electromagnetic radiation of 300

MHz (300000000 Hz)

ndash 13C is approximately 000715 calmol which

corresponds to electromagnetic radiation of

75MHz (75000000 Hz)

ndash This E is quite smallhelliplow frequency

radiation induces ldquofliprdquo (resonance)

Chemistry 328N

ldquoResonancerdquo The transition from the lower state to the higher

occurs at unique combinations of magnetic field and frequency of electromagnetic radiation

When placed in a magnetic field of strength B a particle with a net spin can absorb a photon of frequency n The frequency n depends on the gyromagnetic ratio of the particle

n = B

For hydrogen = 4258 MHz Tesla

Allows you to calculate ldquospectrometer frequencyrdquo for 1H

This is the frequency at which ldquonakedrdquo 1H resonates in that machine

Chemistry 328N

Some Proportionality Constants

Gyromagnetic Ratio n = B

ndash For 1H = 4258 MHzT

Planckrsquos Constant E = h n

Speed of light n = c l or c = n l

Chemical Shift 119889(119901119901119898) =∆n

119878119901119890119888119905119903119900119898119890119905119890119903 119891119903119890119902119906119890119899119888119910

Chemistry 328N

NMR Spectrometer

Chemistry 328N

In principle we could hold field constant and scan frequency looking

for resonance but it is equally effective to scan field strength and hold

frequency constant

Chemistry 328N

500MHz 1H-nmr Spectrometer

Magnet

Chemistry 328N

httpwwwjeolusacomRESOURCESAnalyticalInstrumentsNMRMagnetDestructiontabid390Defaultaspx

Chemistry 328N

800 MHz machine at UH

Highest Frequency in 2013

The first Avance 1000 system was

delivered to the new lsquoCentre de RMN agrave

Tregraves Hauts Champsrsquo in Lyon France

1020 MHz nmr

June 2015

Weight 15 tons

Chemistry 328N

The 100MHz nmr Chart

1000 900 800 700 600 500 400 300 200 100 00

10

20

30

40

50

60

70

80

90

000

Si CH3

CH3

CH3

CH3

Frequency

field

The TMS resonance is defined as having ldquo0rdquo frequency

Chemistry 328N

100MHz Spectrum

450 400 350 300 250 200 150 100 50 00

5

10

15

20

Hz

CH3 Cl

325 320 315 310 305 300 295 290 285 2800

5

10

15

2030400

304 Hz

Chemistry 328N

100MHz nmr Spectrum

450 400 350 300 250 200 150 100 50 00

5

10

15

20

CH3 Br

275 270 265 260 2550

5

10

15

20

26850

Hz2685Hz

Chemistry 328N

Nuclear Magnetic Resonance

If we were dealing with 1H nuclei isolatedfrom all other atoms and electrons anycombination of applied field and radiation thatproduces a signal for one 1H would produce asignal for all 1H The same for 13C nuclei

But helliphydrogens in organic molecules are notisolated from all other atoms they aresurrounded by electrons which are caused tocirculate by the presence of the applied field

Chemistry 328N

Nuclear Magnetic Resonance

The circulation of electrons around anucleus in an applied field is calleddiamagnetic current

This current generates a field that opposesthe applied field diamagnetic nuclearshielding results Lenzrsquos Law

The difference in resonance frequenciesbetween the various hydrogen nuclei withina molecule is due to shieldingdeshielding isvery small but very important

Chemistry 328N

Lenzrsquos Law

Heinrich Lenz

1804-1865

Chemistry 328N

Conditions for Resonance

It is the frequency of the radiation and the

NET field at the nucleus that matters

The NET field is the sum of all incident

magnetic fields including those from

ndash The Giant Magnet (applied field)

ndash Diamagnetic Shielding field (electrons)

ndash Coupling (spin fields of adjacent nuclei)

ndash credit card strips earthrsquos field etchellip

Page 4: OC 2/e 12 - University of Texas at Austinwillson.cm.utexas.edu/Teaching/Chem328N/Files/Lecture 03... · 2016. 1. 29. · Born, 1856 in Smiljan, Lika (Austria-Hungary) Died 1943 in

Chemistry 328N

Electromagnetic Radiation

c=nl Where C = 300 x 108 ms

ln

hchE == Where h = 9537 x 10-14 kcal secmol

See examples of calculations in sections 121 amp122

Important relationships

Chemistry 328N

Absorbance promotes atom or molecule to higher energy state

Chemistry 328N

Molecular Spectroscopy

We study three types of molecular spectroscopy

nuclear spin energy levels

vibrational energy levels

electronic energy levels

radio frequency

infrared

ultraviolet-visible

Absorption of Radiation Results

in Transition Between

Region of the

Spectrum

Chemistry 328N

Absorption of electromagnetic radiation

Described by quantum mechanical theories

Only discrete (unique) energy states are

allowed (accessible)

Therefore only discrete (unique) amounts of

radiation can be absorbed (or emitted)

How many potential energy states are

available to the ball

Chemistry 328N

Summarybull Molecular Spectroscopy Concept

ndash Discrete transitions in energy levels

ndash Transitions with varying energy (areas of spectrum)bull Nmr nuclear spin radio frequency region

bull IR vibration infrared region

bull UV-Vis electronic transitions UV to visible

bull Please know relationships between frequency wave

length and energy

bull Know length scale conversionshellipmicron

millimeter nanometer angstrom

Chemistry 328N

NMR Spectroscopy

Chemistry 328N

Spin States

Electrons have a spin quantum number of 12

with allowed values of +12 and -12

ndash One can consider this as spinning charge that

creates an associated magnetic field

ndash Electrons therefore behave like tiny bar magnets

ndash Remember the Pauli exclusion principle

Spin ldquouprdquo and spin ldquodownrdquo

Chemistry 328N

Nuclear Spin States Nuclei with an odd mass an odd atomic number

or both also have a net spin and a resulting nuclear

magnetic moment

The allowed nuclear spin states are determined by

the spin quantum number I of the nucleus

For each I there are 2I + 1 spin states

If I = 12 there are two allowed spin states

Chemistry 328N

Nuclear Spins The shell model for the nucleus tells us that

nucleons just like electrons fill orbitals

When the number of protons or neutrons

equals 2 8 20 28 50 82 and 126 orbitals

are filled Because nucleons have spin just

like electrons do their spin can pair up

when the orbitals are being filled and cancel

out

Chemistry 328N

Nuclear Spins1 If the number of neutrons and the number

of protons are both even then the nucleus

has NO spin He for example has no spin

2 If the number of neutrons plus the number

of protons is odd then the nucleus has a

half-integer spin (ie 12 32 52) (H and 13C for example are both 12)

3 If the number of neutrons and the number

of protons are both odd then the nucleus

has an integer spin (ie 1 2 3) (Deuterium

or N for example)

Chemistry 328N

Nuclear Spins in a Magnetic Field

Within a collection of 1H or 13C atoms nuclear spins are random in orientation

When placed in a strong external magneticfield the interaction between nuclear spinsand the applied magnetic field is quantizedwith the result that only certain orientationsof the nuclear magnetic moments areallowed

Chemistry 328N

Nuclear Spins in a Magnetic Field

E=hn or n =Eh

Chemistry 328N

Nuclear Magnetic Resonance

If the nucleus is irradiated with radiation

having energy (E=h) that is exactly the

same as the difference between the nuclear

spin states

ndash energy is absorbed and

ndash the nuclear spin is flipped from spin state +12

(with the applied field) to -12 (against the

applied field)

Chemistry 328N

Nuclear Spin States

Spin quantum numbers and allowed nuclear

spin states for selected isotopes of elements

common to organic compounds

Element 1H 2H 12C 13C 14N 16O 31P

number of

spin states

12 1 0 0 0

32S

12 1

2 3 1 2 3 1

12

2 1

nuclear spin

quantum

number ( I )

Chemistry 328N

Serbian-American inventor electrical engineer and scientist

Born 1856 in Smiljan Lika (Austria-Hungary)

Died 1943 in New York City New York (USA)

Inventions a telephone repeater rotating magnetic field principle polyphase

alternating-current system induction motor alternating-current power

transmission Tesla coil transformer wireless communication radio

fluorescent lights and more than 700 other patents

Nikola Tesla

T (Tesla) = W (Weber)

m2

Chemistry 328N

Famous and Controversial picture of Tesla

httpwwwteslasocietycomindexhtml

Chemistry 328N

ldquoThe ray was described as the most important of all Teslarsquos inventions so far It was

said that IT COULD SEND CONSECRATED BEAMS OF PARTICLES THROUGH

FREE AIR and could cause armies of millions to drop dead in their tracks

Wardenclyffe Tower

if constructed would result in

An inexpensive instrument not

bigger than a watch will enable its

bearer to hear anywhere on sea or

land music or song the speech of a

political leader the address of an

eminent man of science or the

sermon of an eloquent clergyman

delivered in some other place

however distant In the same

manner any picture character

drawing or print can be transferred

from one to another place

Tesla ray gun

Chemistry 328N

)( 0BfhE == n

42

At B=10T

E = 4258MHz

Chemistry 328N

Nuclear Spins in B0

In an applied field strength of 705T (BIG)

E between nuclear spin states for

ndash 1H is approximately 00286 calmol which

corresponds to electromagnetic radiation of 300

MHz (300000000 Hz)

ndash 13C is approximately 000715 calmol which

corresponds to electromagnetic radiation of

75MHz (75000000 Hz)

ndash This E is quite smallhelliplow frequency

radiation induces ldquofliprdquo (resonance)

Chemistry 328N

ldquoResonancerdquo The transition from the lower state to the higher

occurs at unique combinations of magnetic field and frequency of electromagnetic radiation

When placed in a magnetic field of strength B a particle with a net spin can absorb a photon of frequency n The frequency n depends on the gyromagnetic ratio of the particle

n = B

For hydrogen = 4258 MHz Tesla

Allows you to calculate ldquospectrometer frequencyrdquo for 1H

This is the frequency at which ldquonakedrdquo 1H resonates in that machine

Chemistry 328N

Some Proportionality Constants

Gyromagnetic Ratio n = B

ndash For 1H = 4258 MHzT

Planckrsquos Constant E = h n

Speed of light n = c l or c = n l

Chemical Shift 119889(119901119901119898) =∆n

119878119901119890119888119905119903119900119898119890119905119890119903 119891119903119890119902119906119890119899119888119910

Chemistry 328N

NMR Spectrometer

Chemistry 328N

In principle we could hold field constant and scan frequency looking

for resonance but it is equally effective to scan field strength and hold

frequency constant

Chemistry 328N

500MHz 1H-nmr Spectrometer

Magnet

Chemistry 328N

httpwwwjeolusacomRESOURCESAnalyticalInstrumentsNMRMagnetDestructiontabid390Defaultaspx

Chemistry 328N

800 MHz machine at UH

Highest Frequency in 2013

The first Avance 1000 system was

delivered to the new lsquoCentre de RMN agrave

Tregraves Hauts Champsrsquo in Lyon France

1020 MHz nmr

June 2015

Weight 15 tons

Chemistry 328N

The 100MHz nmr Chart

1000 900 800 700 600 500 400 300 200 100 00

10

20

30

40

50

60

70

80

90

000

Si CH3

CH3

CH3

CH3

Frequency

field

The TMS resonance is defined as having ldquo0rdquo frequency

Chemistry 328N

100MHz Spectrum

450 400 350 300 250 200 150 100 50 00

5

10

15

20

Hz

CH3 Cl

325 320 315 310 305 300 295 290 285 2800

5

10

15

2030400

304 Hz

Chemistry 328N

100MHz nmr Spectrum

450 400 350 300 250 200 150 100 50 00

5

10

15

20

CH3 Br

275 270 265 260 2550

5

10

15

20

26850

Hz2685Hz

Chemistry 328N

Nuclear Magnetic Resonance

If we were dealing with 1H nuclei isolatedfrom all other atoms and electrons anycombination of applied field and radiation thatproduces a signal for one 1H would produce asignal for all 1H The same for 13C nuclei

But helliphydrogens in organic molecules are notisolated from all other atoms they aresurrounded by electrons which are caused tocirculate by the presence of the applied field

Chemistry 328N

Nuclear Magnetic Resonance

The circulation of electrons around anucleus in an applied field is calleddiamagnetic current

This current generates a field that opposesthe applied field diamagnetic nuclearshielding results Lenzrsquos Law

The difference in resonance frequenciesbetween the various hydrogen nuclei withina molecule is due to shieldingdeshielding isvery small but very important

Chemistry 328N

Lenzrsquos Law

Heinrich Lenz

1804-1865

Chemistry 328N

Conditions for Resonance

It is the frequency of the radiation and the

NET field at the nucleus that matters

The NET field is the sum of all incident

magnetic fields including those from

ndash The Giant Magnet (applied field)

ndash Diamagnetic Shielding field (electrons)

ndash Coupling (spin fields of adjacent nuclei)

ndash credit card strips earthrsquos field etchellip

Page 5: OC 2/e 12 - University of Texas at Austinwillson.cm.utexas.edu/Teaching/Chem328N/Files/Lecture 03... · 2016. 1. 29. · Born, 1856 in Smiljan, Lika (Austria-Hungary) Died 1943 in

Chemistry 328N

Absorbance promotes atom or molecule to higher energy state

Chemistry 328N

Molecular Spectroscopy

We study three types of molecular spectroscopy

nuclear spin energy levels

vibrational energy levels

electronic energy levels

radio frequency

infrared

ultraviolet-visible

Absorption of Radiation Results

in Transition Between

Region of the

Spectrum

Chemistry 328N

Absorption of electromagnetic radiation

Described by quantum mechanical theories

Only discrete (unique) energy states are

allowed (accessible)

Therefore only discrete (unique) amounts of

radiation can be absorbed (or emitted)

How many potential energy states are

available to the ball

Chemistry 328N

Summarybull Molecular Spectroscopy Concept

ndash Discrete transitions in energy levels

ndash Transitions with varying energy (areas of spectrum)bull Nmr nuclear spin radio frequency region

bull IR vibration infrared region

bull UV-Vis electronic transitions UV to visible

bull Please know relationships between frequency wave

length and energy

bull Know length scale conversionshellipmicron

millimeter nanometer angstrom

Chemistry 328N

NMR Spectroscopy

Chemistry 328N

Spin States

Electrons have a spin quantum number of 12

with allowed values of +12 and -12

ndash One can consider this as spinning charge that

creates an associated magnetic field

ndash Electrons therefore behave like tiny bar magnets

ndash Remember the Pauli exclusion principle

Spin ldquouprdquo and spin ldquodownrdquo

Chemistry 328N

Nuclear Spin States Nuclei with an odd mass an odd atomic number

or both also have a net spin and a resulting nuclear

magnetic moment

The allowed nuclear spin states are determined by

the spin quantum number I of the nucleus

For each I there are 2I + 1 spin states

If I = 12 there are two allowed spin states

Chemistry 328N

Nuclear Spins The shell model for the nucleus tells us that

nucleons just like electrons fill orbitals

When the number of protons or neutrons

equals 2 8 20 28 50 82 and 126 orbitals

are filled Because nucleons have spin just

like electrons do their spin can pair up

when the orbitals are being filled and cancel

out

Chemistry 328N

Nuclear Spins1 If the number of neutrons and the number

of protons are both even then the nucleus

has NO spin He for example has no spin

2 If the number of neutrons plus the number

of protons is odd then the nucleus has a

half-integer spin (ie 12 32 52) (H and 13C for example are both 12)

3 If the number of neutrons and the number

of protons are both odd then the nucleus

has an integer spin (ie 1 2 3) (Deuterium

or N for example)

Chemistry 328N

Nuclear Spins in a Magnetic Field

Within a collection of 1H or 13C atoms nuclear spins are random in orientation

When placed in a strong external magneticfield the interaction between nuclear spinsand the applied magnetic field is quantizedwith the result that only certain orientationsof the nuclear magnetic moments areallowed

Chemistry 328N

Nuclear Spins in a Magnetic Field

E=hn or n =Eh

Chemistry 328N

Nuclear Magnetic Resonance

If the nucleus is irradiated with radiation

having energy (E=h) that is exactly the

same as the difference between the nuclear

spin states

ndash energy is absorbed and

ndash the nuclear spin is flipped from spin state +12

(with the applied field) to -12 (against the

applied field)

Chemistry 328N

Nuclear Spin States

Spin quantum numbers and allowed nuclear

spin states for selected isotopes of elements

common to organic compounds

Element 1H 2H 12C 13C 14N 16O 31P

number of

spin states

12 1 0 0 0

32S

12 1

2 3 1 2 3 1

12

2 1

nuclear spin

quantum

number ( I )

Chemistry 328N

Serbian-American inventor electrical engineer and scientist

Born 1856 in Smiljan Lika (Austria-Hungary)

Died 1943 in New York City New York (USA)

Inventions a telephone repeater rotating magnetic field principle polyphase

alternating-current system induction motor alternating-current power

transmission Tesla coil transformer wireless communication radio

fluorescent lights and more than 700 other patents

Nikola Tesla

T (Tesla) = W (Weber)

m2

Chemistry 328N

Famous and Controversial picture of Tesla

httpwwwteslasocietycomindexhtml

Chemistry 328N

ldquoThe ray was described as the most important of all Teslarsquos inventions so far It was

said that IT COULD SEND CONSECRATED BEAMS OF PARTICLES THROUGH

FREE AIR and could cause armies of millions to drop dead in their tracks

Wardenclyffe Tower

if constructed would result in

An inexpensive instrument not

bigger than a watch will enable its

bearer to hear anywhere on sea or

land music or song the speech of a

political leader the address of an

eminent man of science or the

sermon of an eloquent clergyman

delivered in some other place

however distant In the same

manner any picture character

drawing or print can be transferred

from one to another place

Tesla ray gun

Chemistry 328N

)( 0BfhE == n

42

At B=10T

E = 4258MHz

Chemistry 328N

Nuclear Spins in B0

In an applied field strength of 705T (BIG)

E between nuclear spin states for

ndash 1H is approximately 00286 calmol which

corresponds to electromagnetic radiation of 300

MHz (300000000 Hz)

ndash 13C is approximately 000715 calmol which

corresponds to electromagnetic radiation of

75MHz (75000000 Hz)

ndash This E is quite smallhelliplow frequency

radiation induces ldquofliprdquo (resonance)

Chemistry 328N

ldquoResonancerdquo The transition from the lower state to the higher

occurs at unique combinations of magnetic field and frequency of electromagnetic radiation

When placed in a magnetic field of strength B a particle with a net spin can absorb a photon of frequency n The frequency n depends on the gyromagnetic ratio of the particle

n = B

For hydrogen = 4258 MHz Tesla

Allows you to calculate ldquospectrometer frequencyrdquo for 1H

This is the frequency at which ldquonakedrdquo 1H resonates in that machine

Chemistry 328N

Some Proportionality Constants

Gyromagnetic Ratio n = B

ndash For 1H = 4258 MHzT

Planckrsquos Constant E = h n

Speed of light n = c l or c = n l

Chemical Shift 119889(119901119901119898) =∆n

119878119901119890119888119905119903119900119898119890119905119890119903 119891119903119890119902119906119890119899119888119910

Chemistry 328N

NMR Spectrometer

Chemistry 328N

In principle we could hold field constant and scan frequency looking

for resonance but it is equally effective to scan field strength and hold

frequency constant

Chemistry 328N

500MHz 1H-nmr Spectrometer

Magnet

Chemistry 328N

httpwwwjeolusacomRESOURCESAnalyticalInstrumentsNMRMagnetDestructiontabid390Defaultaspx

Chemistry 328N

800 MHz machine at UH

Highest Frequency in 2013

The first Avance 1000 system was

delivered to the new lsquoCentre de RMN agrave

Tregraves Hauts Champsrsquo in Lyon France

1020 MHz nmr

June 2015

Weight 15 tons

Chemistry 328N

The 100MHz nmr Chart

1000 900 800 700 600 500 400 300 200 100 00

10

20

30

40

50

60

70

80

90

000

Si CH3

CH3

CH3

CH3

Frequency

field

The TMS resonance is defined as having ldquo0rdquo frequency

Chemistry 328N

100MHz Spectrum

450 400 350 300 250 200 150 100 50 00

5

10

15

20

Hz

CH3 Cl

325 320 315 310 305 300 295 290 285 2800

5

10

15

2030400

304 Hz

Chemistry 328N

100MHz nmr Spectrum

450 400 350 300 250 200 150 100 50 00

5

10

15

20

CH3 Br

275 270 265 260 2550

5

10

15

20

26850

Hz2685Hz

Chemistry 328N

Nuclear Magnetic Resonance

If we were dealing with 1H nuclei isolatedfrom all other atoms and electrons anycombination of applied field and radiation thatproduces a signal for one 1H would produce asignal for all 1H The same for 13C nuclei

But helliphydrogens in organic molecules are notisolated from all other atoms they aresurrounded by electrons which are caused tocirculate by the presence of the applied field

Chemistry 328N

Nuclear Magnetic Resonance

The circulation of electrons around anucleus in an applied field is calleddiamagnetic current

This current generates a field that opposesthe applied field diamagnetic nuclearshielding results Lenzrsquos Law

The difference in resonance frequenciesbetween the various hydrogen nuclei withina molecule is due to shieldingdeshielding isvery small but very important

Chemistry 328N

Lenzrsquos Law

Heinrich Lenz

1804-1865

Chemistry 328N

Conditions for Resonance

It is the frequency of the radiation and the

NET field at the nucleus that matters

The NET field is the sum of all incident

magnetic fields including those from

ndash The Giant Magnet (applied field)

ndash Diamagnetic Shielding field (electrons)

ndash Coupling (spin fields of adjacent nuclei)

ndash credit card strips earthrsquos field etchellip

Page 6: OC 2/e 12 - University of Texas at Austinwillson.cm.utexas.edu/Teaching/Chem328N/Files/Lecture 03... · 2016. 1. 29. · Born, 1856 in Smiljan, Lika (Austria-Hungary) Died 1943 in

Chemistry 328N

Molecular Spectroscopy

We study three types of molecular spectroscopy

nuclear spin energy levels

vibrational energy levels

electronic energy levels

radio frequency

infrared

ultraviolet-visible

Absorption of Radiation Results

in Transition Between

Region of the

Spectrum

Chemistry 328N

Absorption of electromagnetic radiation

Described by quantum mechanical theories

Only discrete (unique) energy states are

allowed (accessible)

Therefore only discrete (unique) amounts of

radiation can be absorbed (or emitted)

How many potential energy states are

available to the ball

Chemistry 328N

Summarybull Molecular Spectroscopy Concept

ndash Discrete transitions in energy levels

ndash Transitions with varying energy (areas of spectrum)bull Nmr nuclear spin radio frequency region

bull IR vibration infrared region

bull UV-Vis electronic transitions UV to visible

bull Please know relationships between frequency wave

length and energy

bull Know length scale conversionshellipmicron

millimeter nanometer angstrom

Chemistry 328N

NMR Spectroscopy

Chemistry 328N

Spin States

Electrons have a spin quantum number of 12

with allowed values of +12 and -12

ndash One can consider this as spinning charge that

creates an associated magnetic field

ndash Electrons therefore behave like tiny bar magnets

ndash Remember the Pauli exclusion principle

Spin ldquouprdquo and spin ldquodownrdquo

Chemistry 328N

Nuclear Spin States Nuclei with an odd mass an odd atomic number

or both also have a net spin and a resulting nuclear

magnetic moment

The allowed nuclear spin states are determined by

the spin quantum number I of the nucleus

For each I there are 2I + 1 spin states

If I = 12 there are two allowed spin states

Chemistry 328N

Nuclear Spins The shell model for the nucleus tells us that

nucleons just like electrons fill orbitals

When the number of protons or neutrons

equals 2 8 20 28 50 82 and 126 orbitals

are filled Because nucleons have spin just

like electrons do their spin can pair up

when the orbitals are being filled and cancel

out

Chemistry 328N

Nuclear Spins1 If the number of neutrons and the number

of protons are both even then the nucleus

has NO spin He for example has no spin

2 If the number of neutrons plus the number

of protons is odd then the nucleus has a

half-integer spin (ie 12 32 52) (H and 13C for example are both 12)

3 If the number of neutrons and the number

of protons are both odd then the nucleus

has an integer spin (ie 1 2 3) (Deuterium

or N for example)

Chemistry 328N

Nuclear Spins in a Magnetic Field

Within a collection of 1H or 13C atoms nuclear spins are random in orientation

When placed in a strong external magneticfield the interaction between nuclear spinsand the applied magnetic field is quantizedwith the result that only certain orientationsof the nuclear magnetic moments areallowed

Chemistry 328N

Nuclear Spins in a Magnetic Field

E=hn or n =Eh

Chemistry 328N

Nuclear Magnetic Resonance

If the nucleus is irradiated with radiation

having energy (E=h) that is exactly the

same as the difference between the nuclear

spin states

ndash energy is absorbed and

ndash the nuclear spin is flipped from spin state +12

(with the applied field) to -12 (against the

applied field)

Chemistry 328N

Nuclear Spin States

Spin quantum numbers and allowed nuclear

spin states for selected isotopes of elements

common to organic compounds

Element 1H 2H 12C 13C 14N 16O 31P

number of

spin states

12 1 0 0 0

32S

12 1

2 3 1 2 3 1

12

2 1

nuclear spin

quantum

number ( I )

Chemistry 328N

Serbian-American inventor electrical engineer and scientist

Born 1856 in Smiljan Lika (Austria-Hungary)

Died 1943 in New York City New York (USA)

Inventions a telephone repeater rotating magnetic field principle polyphase

alternating-current system induction motor alternating-current power

transmission Tesla coil transformer wireless communication radio

fluorescent lights and more than 700 other patents

Nikola Tesla

T (Tesla) = W (Weber)

m2

Chemistry 328N

Famous and Controversial picture of Tesla

httpwwwteslasocietycomindexhtml

Chemistry 328N

ldquoThe ray was described as the most important of all Teslarsquos inventions so far It was

said that IT COULD SEND CONSECRATED BEAMS OF PARTICLES THROUGH

FREE AIR and could cause armies of millions to drop dead in their tracks

Wardenclyffe Tower

if constructed would result in

An inexpensive instrument not

bigger than a watch will enable its

bearer to hear anywhere on sea or

land music or song the speech of a

political leader the address of an

eminent man of science or the

sermon of an eloquent clergyman

delivered in some other place

however distant In the same

manner any picture character

drawing or print can be transferred

from one to another place

Tesla ray gun

Chemistry 328N

)( 0BfhE == n

42

At B=10T

E = 4258MHz

Chemistry 328N

Nuclear Spins in B0

In an applied field strength of 705T (BIG)

E between nuclear spin states for

ndash 1H is approximately 00286 calmol which

corresponds to electromagnetic radiation of 300

MHz (300000000 Hz)

ndash 13C is approximately 000715 calmol which

corresponds to electromagnetic radiation of

75MHz (75000000 Hz)

ndash This E is quite smallhelliplow frequency

radiation induces ldquofliprdquo (resonance)

Chemistry 328N

ldquoResonancerdquo The transition from the lower state to the higher

occurs at unique combinations of magnetic field and frequency of electromagnetic radiation

When placed in a magnetic field of strength B a particle with a net spin can absorb a photon of frequency n The frequency n depends on the gyromagnetic ratio of the particle

n = B

For hydrogen = 4258 MHz Tesla

Allows you to calculate ldquospectrometer frequencyrdquo for 1H

This is the frequency at which ldquonakedrdquo 1H resonates in that machine

Chemistry 328N

Some Proportionality Constants

Gyromagnetic Ratio n = B

ndash For 1H = 4258 MHzT

Planckrsquos Constant E = h n

Speed of light n = c l or c = n l

Chemical Shift 119889(119901119901119898) =∆n

119878119901119890119888119905119903119900119898119890119905119890119903 119891119903119890119902119906119890119899119888119910

Chemistry 328N

NMR Spectrometer

Chemistry 328N

In principle we could hold field constant and scan frequency looking

for resonance but it is equally effective to scan field strength and hold

frequency constant

Chemistry 328N

500MHz 1H-nmr Spectrometer

Magnet

Chemistry 328N

httpwwwjeolusacomRESOURCESAnalyticalInstrumentsNMRMagnetDestructiontabid390Defaultaspx

Chemistry 328N

800 MHz machine at UH

Highest Frequency in 2013

The first Avance 1000 system was

delivered to the new lsquoCentre de RMN agrave

Tregraves Hauts Champsrsquo in Lyon France

1020 MHz nmr

June 2015

Weight 15 tons

Chemistry 328N

The 100MHz nmr Chart

1000 900 800 700 600 500 400 300 200 100 00

10

20

30

40

50

60

70

80

90

000

Si CH3

CH3

CH3

CH3

Frequency

field

The TMS resonance is defined as having ldquo0rdquo frequency

Chemistry 328N

100MHz Spectrum

450 400 350 300 250 200 150 100 50 00

5

10

15

20

Hz

CH3 Cl

325 320 315 310 305 300 295 290 285 2800

5

10

15

2030400

304 Hz

Chemistry 328N

100MHz nmr Spectrum

450 400 350 300 250 200 150 100 50 00

5

10

15

20

CH3 Br

275 270 265 260 2550

5

10

15

20

26850

Hz2685Hz

Chemistry 328N

Nuclear Magnetic Resonance

If we were dealing with 1H nuclei isolatedfrom all other atoms and electrons anycombination of applied field and radiation thatproduces a signal for one 1H would produce asignal for all 1H The same for 13C nuclei

But helliphydrogens in organic molecules are notisolated from all other atoms they aresurrounded by electrons which are caused tocirculate by the presence of the applied field

Chemistry 328N

Nuclear Magnetic Resonance

The circulation of electrons around anucleus in an applied field is calleddiamagnetic current

This current generates a field that opposesthe applied field diamagnetic nuclearshielding results Lenzrsquos Law

The difference in resonance frequenciesbetween the various hydrogen nuclei withina molecule is due to shieldingdeshielding isvery small but very important

Chemistry 328N

Lenzrsquos Law

Heinrich Lenz

1804-1865

Chemistry 328N

Conditions for Resonance

It is the frequency of the radiation and the

NET field at the nucleus that matters

The NET field is the sum of all incident

magnetic fields including those from

ndash The Giant Magnet (applied field)

ndash Diamagnetic Shielding field (electrons)

ndash Coupling (spin fields of adjacent nuclei)

ndash credit card strips earthrsquos field etchellip

Page 7: OC 2/e 12 - University of Texas at Austinwillson.cm.utexas.edu/Teaching/Chem328N/Files/Lecture 03... · 2016. 1. 29. · Born, 1856 in Smiljan, Lika (Austria-Hungary) Died 1943 in

Chemistry 328N

Absorption of electromagnetic radiation

Described by quantum mechanical theories

Only discrete (unique) energy states are

allowed (accessible)

Therefore only discrete (unique) amounts of

radiation can be absorbed (or emitted)

How many potential energy states are

available to the ball

Chemistry 328N

Summarybull Molecular Spectroscopy Concept

ndash Discrete transitions in energy levels

ndash Transitions with varying energy (areas of spectrum)bull Nmr nuclear spin radio frequency region

bull IR vibration infrared region

bull UV-Vis electronic transitions UV to visible

bull Please know relationships between frequency wave

length and energy

bull Know length scale conversionshellipmicron

millimeter nanometer angstrom

Chemistry 328N

NMR Spectroscopy

Chemistry 328N

Spin States

Electrons have a spin quantum number of 12

with allowed values of +12 and -12

ndash One can consider this as spinning charge that

creates an associated magnetic field

ndash Electrons therefore behave like tiny bar magnets

ndash Remember the Pauli exclusion principle

Spin ldquouprdquo and spin ldquodownrdquo

Chemistry 328N

Nuclear Spin States Nuclei with an odd mass an odd atomic number

or both also have a net spin and a resulting nuclear

magnetic moment

The allowed nuclear spin states are determined by

the spin quantum number I of the nucleus

For each I there are 2I + 1 spin states

If I = 12 there are two allowed spin states

Chemistry 328N

Nuclear Spins The shell model for the nucleus tells us that

nucleons just like electrons fill orbitals

When the number of protons or neutrons

equals 2 8 20 28 50 82 and 126 orbitals

are filled Because nucleons have spin just

like electrons do their spin can pair up

when the orbitals are being filled and cancel

out

Chemistry 328N

Nuclear Spins1 If the number of neutrons and the number

of protons are both even then the nucleus

has NO spin He for example has no spin

2 If the number of neutrons plus the number

of protons is odd then the nucleus has a

half-integer spin (ie 12 32 52) (H and 13C for example are both 12)

3 If the number of neutrons and the number

of protons are both odd then the nucleus

has an integer spin (ie 1 2 3) (Deuterium

or N for example)

Chemistry 328N

Nuclear Spins in a Magnetic Field

Within a collection of 1H or 13C atoms nuclear spins are random in orientation

When placed in a strong external magneticfield the interaction between nuclear spinsand the applied magnetic field is quantizedwith the result that only certain orientationsof the nuclear magnetic moments areallowed

Chemistry 328N

Nuclear Spins in a Magnetic Field

E=hn or n =Eh

Chemistry 328N

Nuclear Magnetic Resonance

If the nucleus is irradiated with radiation

having energy (E=h) that is exactly the

same as the difference between the nuclear

spin states

ndash energy is absorbed and

ndash the nuclear spin is flipped from spin state +12

(with the applied field) to -12 (against the

applied field)

Chemistry 328N

Nuclear Spin States

Spin quantum numbers and allowed nuclear

spin states for selected isotopes of elements

common to organic compounds

Element 1H 2H 12C 13C 14N 16O 31P

number of

spin states

12 1 0 0 0

32S

12 1

2 3 1 2 3 1

12

2 1

nuclear spin

quantum

number ( I )

Chemistry 328N

Serbian-American inventor electrical engineer and scientist

Born 1856 in Smiljan Lika (Austria-Hungary)

Died 1943 in New York City New York (USA)

Inventions a telephone repeater rotating magnetic field principle polyphase

alternating-current system induction motor alternating-current power

transmission Tesla coil transformer wireless communication radio

fluorescent lights and more than 700 other patents

Nikola Tesla

T (Tesla) = W (Weber)

m2

Chemistry 328N

Famous and Controversial picture of Tesla

httpwwwteslasocietycomindexhtml

Chemistry 328N

ldquoThe ray was described as the most important of all Teslarsquos inventions so far It was

said that IT COULD SEND CONSECRATED BEAMS OF PARTICLES THROUGH

FREE AIR and could cause armies of millions to drop dead in their tracks

Wardenclyffe Tower

if constructed would result in

An inexpensive instrument not

bigger than a watch will enable its

bearer to hear anywhere on sea or

land music or song the speech of a

political leader the address of an

eminent man of science or the

sermon of an eloquent clergyman

delivered in some other place

however distant In the same

manner any picture character

drawing or print can be transferred

from one to another place

Tesla ray gun

Chemistry 328N

)( 0BfhE == n

42

At B=10T

E = 4258MHz

Chemistry 328N

Nuclear Spins in B0

In an applied field strength of 705T (BIG)

E between nuclear spin states for

ndash 1H is approximately 00286 calmol which

corresponds to electromagnetic radiation of 300

MHz (300000000 Hz)

ndash 13C is approximately 000715 calmol which

corresponds to electromagnetic radiation of

75MHz (75000000 Hz)

ndash This E is quite smallhelliplow frequency

radiation induces ldquofliprdquo (resonance)

Chemistry 328N

ldquoResonancerdquo The transition from the lower state to the higher

occurs at unique combinations of magnetic field and frequency of electromagnetic radiation

When placed in a magnetic field of strength B a particle with a net spin can absorb a photon of frequency n The frequency n depends on the gyromagnetic ratio of the particle

n = B

For hydrogen = 4258 MHz Tesla

Allows you to calculate ldquospectrometer frequencyrdquo for 1H

This is the frequency at which ldquonakedrdquo 1H resonates in that machine

Chemistry 328N

Some Proportionality Constants

Gyromagnetic Ratio n = B

ndash For 1H = 4258 MHzT

Planckrsquos Constant E = h n

Speed of light n = c l or c = n l

Chemical Shift 119889(119901119901119898) =∆n

119878119901119890119888119905119903119900119898119890119905119890119903 119891119903119890119902119906119890119899119888119910

Chemistry 328N

NMR Spectrometer

Chemistry 328N

In principle we could hold field constant and scan frequency looking

for resonance but it is equally effective to scan field strength and hold

frequency constant

Chemistry 328N

500MHz 1H-nmr Spectrometer

Magnet

Chemistry 328N

httpwwwjeolusacomRESOURCESAnalyticalInstrumentsNMRMagnetDestructiontabid390Defaultaspx

Chemistry 328N

800 MHz machine at UH

Highest Frequency in 2013

The first Avance 1000 system was

delivered to the new lsquoCentre de RMN agrave

Tregraves Hauts Champsrsquo in Lyon France

1020 MHz nmr

June 2015

Weight 15 tons

Chemistry 328N

The 100MHz nmr Chart

1000 900 800 700 600 500 400 300 200 100 00

10

20

30

40

50

60

70

80

90

000

Si CH3

CH3

CH3

CH3

Frequency

field

The TMS resonance is defined as having ldquo0rdquo frequency

Chemistry 328N

100MHz Spectrum

450 400 350 300 250 200 150 100 50 00

5

10

15

20

Hz

CH3 Cl

325 320 315 310 305 300 295 290 285 2800

5

10

15

2030400

304 Hz

Chemistry 328N

100MHz nmr Spectrum

450 400 350 300 250 200 150 100 50 00

5

10

15

20

CH3 Br

275 270 265 260 2550

5

10

15

20

26850

Hz2685Hz

Chemistry 328N

Nuclear Magnetic Resonance

If we were dealing with 1H nuclei isolatedfrom all other atoms and electrons anycombination of applied field and radiation thatproduces a signal for one 1H would produce asignal for all 1H The same for 13C nuclei

But helliphydrogens in organic molecules are notisolated from all other atoms they aresurrounded by electrons which are caused tocirculate by the presence of the applied field

Chemistry 328N

Nuclear Magnetic Resonance

The circulation of electrons around anucleus in an applied field is calleddiamagnetic current

This current generates a field that opposesthe applied field diamagnetic nuclearshielding results Lenzrsquos Law

The difference in resonance frequenciesbetween the various hydrogen nuclei withina molecule is due to shieldingdeshielding isvery small but very important

Chemistry 328N

Lenzrsquos Law

Heinrich Lenz

1804-1865

Chemistry 328N

Conditions for Resonance

It is the frequency of the radiation and the

NET field at the nucleus that matters

The NET field is the sum of all incident

magnetic fields including those from

ndash The Giant Magnet (applied field)

ndash Diamagnetic Shielding field (electrons)

ndash Coupling (spin fields of adjacent nuclei)

ndash credit card strips earthrsquos field etchellip

Page 8: OC 2/e 12 - University of Texas at Austinwillson.cm.utexas.edu/Teaching/Chem328N/Files/Lecture 03... · 2016. 1. 29. · Born, 1856 in Smiljan, Lika (Austria-Hungary) Died 1943 in

Chemistry 328N

Summarybull Molecular Spectroscopy Concept

ndash Discrete transitions in energy levels

ndash Transitions with varying energy (areas of spectrum)bull Nmr nuclear spin radio frequency region

bull IR vibration infrared region

bull UV-Vis electronic transitions UV to visible

bull Please know relationships between frequency wave

length and energy

bull Know length scale conversionshellipmicron

millimeter nanometer angstrom

Chemistry 328N

NMR Spectroscopy

Chemistry 328N

Spin States

Electrons have a spin quantum number of 12

with allowed values of +12 and -12

ndash One can consider this as spinning charge that

creates an associated magnetic field

ndash Electrons therefore behave like tiny bar magnets

ndash Remember the Pauli exclusion principle

Spin ldquouprdquo and spin ldquodownrdquo

Chemistry 328N

Nuclear Spin States Nuclei with an odd mass an odd atomic number

or both also have a net spin and a resulting nuclear

magnetic moment

The allowed nuclear spin states are determined by

the spin quantum number I of the nucleus

For each I there are 2I + 1 spin states

If I = 12 there are two allowed spin states

Chemistry 328N

Nuclear Spins The shell model for the nucleus tells us that

nucleons just like electrons fill orbitals

When the number of protons or neutrons

equals 2 8 20 28 50 82 and 126 orbitals

are filled Because nucleons have spin just

like electrons do their spin can pair up

when the orbitals are being filled and cancel

out

Chemistry 328N

Nuclear Spins1 If the number of neutrons and the number

of protons are both even then the nucleus

has NO spin He for example has no spin

2 If the number of neutrons plus the number

of protons is odd then the nucleus has a

half-integer spin (ie 12 32 52) (H and 13C for example are both 12)

3 If the number of neutrons and the number

of protons are both odd then the nucleus

has an integer spin (ie 1 2 3) (Deuterium

or N for example)

Chemistry 328N

Nuclear Spins in a Magnetic Field

Within a collection of 1H or 13C atoms nuclear spins are random in orientation

When placed in a strong external magneticfield the interaction between nuclear spinsand the applied magnetic field is quantizedwith the result that only certain orientationsof the nuclear magnetic moments areallowed

Chemistry 328N

Nuclear Spins in a Magnetic Field

E=hn or n =Eh

Chemistry 328N

Nuclear Magnetic Resonance

If the nucleus is irradiated with radiation

having energy (E=h) that is exactly the

same as the difference between the nuclear

spin states

ndash energy is absorbed and

ndash the nuclear spin is flipped from spin state +12

(with the applied field) to -12 (against the

applied field)

Chemistry 328N

Nuclear Spin States

Spin quantum numbers and allowed nuclear

spin states for selected isotopes of elements

common to organic compounds

Element 1H 2H 12C 13C 14N 16O 31P

number of

spin states

12 1 0 0 0

32S

12 1

2 3 1 2 3 1

12

2 1

nuclear spin

quantum

number ( I )

Chemistry 328N

Serbian-American inventor electrical engineer and scientist

Born 1856 in Smiljan Lika (Austria-Hungary)

Died 1943 in New York City New York (USA)

Inventions a telephone repeater rotating magnetic field principle polyphase

alternating-current system induction motor alternating-current power

transmission Tesla coil transformer wireless communication radio

fluorescent lights and more than 700 other patents

Nikola Tesla

T (Tesla) = W (Weber)

m2

Chemistry 328N

Famous and Controversial picture of Tesla

httpwwwteslasocietycomindexhtml

Chemistry 328N

ldquoThe ray was described as the most important of all Teslarsquos inventions so far It was

said that IT COULD SEND CONSECRATED BEAMS OF PARTICLES THROUGH

FREE AIR and could cause armies of millions to drop dead in their tracks

Wardenclyffe Tower

if constructed would result in

An inexpensive instrument not

bigger than a watch will enable its

bearer to hear anywhere on sea or

land music or song the speech of a

political leader the address of an

eminent man of science or the

sermon of an eloquent clergyman

delivered in some other place

however distant In the same

manner any picture character

drawing or print can be transferred

from one to another place

Tesla ray gun

Chemistry 328N

)( 0BfhE == n

42

At B=10T

E = 4258MHz

Chemistry 328N

Nuclear Spins in B0

In an applied field strength of 705T (BIG)

E between nuclear spin states for

ndash 1H is approximately 00286 calmol which

corresponds to electromagnetic radiation of 300

MHz (300000000 Hz)

ndash 13C is approximately 000715 calmol which

corresponds to electromagnetic radiation of

75MHz (75000000 Hz)

ndash This E is quite smallhelliplow frequency

radiation induces ldquofliprdquo (resonance)

Chemistry 328N

ldquoResonancerdquo The transition from the lower state to the higher

occurs at unique combinations of magnetic field and frequency of electromagnetic radiation

When placed in a magnetic field of strength B a particle with a net spin can absorb a photon of frequency n The frequency n depends on the gyromagnetic ratio of the particle

n = B

For hydrogen = 4258 MHz Tesla

Allows you to calculate ldquospectrometer frequencyrdquo for 1H

This is the frequency at which ldquonakedrdquo 1H resonates in that machine

Chemistry 328N

Some Proportionality Constants

Gyromagnetic Ratio n = B

ndash For 1H = 4258 MHzT

Planckrsquos Constant E = h n

Speed of light n = c l or c = n l

Chemical Shift 119889(119901119901119898) =∆n

119878119901119890119888119905119903119900119898119890119905119890119903 119891119903119890119902119906119890119899119888119910

Chemistry 328N

NMR Spectrometer

Chemistry 328N

In principle we could hold field constant and scan frequency looking

for resonance but it is equally effective to scan field strength and hold

frequency constant

Chemistry 328N

500MHz 1H-nmr Spectrometer

Magnet

Chemistry 328N

httpwwwjeolusacomRESOURCESAnalyticalInstrumentsNMRMagnetDestructiontabid390Defaultaspx

Chemistry 328N

800 MHz machine at UH

Highest Frequency in 2013

The first Avance 1000 system was

delivered to the new lsquoCentre de RMN agrave

Tregraves Hauts Champsrsquo in Lyon France

1020 MHz nmr

June 2015

Weight 15 tons

Chemistry 328N

The 100MHz nmr Chart

1000 900 800 700 600 500 400 300 200 100 00

10

20

30

40

50

60

70

80

90

000

Si CH3

CH3

CH3

CH3

Frequency

field

The TMS resonance is defined as having ldquo0rdquo frequency

Chemistry 328N

100MHz Spectrum

450 400 350 300 250 200 150 100 50 00

5

10

15

20

Hz

CH3 Cl

325 320 315 310 305 300 295 290 285 2800

5

10

15

2030400

304 Hz

Chemistry 328N

100MHz nmr Spectrum

450 400 350 300 250 200 150 100 50 00

5

10

15

20

CH3 Br

275 270 265 260 2550

5

10

15

20

26850

Hz2685Hz

Chemistry 328N

Nuclear Magnetic Resonance

If we were dealing with 1H nuclei isolatedfrom all other atoms and electrons anycombination of applied field and radiation thatproduces a signal for one 1H would produce asignal for all 1H The same for 13C nuclei

But helliphydrogens in organic molecules are notisolated from all other atoms they aresurrounded by electrons which are caused tocirculate by the presence of the applied field

Chemistry 328N

Nuclear Magnetic Resonance

The circulation of electrons around anucleus in an applied field is calleddiamagnetic current

This current generates a field that opposesthe applied field diamagnetic nuclearshielding results Lenzrsquos Law

The difference in resonance frequenciesbetween the various hydrogen nuclei withina molecule is due to shieldingdeshielding isvery small but very important

Chemistry 328N

Lenzrsquos Law

Heinrich Lenz

1804-1865

Chemistry 328N

Conditions for Resonance

It is the frequency of the radiation and the

NET field at the nucleus that matters

The NET field is the sum of all incident

magnetic fields including those from

ndash The Giant Magnet (applied field)

ndash Diamagnetic Shielding field (electrons)

ndash Coupling (spin fields of adjacent nuclei)

ndash credit card strips earthrsquos field etchellip

Page 9: OC 2/e 12 - University of Texas at Austinwillson.cm.utexas.edu/Teaching/Chem328N/Files/Lecture 03... · 2016. 1. 29. · Born, 1856 in Smiljan, Lika (Austria-Hungary) Died 1943 in

Chemistry 328N

NMR Spectroscopy

Chemistry 328N

Spin States

Electrons have a spin quantum number of 12

with allowed values of +12 and -12

ndash One can consider this as spinning charge that

creates an associated magnetic field

ndash Electrons therefore behave like tiny bar magnets

ndash Remember the Pauli exclusion principle

Spin ldquouprdquo and spin ldquodownrdquo

Chemistry 328N

Nuclear Spin States Nuclei with an odd mass an odd atomic number

or both also have a net spin and a resulting nuclear

magnetic moment

The allowed nuclear spin states are determined by

the spin quantum number I of the nucleus

For each I there are 2I + 1 spin states

If I = 12 there are two allowed spin states

Chemistry 328N

Nuclear Spins The shell model for the nucleus tells us that

nucleons just like electrons fill orbitals

When the number of protons or neutrons

equals 2 8 20 28 50 82 and 126 orbitals

are filled Because nucleons have spin just

like electrons do their spin can pair up

when the orbitals are being filled and cancel

out

Chemistry 328N

Nuclear Spins1 If the number of neutrons and the number

of protons are both even then the nucleus

has NO spin He for example has no spin

2 If the number of neutrons plus the number

of protons is odd then the nucleus has a

half-integer spin (ie 12 32 52) (H and 13C for example are both 12)

3 If the number of neutrons and the number

of protons are both odd then the nucleus

has an integer spin (ie 1 2 3) (Deuterium

or N for example)

Chemistry 328N

Nuclear Spins in a Magnetic Field

Within a collection of 1H or 13C atoms nuclear spins are random in orientation

When placed in a strong external magneticfield the interaction between nuclear spinsand the applied magnetic field is quantizedwith the result that only certain orientationsof the nuclear magnetic moments areallowed

Chemistry 328N

Nuclear Spins in a Magnetic Field

E=hn or n =Eh

Chemistry 328N

Nuclear Magnetic Resonance

If the nucleus is irradiated with radiation

having energy (E=h) that is exactly the

same as the difference between the nuclear

spin states

ndash energy is absorbed and

ndash the nuclear spin is flipped from spin state +12

(with the applied field) to -12 (against the

applied field)

Chemistry 328N

Nuclear Spin States

Spin quantum numbers and allowed nuclear

spin states for selected isotopes of elements

common to organic compounds

Element 1H 2H 12C 13C 14N 16O 31P

number of

spin states

12 1 0 0 0

32S

12 1

2 3 1 2 3 1

12

2 1

nuclear spin

quantum

number ( I )

Chemistry 328N

Serbian-American inventor electrical engineer and scientist

Born 1856 in Smiljan Lika (Austria-Hungary)

Died 1943 in New York City New York (USA)

Inventions a telephone repeater rotating magnetic field principle polyphase

alternating-current system induction motor alternating-current power

transmission Tesla coil transformer wireless communication radio

fluorescent lights and more than 700 other patents

Nikola Tesla

T (Tesla) = W (Weber)

m2

Chemistry 328N

Famous and Controversial picture of Tesla

httpwwwteslasocietycomindexhtml

Chemistry 328N

ldquoThe ray was described as the most important of all Teslarsquos inventions so far It was

said that IT COULD SEND CONSECRATED BEAMS OF PARTICLES THROUGH

FREE AIR and could cause armies of millions to drop dead in their tracks

Wardenclyffe Tower

if constructed would result in

An inexpensive instrument not

bigger than a watch will enable its

bearer to hear anywhere on sea or

land music or song the speech of a

political leader the address of an

eminent man of science or the

sermon of an eloquent clergyman

delivered in some other place

however distant In the same

manner any picture character

drawing or print can be transferred

from one to another place

Tesla ray gun

Chemistry 328N

)( 0BfhE == n

42

At B=10T

E = 4258MHz

Chemistry 328N

Nuclear Spins in B0

In an applied field strength of 705T (BIG)

E between nuclear spin states for

ndash 1H is approximately 00286 calmol which

corresponds to electromagnetic radiation of 300

MHz (300000000 Hz)

ndash 13C is approximately 000715 calmol which

corresponds to electromagnetic radiation of

75MHz (75000000 Hz)

ndash This E is quite smallhelliplow frequency

radiation induces ldquofliprdquo (resonance)

Chemistry 328N

ldquoResonancerdquo The transition from the lower state to the higher

occurs at unique combinations of magnetic field and frequency of electromagnetic radiation

When placed in a magnetic field of strength B a particle with a net spin can absorb a photon of frequency n The frequency n depends on the gyromagnetic ratio of the particle

n = B

For hydrogen = 4258 MHz Tesla

Allows you to calculate ldquospectrometer frequencyrdquo for 1H

This is the frequency at which ldquonakedrdquo 1H resonates in that machine

Chemistry 328N

Some Proportionality Constants

Gyromagnetic Ratio n = B

ndash For 1H = 4258 MHzT

Planckrsquos Constant E = h n

Speed of light n = c l or c = n l

Chemical Shift 119889(119901119901119898) =∆n

119878119901119890119888119905119903119900119898119890119905119890119903 119891119903119890119902119906119890119899119888119910

Chemistry 328N

NMR Spectrometer

Chemistry 328N

In principle we could hold field constant and scan frequency looking

for resonance but it is equally effective to scan field strength and hold

frequency constant

Chemistry 328N

500MHz 1H-nmr Spectrometer

Magnet

Chemistry 328N

httpwwwjeolusacomRESOURCESAnalyticalInstrumentsNMRMagnetDestructiontabid390Defaultaspx

Chemistry 328N

800 MHz machine at UH

Highest Frequency in 2013

The first Avance 1000 system was

delivered to the new lsquoCentre de RMN agrave

Tregraves Hauts Champsrsquo in Lyon France

1020 MHz nmr

June 2015

Weight 15 tons

Chemistry 328N

The 100MHz nmr Chart

1000 900 800 700 600 500 400 300 200 100 00

10

20

30

40

50

60

70

80

90

000

Si CH3

CH3

CH3

CH3

Frequency

field

The TMS resonance is defined as having ldquo0rdquo frequency

Chemistry 328N

100MHz Spectrum

450 400 350 300 250 200 150 100 50 00

5

10

15

20

Hz

CH3 Cl

325 320 315 310 305 300 295 290 285 2800

5

10

15

2030400

304 Hz

Chemistry 328N

100MHz nmr Spectrum

450 400 350 300 250 200 150 100 50 00

5

10

15

20

CH3 Br

275 270 265 260 2550

5

10

15

20

26850

Hz2685Hz

Chemistry 328N

Nuclear Magnetic Resonance

If we were dealing with 1H nuclei isolatedfrom all other atoms and electrons anycombination of applied field and radiation thatproduces a signal for one 1H would produce asignal for all 1H The same for 13C nuclei

But helliphydrogens in organic molecules are notisolated from all other atoms they aresurrounded by electrons which are caused tocirculate by the presence of the applied field

Chemistry 328N

Nuclear Magnetic Resonance

The circulation of electrons around anucleus in an applied field is calleddiamagnetic current

This current generates a field that opposesthe applied field diamagnetic nuclearshielding results Lenzrsquos Law

The difference in resonance frequenciesbetween the various hydrogen nuclei withina molecule is due to shieldingdeshielding isvery small but very important

Chemistry 328N

Lenzrsquos Law

Heinrich Lenz

1804-1865

Chemistry 328N

Conditions for Resonance

It is the frequency of the radiation and the

NET field at the nucleus that matters

The NET field is the sum of all incident

magnetic fields including those from

ndash The Giant Magnet (applied field)

ndash Diamagnetic Shielding field (electrons)

ndash Coupling (spin fields of adjacent nuclei)

ndash credit card strips earthrsquos field etchellip

Page 10: OC 2/e 12 - University of Texas at Austinwillson.cm.utexas.edu/Teaching/Chem328N/Files/Lecture 03... · 2016. 1. 29. · Born, 1856 in Smiljan, Lika (Austria-Hungary) Died 1943 in

Chemistry 328N

Spin States

Electrons have a spin quantum number of 12

with allowed values of +12 and -12

ndash One can consider this as spinning charge that

creates an associated magnetic field

ndash Electrons therefore behave like tiny bar magnets

ndash Remember the Pauli exclusion principle

Spin ldquouprdquo and spin ldquodownrdquo

Chemistry 328N

Nuclear Spin States Nuclei with an odd mass an odd atomic number

or both also have a net spin and a resulting nuclear

magnetic moment

The allowed nuclear spin states are determined by

the spin quantum number I of the nucleus

For each I there are 2I + 1 spin states

If I = 12 there are two allowed spin states

Chemistry 328N

Nuclear Spins The shell model for the nucleus tells us that

nucleons just like electrons fill orbitals

When the number of protons or neutrons

equals 2 8 20 28 50 82 and 126 orbitals

are filled Because nucleons have spin just

like electrons do their spin can pair up

when the orbitals are being filled and cancel

out

Chemistry 328N

Nuclear Spins1 If the number of neutrons and the number

of protons are both even then the nucleus

has NO spin He for example has no spin

2 If the number of neutrons plus the number

of protons is odd then the nucleus has a

half-integer spin (ie 12 32 52) (H and 13C for example are both 12)

3 If the number of neutrons and the number

of protons are both odd then the nucleus

has an integer spin (ie 1 2 3) (Deuterium

or N for example)

Chemistry 328N

Nuclear Spins in a Magnetic Field

Within a collection of 1H or 13C atoms nuclear spins are random in orientation

When placed in a strong external magneticfield the interaction between nuclear spinsand the applied magnetic field is quantizedwith the result that only certain orientationsof the nuclear magnetic moments areallowed

Chemistry 328N

Nuclear Spins in a Magnetic Field

E=hn or n =Eh

Chemistry 328N

Nuclear Magnetic Resonance

If the nucleus is irradiated with radiation

having energy (E=h) that is exactly the

same as the difference between the nuclear

spin states

ndash energy is absorbed and

ndash the nuclear spin is flipped from spin state +12

(with the applied field) to -12 (against the

applied field)

Chemistry 328N

Nuclear Spin States

Spin quantum numbers and allowed nuclear

spin states for selected isotopes of elements

common to organic compounds

Element 1H 2H 12C 13C 14N 16O 31P

number of

spin states

12 1 0 0 0

32S

12 1

2 3 1 2 3 1

12

2 1

nuclear spin

quantum

number ( I )

Chemistry 328N

Serbian-American inventor electrical engineer and scientist

Born 1856 in Smiljan Lika (Austria-Hungary)

Died 1943 in New York City New York (USA)

Inventions a telephone repeater rotating magnetic field principle polyphase

alternating-current system induction motor alternating-current power

transmission Tesla coil transformer wireless communication radio

fluorescent lights and more than 700 other patents

Nikola Tesla

T (Tesla) = W (Weber)

m2

Chemistry 328N

Famous and Controversial picture of Tesla

httpwwwteslasocietycomindexhtml

Chemistry 328N

ldquoThe ray was described as the most important of all Teslarsquos inventions so far It was

said that IT COULD SEND CONSECRATED BEAMS OF PARTICLES THROUGH

FREE AIR and could cause armies of millions to drop dead in their tracks

Wardenclyffe Tower

if constructed would result in

An inexpensive instrument not

bigger than a watch will enable its

bearer to hear anywhere on sea or

land music or song the speech of a

political leader the address of an

eminent man of science or the

sermon of an eloquent clergyman

delivered in some other place

however distant In the same

manner any picture character

drawing or print can be transferred

from one to another place

Tesla ray gun

Chemistry 328N

)( 0BfhE == n

42

At B=10T

E = 4258MHz

Chemistry 328N

Nuclear Spins in B0

In an applied field strength of 705T (BIG)

E between nuclear spin states for

ndash 1H is approximately 00286 calmol which

corresponds to electromagnetic radiation of 300

MHz (300000000 Hz)

ndash 13C is approximately 000715 calmol which

corresponds to electromagnetic radiation of

75MHz (75000000 Hz)

ndash This E is quite smallhelliplow frequency

radiation induces ldquofliprdquo (resonance)

Chemistry 328N

ldquoResonancerdquo The transition from the lower state to the higher

occurs at unique combinations of magnetic field and frequency of electromagnetic radiation

When placed in a magnetic field of strength B a particle with a net spin can absorb a photon of frequency n The frequency n depends on the gyromagnetic ratio of the particle

n = B

For hydrogen = 4258 MHz Tesla

Allows you to calculate ldquospectrometer frequencyrdquo for 1H

This is the frequency at which ldquonakedrdquo 1H resonates in that machine

Chemistry 328N

Some Proportionality Constants

Gyromagnetic Ratio n = B

ndash For 1H = 4258 MHzT

Planckrsquos Constant E = h n

Speed of light n = c l or c = n l

Chemical Shift 119889(119901119901119898) =∆n

119878119901119890119888119905119903119900119898119890119905119890119903 119891119903119890119902119906119890119899119888119910

Chemistry 328N

NMR Spectrometer

Chemistry 328N

In principle we could hold field constant and scan frequency looking

for resonance but it is equally effective to scan field strength and hold

frequency constant

Chemistry 328N

500MHz 1H-nmr Spectrometer

Magnet

Chemistry 328N

httpwwwjeolusacomRESOURCESAnalyticalInstrumentsNMRMagnetDestructiontabid390Defaultaspx

Chemistry 328N

800 MHz machine at UH

Highest Frequency in 2013

The first Avance 1000 system was

delivered to the new lsquoCentre de RMN agrave

Tregraves Hauts Champsrsquo in Lyon France

1020 MHz nmr

June 2015

Weight 15 tons

Chemistry 328N

The 100MHz nmr Chart

1000 900 800 700 600 500 400 300 200 100 00

10

20

30

40

50

60

70

80

90

000

Si CH3

CH3

CH3

CH3

Frequency

field

The TMS resonance is defined as having ldquo0rdquo frequency

Chemistry 328N

100MHz Spectrum

450 400 350 300 250 200 150 100 50 00

5

10

15

20

Hz

CH3 Cl

325 320 315 310 305 300 295 290 285 2800

5

10

15

2030400

304 Hz

Chemistry 328N

100MHz nmr Spectrum

450 400 350 300 250 200 150 100 50 00

5

10

15

20

CH3 Br

275 270 265 260 2550

5

10

15

20

26850

Hz2685Hz

Chemistry 328N

Nuclear Magnetic Resonance

If we were dealing with 1H nuclei isolatedfrom all other atoms and electrons anycombination of applied field and radiation thatproduces a signal for one 1H would produce asignal for all 1H The same for 13C nuclei

But helliphydrogens in organic molecules are notisolated from all other atoms they aresurrounded by electrons which are caused tocirculate by the presence of the applied field

Chemistry 328N

Nuclear Magnetic Resonance

The circulation of electrons around anucleus in an applied field is calleddiamagnetic current

This current generates a field that opposesthe applied field diamagnetic nuclearshielding results Lenzrsquos Law

The difference in resonance frequenciesbetween the various hydrogen nuclei withina molecule is due to shieldingdeshielding isvery small but very important

Chemistry 328N

Lenzrsquos Law

Heinrich Lenz

1804-1865

Chemistry 328N

Conditions for Resonance

It is the frequency of the radiation and the

NET field at the nucleus that matters

The NET field is the sum of all incident

magnetic fields including those from

ndash The Giant Magnet (applied field)

ndash Diamagnetic Shielding field (electrons)

ndash Coupling (spin fields of adjacent nuclei)

ndash credit card strips earthrsquos field etchellip

Page 11: OC 2/e 12 - University of Texas at Austinwillson.cm.utexas.edu/Teaching/Chem328N/Files/Lecture 03... · 2016. 1. 29. · Born, 1856 in Smiljan, Lika (Austria-Hungary) Died 1943 in

Chemistry 328N

Nuclear Spin States Nuclei with an odd mass an odd atomic number

or both also have a net spin and a resulting nuclear

magnetic moment

The allowed nuclear spin states are determined by

the spin quantum number I of the nucleus

For each I there are 2I + 1 spin states

If I = 12 there are two allowed spin states

Chemistry 328N

Nuclear Spins The shell model for the nucleus tells us that

nucleons just like electrons fill orbitals

When the number of protons or neutrons

equals 2 8 20 28 50 82 and 126 orbitals

are filled Because nucleons have spin just

like electrons do their spin can pair up

when the orbitals are being filled and cancel

out

Chemistry 328N

Nuclear Spins1 If the number of neutrons and the number

of protons are both even then the nucleus

has NO spin He for example has no spin

2 If the number of neutrons plus the number

of protons is odd then the nucleus has a

half-integer spin (ie 12 32 52) (H and 13C for example are both 12)

3 If the number of neutrons and the number

of protons are both odd then the nucleus

has an integer spin (ie 1 2 3) (Deuterium

or N for example)

Chemistry 328N

Nuclear Spins in a Magnetic Field

Within a collection of 1H or 13C atoms nuclear spins are random in orientation

When placed in a strong external magneticfield the interaction between nuclear spinsand the applied magnetic field is quantizedwith the result that only certain orientationsof the nuclear magnetic moments areallowed

Chemistry 328N

Nuclear Spins in a Magnetic Field

E=hn or n =Eh

Chemistry 328N

Nuclear Magnetic Resonance

If the nucleus is irradiated with radiation

having energy (E=h) that is exactly the

same as the difference between the nuclear

spin states

ndash energy is absorbed and

ndash the nuclear spin is flipped from spin state +12

(with the applied field) to -12 (against the

applied field)

Chemistry 328N

Nuclear Spin States

Spin quantum numbers and allowed nuclear

spin states for selected isotopes of elements

common to organic compounds

Element 1H 2H 12C 13C 14N 16O 31P

number of

spin states

12 1 0 0 0

32S

12 1

2 3 1 2 3 1

12

2 1

nuclear spin

quantum

number ( I )

Chemistry 328N

Serbian-American inventor electrical engineer and scientist

Born 1856 in Smiljan Lika (Austria-Hungary)

Died 1943 in New York City New York (USA)

Inventions a telephone repeater rotating magnetic field principle polyphase

alternating-current system induction motor alternating-current power

transmission Tesla coil transformer wireless communication radio

fluorescent lights and more than 700 other patents

Nikola Tesla

T (Tesla) = W (Weber)

m2

Chemistry 328N

Famous and Controversial picture of Tesla

httpwwwteslasocietycomindexhtml

Chemistry 328N

ldquoThe ray was described as the most important of all Teslarsquos inventions so far It was

said that IT COULD SEND CONSECRATED BEAMS OF PARTICLES THROUGH

FREE AIR and could cause armies of millions to drop dead in their tracks

Wardenclyffe Tower

if constructed would result in

An inexpensive instrument not

bigger than a watch will enable its

bearer to hear anywhere on sea or

land music or song the speech of a

political leader the address of an

eminent man of science or the

sermon of an eloquent clergyman

delivered in some other place

however distant In the same

manner any picture character

drawing or print can be transferred

from one to another place

Tesla ray gun

Chemistry 328N

)( 0BfhE == n

42

At B=10T

E = 4258MHz

Chemistry 328N

Nuclear Spins in B0

In an applied field strength of 705T (BIG)

E between nuclear spin states for

ndash 1H is approximately 00286 calmol which

corresponds to electromagnetic radiation of 300

MHz (300000000 Hz)

ndash 13C is approximately 000715 calmol which

corresponds to electromagnetic radiation of

75MHz (75000000 Hz)

ndash This E is quite smallhelliplow frequency

radiation induces ldquofliprdquo (resonance)

Chemistry 328N

ldquoResonancerdquo The transition from the lower state to the higher

occurs at unique combinations of magnetic field and frequency of electromagnetic radiation

When placed in a magnetic field of strength B a particle with a net spin can absorb a photon of frequency n The frequency n depends on the gyromagnetic ratio of the particle

n = B

For hydrogen = 4258 MHz Tesla

Allows you to calculate ldquospectrometer frequencyrdquo for 1H

This is the frequency at which ldquonakedrdquo 1H resonates in that machine

Chemistry 328N

Some Proportionality Constants

Gyromagnetic Ratio n = B

ndash For 1H = 4258 MHzT

Planckrsquos Constant E = h n

Speed of light n = c l or c = n l

Chemical Shift 119889(119901119901119898) =∆n

119878119901119890119888119905119903119900119898119890119905119890119903 119891119903119890119902119906119890119899119888119910

Chemistry 328N

NMR Spectrometer

Chemistry 328N

In principle we could hold field constant and scan frequency looking

for resonance but it is equally effective to scan field strength and hold

frequency constant

Chemistry 328N

500MHz 1H-nmr Spectrometer

Magnet

Chemistry 328N

httpwwwjeolusacomRESOURCESAnalyticalInstrumentsNMRMagnetDestructiontabid390Defaultaspx

Chemistry 328N

800 MHz machine at UH

Highest Frequency in 2013

The first Avance 1000 system was

delivered to the new lsquoCentre de RMN agrave

Tregraves Hauts Champsrsquo in Lyon France

1020 MHz nmr

June 2015

Weight 15 tons

Chemistry 328N

The 100MHz nmr Chart

1000 900 800 700 600 500 400 300 200 100 00

10

20

30

40

50

60

70

80

90

000

Si CH3

CH3

CH3

CH3

Frequency

field

The TMS resonance is defined as having ldquo0rdquo frequency

Chemistry 328N

100MHz Spectrum

450 400 350 300 250 200 150 100 50 00

5

10

15

20

Hz

CH3 Cl

325 320 315 310 305 300 295 290 285 2800

5

10

15

2030400

304 Hz

Chemistry 328N

100MHz nmr Spectrum

450 400 350 300 250 200 150 100 50 00

5

10

15

20

CH3 Br

275 270 265 260 2550

5

10

15

20

26850

Hz2685Hz

Chemistry 328N

Nuclear Magnetic Resonance

If we were dealing with 1H nuclei isolatedfrom all other atoms and electrons anycombination of applied field and radiation thatproduces a signal for one 1H would produce asignal for all 1H The same for 13C nuclei

But helliphydrogens in organic molecules are notisolated from all other atoms they aresurrounded by electrons which are caused tocirculate by the presence of the applied field

Chemistry 328N

Nuclear Magnetic Resonance

The circulation of electrons around anucleus in an applied field is calleddiamagnetic current

This current generates a field that opposesthe applied field diamagnetic nuclearshielding results Lenzrsquos Law

The difference in resonance frequenciesbetween the various hydrogen nuclei withina molecule is due to shieldingdeshielding isvery small but very important

Chemistry 328N

Lenzrsquos Law

Heinrich Lenz

1804-1865

Chemistry 328N

Conditions for Resonance

It is the frequency of the radiation and the

NET field at the nucleus that matters

The NET field is the sum of all incident

magnetic fields including those from

ndash The Giant Magnet (applied field)

ndash Diamagnetic Shielding field (electrons)

ndash Coupling (spin fields of adjacent nuclei)

ndash credit card strips earthrsquos field etchellip

Page 12: OC 2/e 12 - University of Texas at Austinwillson.cm.utexas.edu/Teaching/Chem328N/Files/Lecture 03... · 2016. 1. 29. · Born, 1856 in Smiljan, Lika (Austria-Hungary) Died 1943 in

Chemistry 328N

Nuclear Spins The shell model for the nucleus tells us that

nucleons just like electrons fill orbitals

When the number of protons or neutrons

equals 2 8 20 28 50 82 and 126 orbitals

are filled Because nucleons have spin just

like electrons do their spin can pair up

when the orbitals are being filled and cancel

out

Chemistry 328N

Nuclear Spins1 If the number of neutrons and the number

of protons are both even then the nucleus

has NO spin He for example has no spin

2 If the number of neutrons plus the number

of protons is odd then the nucleus has a

half-integer spin (ie 12 32 52) (H and 13C for example are both 12)

3 If the number of neutrons and the number

of protons are both odd then the nucleus

has an integer spin (ie 1 2 3) (Deuterium

or N for example)

Chemistry 328N

Nuclear Spins in a Magnetic Field

Within a collection of 1H or 13C atoms nuclear spins are random in orientation

When placed in a strong external magneticfield the interaction between nuclear spinsand the applied magnetic field is quantizedwith the result that only certain orientationsof the nuclear magnetic moments areallowed

Chemistry 328N

Nuclear Spins in a Magnetic Field

E=hn or n =Eh

Chemistry 328N

Nuclear Magnetic Resonance

If the nucleus is irradiated with radiation

having energy (E=h) that is exactly the

same as the difference between the nuclear

spin states

ndash energy is absorbed and

ndash the nuclear spin is flipped from spin state +12

(with the applied field) to -12 (against the

applied field)

Chemistry 328N

Nuclear Spin States

Spin quantum numbers and allowed nuclear

spin states for selected isotopes of elements

common to organic compounds

Element 1H 2H 12C 13C 14N 16O 31P

number of

spin states

12 1 0 0 0

32S

12 1

2 3 1 2 3 1

12

2 1

nuclear spin

quantum

number ( I )

Chemistry 328N

Serbian-American inventor electrical engineer and scientist

Born 1856 in Smiljan Lika (Austria-Hungary)

Died 1943 in New York City New York (USA)

Inventions a telephone repeater rotating magnetic field principle polyphase

alternating-current system induction motor alternating-current power

transmission Tesla coil transformer wireless communication radio

fluorescent lights and more than 700 other patents

Nikola Tesla

T (Tesla) = W (Weber)

m2

Chemistry 328N

Famous and Controversial picture of Tesla

httpwwwteslasocietycomindexhtml

Chemistry 328N

ldquoThe ray was described as the most important of all Teslarsquos inventions so far It was

said that IT COULD SEND CONSECRATED BEAMS OF PARTICLES THROUGH

FREE AIR and could cause armies of millions to drop dead in their tracks

Wardenclyffe Tower

if constructed would result in

An inexpensive instrument not

bigger than a watch will enable its

bearer to hear anywhere on sea or

land music or song the speech of a

political leader the address of an

eminent man of science or the

sermon of an eloquent clergyman

delivered in some other place

however distant In the same

manner any picture character

drawing or print can be transferred

from one to another place

Tesla ray gun

Chemistry 328N

)( 0BfhE == n

42

At B=10T

E = 4258MHz

Chemistry 328N

Nuclear Spins in B0

In an applied field strength of 705T (BIG)

E between nuclear spin states for

ndash 1H is approximately 00286 calmol which

corresponds to electromagnetic radiation of 300

MHz (300000000 Hz)

ndash 13C is approximately 000715 calmol which

corresponds to electromagnetic radiation of

75MHz (75000000 Hz)

ndash This E is quite smallhelliplow frequency

radiation induces ldquofliprdquo (resonance)

Chemistry 328N

ldquoResonancerdquo The transition from the lower state to the higher

occurs at unique combinations of magnetic field and frequency of electromagnetic radiation

When placed in a magnetic field of strength B a particle with a net spin can absorb a photon of frequency n The frequency n depends on the gyromagnetic ratio of the particle

n = B

For hydrogen = 4258 MHz Tesla

Allows you to calculate ldquospectrometer frequencyrdquo for 1H

This is the frequency at which ldquonakedrdquo 1H resonates in that machine

Chemistry 328N

Some Proportionality Constants

Gyromagnetic Ratio n = B

ndash For 1H = 4258 MHzT

Planckrsquos Constant E = h n

Speed of light n = c l or c = n l

Chemical Shift 119889(119901119901119898) =∆n

119878119901119890119888119905119903119900119898119890119905119890119903 119891119903119890119902119906119890119899119888119910

Chemistry 328N

NMR Spectrometer

Chemistry 328N

In principle we could hold field constant and scan frequency looking

for resonance but it is equally effective to scan field strength and hold

frequency constant

Chemistry 328N

500MHz 1H-nmr Spectrometer

Magnet

Chemistry 328N

httpwwwjeolusacomRESOURCESAnalyticalInstrumentsNMRMagnetDestructiontabid390Defaultaspx

Chemistry 328N

800 MHz machine at UH

Highest Frequency in 2013

The first Avance 1000 system was

delivered to the new lsquoCentre de RMN agrave

Tregraves Hauts Champsrsquo in Lyon France

1020 MHz nmr

June 2015

Weight 15 tons

Chemistry 328N

The 100MHz nmr Chart

1000 900 800 700 600 500 400 300 200 100 00

10

20

30

40

50

60

70

80

90

000

Si CH3

CH3

CH3

CH3

Frequency

field

The TMS resonance is defined as having ldquo0rdquo frequency

Chemistry 328N

100MHz Spectrum

450 400 350 300 250 200 150 100 50 00

5

10

15

20

Hz

CH3 Cl

325 320 315 310 305 300 295 290 285 2800

5

10

15

2030400

304 Hz

Chemistry 328N

100MHz nmr Spectrum

450 400 350 300 250 200 150 100 50 00

5

10

15

20

CH3 Br

275 270 265 260 2550

5

10

15

20

26850

Hz2685Hz

Chemistry 328N

Nuclear Magnetic Resonance

If we were dealing with 1H nuclei isolatedfrom all other atoms and electrons anycombination of applied field and radiation thatproduces a signal for one 1H would produce asignal for all 1H The same for 13C nuclei

But helliphydrogens in organic molecules are notisolated from all other atoms they aresurrounded by electrons which are caused tocirculate by the presence of the applied field

Chemistry 328N

Nuclear Magnetic Resonance

The circulation of electrons around anucleus in an applied field is calleddiamagnetic current

This current generates a field that opposesthe applied field diamagnetic nuclearshielding results Lenzrsquos Law

The difference in resonance frequenciesbetween the various hydrogen nuclei withina molecule is due to shieldingdeshielding isvery small but very important

Chemistry 328N

Lenzrsquos Law

Heinrich Lenz

1804-1865

Chemistry 328N

Conditions for Resonance

It is the frequency of the radiation and the

NET field at the nucleus that matters

The NET field is the sum of all incident

magnetic fields including those from

ndash The Giant Magnet (applied field)

ndash Diamagnetic Shielding field (electrons)

ndash Coupling (spin fields of adjacent nuclei)

ndash credit card strips earthrsquos field etchellip

Page 13: OC 2/e 12 - University of Texas at Austinwillson.cm.utexas.edu/Teaching/Chem328N/Files/Lecture 03... · 2016. 1. 29. · Born, 1856 in Smiljan, Lika (Austria-Hungary) Died 1943 in

Chemistry 328N

Nuclear Spins1 If the number of neutrons and the number

of protons are both even then the nucleus

has NO spin He for example has no spin

2 If the number of neutrons plus the number

of protons is odd then the nucleus has a

half-integer spin (ie 12 32 52) (H and 13C for example are both 12)

3 If the number of neutrons and the number

of protons are both odd then the nucleus

has an integer spin (ie 1 2 3) (Deuterium

or N for example)

Chemistry 328N

Nuclear Spins in a Magnetic Field

Within a collection of 1H or 13C atoms nuclear spins are random in orientation

When placed in a strong external magneticfield the interaction between nuclear spinsand the applied magnetic field is quantizedwith the result that only certain orientationsof the nuclear magnetic moments areallowed

Chemistry 328N

Nuclear Spins in a Magnetic Field

E=hn or n =Eh

Chemistry 328N

Nuclear Magnetic Resonance

If the nucleus is irradiated with radiation

having energy (E=h) that is exactly the

same as the difference between the nuclear

spin states

ndash energy is absorbed and

ndash the nuclear spin is flipped from spin state +12

(with the applied field) to -12 (against the

applied field)

Chemistry 328N

Nuclear Spin States

Spin quantum numbers and allowed nuclear

spin states for selected isotopes of elements

common to organic compounds

Element 1H 2H 12C 13C 14N 16O 31P

number of

spin states

12 1 0 0 0

32S

12 1

2 3 1 2 3 1

12

2 1

nuclear spin

quantum

number ( I )

Chemistry 328N

Serbian-American inventor electrical engineer and scientist

Born 1856 in Smiljan Lika (Austria-Hungary)

Died 1943 in New York City New York (USA)

Inventions a telephone repeater rotating magnetic field principle polyphase

alternating-current system induction motor alternating-current power

transmission Tesla coil transformer wireless communication radio

fluorescent lights and more than 700 other patents

Nikola Tesla

T (Tesla) = W (Weber)

m2

Chemistry 328N

Famous and Controversial picture of Tesla

httpwwwteslasocietycomindexhtml

Chemistry 328N

ldquoThe ray was described as the most important of all Teslarsquos inventions so far It was

said that IT COULD SEND CONSECRATED BEAMS OF PARTICLES THROUGH

FREE AIR and could cause armies of millions to drop dead in their tracks

Wardenclyffe Tower

if constructed would result in

An inexpensive instrument not

bigger than a watch will enable its

bearer to hear anywhere on sea or

land music or song the speech of a

political leader the address of an

eminent man of science or the

sermon of an eloquent clergyman

delivered in some other place

however distant In the same

manner any picture character

drawing or print can be transferred

from one to another place

Tesla ray gun

Chemistry 328N

)( 0BfhE == n

42

At B=10T

E = 4258MHz

Chemistry 328N

Nuclear Spins in B0

In an applied field strength of 705T (BIG)

E between nuclear spin states for

ndash 1H is approximately 00286 calmol which

corresponds to electromagnetic radiation of 300

MHz (300000000 Hz)

ndash 13C is approximately 000715 calmol which

corresponds to electromagnetic radiation of

75MHz (75000000 Hz)

ndash This E is quite smallhelliplow frequency

radiation induces ldquofliprdquo (resonance)

Chemistry 328N

ldquoResonancerdquo The transition from the lower state to the higher

occurs at unique combinations of magnetic field and frequency of electromagnetic radiation

When placed in a magnetic field of strength B a particle with a net spin can absorb a photon of frequency n The frequency n depends on the gyromagnetic ratio of the particle

n = B

For hydrogen = 4258 MHz Tesla

Allows you to calculate ldquospectrometer frequencyrdquo for 1H

This is the frequency at which ldquonakedrdquo 1H resonates in that machine

Chemistry 328N

Some Proportionality Constants

Gyromagnetic Ratio n = B

ndash For 1H = 4258 MHzT

Planckrsquos Constant E = h n

Speed of light n = c l or c = n l

Chemical Shift 119889(119901119901119898) =∆n

119878119901119890119888119905119903119900119898119890119905119890119903 119891119903119890119902119906119890119899119888119910

Chemistry 328N

NMR Spectrometer

Chemistry 328N

In principle we could hold field constant and scan frequency looking

for resonance but it is equally effective to scan field strength and hold

frequency constant

Chemistry 328N

500MHz 1H-nmr Spectrometer

Magnet

Chemistry 328N

httpwwwjeolusacomRESOURCESAnalyticalInstrumentsNMRMagnetDestructiontabid390Defaultaspx

Chemistry 328N

800 MHz machine at UH

Highest Frequency in 2013

The first Avance 1000 system was

delivered to the new lsquoCentre de RMN agrave

Tregraves Hauts Champsrsquo in Lyon France

1020 MHz nmr

June 2015

Weight 15 tons

Chemistry 328N

The 100MHz nmr Chart

1000 900 800 700 600 500 400 300 200 100 00

10

20

30

40

50

60

70

80

90

000

Si CH3

CH3

CH3

CH3

Frequency

field

The TMS resonance is defined as having ldquo0rdquo frequency

Chemistry 328N

100MHz Spectrum

450 400 350 300 250 200 150 100 50 00

5

10

15

20

Hz

CH3 Cl

325 320 315 310 305 300 295 290 285 2800

5

10

15

2030400

304 Hz

Chemistry 328N

100MHz nmr Spectrum

450 400 350 300 250 200 150 100 50 00

5

10

15

20

CH3 Br

275 270 265 260 2550

5

10

15

20

26850

Hz2685Hz

Chemistry 328N

Nuclear Magnetic Resonance

If we were dealing with 1H nuclei isolatedfrom all other atoms and electrons anycombination of applied field and radiation thatproduces a signal for one 1H would produce asignal for all 1H The same for 13C nuclei

But helliphydrogens in organic molecules are notisolated from all other atoms they aresurrounded by electrons which are caused tocirculate by the presence of the applied field

Chemistry 328N

Nuclear Magnetic Resonance

The circulation of electrons around anucleus in an applied field is calleddiamagnetic current

This current generates a field that opposesthe applied field diamagnetic nuclearshielding results Lenzrsquos Law

The difference in resonance frequenciesbetween the various hydrogen nuclei withina molecule is due to shieldingdeshielding isvery small but very important

Chemistry 328N

Lenzrsquos Law

Heinrich Lenz

1804-1865

Chemistry 328N

Conditions for Resonance

It is the frequency of the radiation and the

NET field at the nucleus that matters

The NET field is the sum of all incident

magnetic fields including those from

ndash The Giant Magnet (applied field)

ndash Diamagnetic Shielding field (electrons)

ndash Coupling (spin fields of adjacent nuclei)

ndash credit card strips earthrsquos field etchellip

Page 14: OC 2/e 12 - University of Texas at Austinwillson.cm.utexas.edu/Teaching/Chem328N/Files/Lecture 03... · 2016. 1. 29. · Born, 1856 in Smiljan, Lika (Austria-Hungary) Died 1943 in

Chemistry 328N

Nuclear Spins in a Magnetic Field

Within a collection of 1H or 13C atoms nuclear spins are random in orientation

When placed in a strong external magneticfield the interaction between nuclear spinsand the applied magnetic field is quantizedwith the result that only certain orientationsof the nuclear magnetic moments areallowed

Chemistry 328N

Nuclear Spins in a Magnetic Field

E=hn or n =Eh

Chemistry 328N

Nuclear Magnetic Resonance

If the nucleus is irradiated with radiation

having energy (E=h) that is exactly the

same as the difference between the nuclear

spin states

ndash energy is absorbed and

ndash the nuclear spin is flipped from spin state +12

(with the applied field) to -12 (against the

applied field)

Chemistry 328N

Nuclear Spin States

Spin quantum numbers and allowed nuclear

spin states for selected isotopes of elements

common to organic compounds

Element 1H 2H 12C 13C 14N 16O 31P

number of

spin states

12 1 0 0 0

32S

12 1

2 3 1 2 3 1

12

2 1

nuclear spin

quantum

number ( I )

Chemistry 328N

Serbian-American inventor electrical engineer and scientist

Born 1856 in Smiljan Lika (Austria-Hungary)

Died 1943 in New York City New York (USA)

Inventions a telephone repeater rotating magnetic field principle polyphase

alternating-current system induction motor alternating-current power

transmission Tesla coil transformer wireless communication radio

fluorescent lights and more than 700 other patents

Nikola Tesla

T (Tesla) = W (Weber)

m2

Chemistry 328N

Famous and Controversial picture of Tesla

httpwwwteslasocietycomindexhtml

Chemistry 328N

ldquoThe ray was described as the most important of all Teslarsquos inventions so far It was

said that IT COULD SEND CONSECRATED BEAMS OF PARTICLES THROUGH

FREE AIR and could cause armies of millions to drop dead in their tracks

Wardenclyffe Tower

if constructed would result in

An inexpensive instrument not

bigger than a watch will enable its

bearer to hear anywhere on sea or

land music or song the speech of a

political leader the address of an

eminent man of science or the

sermon of an eloquent clergyman

delivered in some other place

however distant In the same

manner any picture character

drawing or print can be transferred

from one to another place

Tesla ray gun

Chemistry 328N

)( 0BfhE == n

42

At B=10T

E = 4258MHz

Chemistry 328N

Nuclear Spins in B0

In an applied field strength of 705T (BIG)

E between nuclear spin states for

ndash 1H is approximately 00286 calmol which

corresponds to electromagnetic radiation of 300

MHz (300000000 Hz)

ndash 13C is approximately 000715 calmol which

corresponds to electromagnetic radiation of

75MHz (75000000 Hz)

ndash This E is quite smallhelliplow frequency

radiation induces ldquofliprdquo (resonance)

Chemistry 328N

ldquoResonancerdquo The transition from the lower state to the higher

occurs at unique combinations of magnetic field and frequency of electromagnetic radiation

When placed in a magnetic field of strength B a particle with a net spin can absorb a photon of frequency n The frequency n depends on the gyromagnetic ratio of the particle

n = B

For hydrogen = 4258 MHz Tesla

Allows you to calculate ldquospectrometer frequencyrdquo for 1H

This is the frequency at which ldquonakedrdquo 1H resonates in that machine

Chemistry 328N

Some Proportionality Constants

Gyromagnetic Ratio n = B

ndash For 1H = 4258 MHzT

Planckrsquos Constant E = h n

Speed of light n = c l or c = n l

Chemical Shift 119889(119901119901119898) =∆n

119878119901119890119888119905119903119900119898119890119905119890119903 119891119903119890119902119906119890119899119888119910

Chemistry 328N

NMR Spectrometer

Chemistry 328N

In principle we could hold field constant and scan frequency looking

for resonance but it is equally effective to scan field strength and hold

frequency constant

Chemistry 328N

500MHz 1H-nmr Spectrometer

Magnet

Chemistry 328N

httpwwwjeolusacomRESOURCESAnalyticalInstrumentsNMRMagnetDestructiontabid390Defaultaspx

Chemistry 328N

800 MHz machine at UH

Highest Frequency in 2013

The first Avance 1000 system was

delivered to the new lsquoCentre de RMN agrave

Tregraves Hauts Champsrsquo in Lyon France

1020 MHz nmr

June 2015

Weight 15 tons

Chemistry 328N

The 100MHz nmr Chart

1000 900 800 700 600 500 400 300 200 100 00

10

20

30

40

50

60

70

80

90

000

Si CH3

CH3

CH3

CH3

Frequency

field

The TMS resonance is defined as having ldquo0rdquo frequency

Chemistry 328N

100MHz Spectrum

450 400 350 300 250 200 150 100 50 00

5

10

15

20

Hz

CH3 Cl

325 320 315 310 305 300 295 290 285 2800

5

10

15

2030400

304 Hz

Chemistry 328N

100MHz nmr Spectrum

450 400 350 300 250 200 150 100 50 00

5

10

15

20

CH3 Br

275 270 265 260 2550

5

10

15

20

26850

Hz2685Hz

Chemistry 328N

Nuclear Magnetic Resonance

If we were dealing with 1H nuclei isolatedfrom all other atoms and electrons anycombination of applied field and radiation thatproduces a signal for one 1H would produce asignal for all 1H The same for 13C nuclei

But helliphydrogens in organic molecules are notisolated from all other atoms they aresurrounded by electrons which are caused tocirculate by the presence of the applied field

Chemistry 328N

Nuclear Magnetic Resonance

The circulation of electrons around anucleus in an applied field is calleddiamagnetic current

This current generates a field that opposesthe applied field diamagnetic nuclearshielding results Lenzrsquos Law

The difference in resonance frequenciesbetween the various hydrogen nuclei withina molecule is due to shieldingdeshielding isvery small but very important

Chemistry 328N

Lenzrsquos Law

Heinrich Lenz

1804-1865

Chemistry 328N

Conditions for Resonance

It is the frequency of the radiation and the

NET field at the nucleus that matters

The NET field is the sum of all incident

magnetic fields including those from

ndash The Giant Magnet (applied field)

ndash Diamagnetic Shielding field (electrons)

ndash Coupling (spin fields of adjacent nuclei)

ndash credit card strips earthrsquos field etchellip

Page 15: OC 2/e 12 - University of Texas at Austinwillson.cm.utexas.edu/Teaching/Chem328N/Files/Lecture 03... · 2016. 1. 29. · Born, 1856 in Smiljan, Lika (Austria-Hungary) Died 1943 in

Chemistry 328N

Nuclear Spins in a Magnetic Field

E=hn or n =Eh

Chemistry 328N

Nuclear Magnetic Resonance

If the nucleus is irradiated with radiation

having energy (E=h) that is exactly the

same as the difference between the nuclear

spin states

ndash energy is absorbed and

ndash the nuclear spin is flipped from spin state +12

(with the applied field) to -12 (against the

applied field)

Chemistry 328N

Nuclear Spin States

Spin quantum numbers and allowed nuclear

spin states for selected isotopes of elements

common to organic compounds

Element 1H 2H 12C 13C 14N 16O 31P

number of

spin states

12 1 0 0 0

32S

12 1

2 3 1 2 3 1

12

2 1

nuclear spin

quantum

number ( I )

Chemistry 328N

Serbian-American inventor electrical engineer and scientist

Born 1856 in Smiljan Lika (Austria-Hungary)

Died 1943 in New York City New York (USA)

Inventions a telephone repeater rotating magnetic field principle polyphase

alternating-current system induction motor alternating-current power

transmission Tesla coil transformer wireless communication radio

fluorescent lights and more than 700 other patents

Nikola Tesla

T (Tesla) = W (Weber)

m2

Chemistry 328N

Famous and Controversial picture of Tesla

httpwwwteslasocietycomindexhtml

Chemistry 328N

ldquoThe ray was described as the most important of all Teslarsquos inventions so far It was

said that IT COULD SEND CONSECRATED BEAMS OF PARTICLES THROUGH

FREE AIR and could cause armies of millions to drop dead in their tracks

Wardenclyffe Tower

if constructed would result in

An inexpensive instrument not

bigger than a watch will enable its

bearer to hear anywhere on sea or

land music or song the speech of a

political leader the address of an

eminent man of science or the

sermon of an eloquent clergyman

delivered in some other place

however distant In the same

manner any picture character

drawing or print can be transferred

from one to another place

Tesla ray gun

Chemistry 328N

)( 0BfhE == n

42

At B=10T

E = 4258MHz

Chemistry 328N

Nuclear Spins in B0

In an applied field strength of 705T (BIG)

E between nuclear spin states for

ndash 1H is approximately 00286 calmol which

corresponds to electromagnetic radiation of 300

MHz (300000000 Hz)

ndash 13C is approximately 000715 calmol which

corresponds to electromagnetic radiation of

75MHz (75000000 Hz)

ndash This E is quite smallhelliplow frequency

radiation induces ldquofliprdquo (resonance)

Chemistry 328N

ldquoResonancerdquo The transition from the lower state to the higher

occurs at unique combinations of magnetic field and frequency of electromagnetic radiation

When placed in a magnetic field of strength B a particle with a net spin can absorb a photon of frequency n The frequency n depends on the gyromagnetic ratio of the particle

n = B

For hydrogen = 4258 MHz Tesla

Allows you to calculate ldquospectrometer frequencyrdquo for 1H

This is the frequency at which ldquonakedrdquo 1H resonates in that machine

Chemistry 328N

Some Proportionality Constants

Gyromagnetic Ratio n = B

ndash For 1H = 4258 MHzT

Planckrsquos Constant E = h n

Speed of light n = c l or c = n l

Chemical Shift 119889(119901119901119898) =∆n

119878119901119890119888119905119903119900119898119890119905119890119903 119891119903119890119902119906119890119899119888119910

Chemistry 328N

NMR Spectrometer

Chemistry 328N

In principle we could hold field constant and scan frequency looking

for resonance but it is equally effective to scan field strength and hold

frequency constant

Chemistry 328N

500MHz 1H-nmr Spectrometer

Magnet

Chemistry 328N

httpwwwjeolusacomRESOURCESAnalyticalInstrumentsNMRMagnetDestructiontabid390Defaultaspx

Chemistry 328N

800 MHz machine at UH

Highest Frequency in 2013

The first Avance 1000 system was

delivered to the new lsquoCentre de RMN agrave

Tregraves Hauts Champsrsquo in Lyon France

1020 MHz nmr

June 2015

Weight 15 tons

Chemistry 328N

The 100MHz nmr Chart

1000 900 800 700 600 500 400 300 200 100 00

10

20

30

40

50

60

70

80

90

000

Si CH3

CH3

CH3

CH3

Frequency

field

The TMS resonance is defined as having ldquo0rdquo frequency

Chemistry 328N

100MHz Spectrum

450 400 350 300 250 200 150 100 50 00

5

10

15

20

Hz

CH3 Cl

325 320 315 310 305 300 295 290 285 2800

5

10

15

2030400

304 Hz

Chemistry 328N

100MHz nmr Spectrum

450 400 350 300 250 200 150 100 50 00

5

10

15

20

CH3 Br

275 270 265 260 2550

5

10

15

20

26850

Hz2685Hz

Chemistry 328N

Nuclear Magnetic Resonance

If we were dealing with 1H nuclei isolatedfrom all other atoms and electrons anycombination of applied field and radiation thatproduces a signal for one 1H would produce asignal for all 1H The same for 13C nuclei

But helliphydrogens in organic molecules are notisolated from all other atoms they aresurrounded by electrons which are caused tocirculate by the presence of the applied field

Chemistry 328N

Nuclear Magnetic Resonance

The circulation of electrons around anucleus in an applied field is calleddiamagnetic current

This current generates a field that opposesthe applied field diamagnetic nuclearshielding results Lenzrsquos Law

The difference in resonance frequenciesbetween the various hydrogen nuclei withina molecule is due to shieldingdeshielding isvery small but very important

Chemistry 328N

Lenzrsquos Law

Heinrich Lenz

1804-1865

Chemistry 328N

Conditions for Resonance

It is the frequency of the radiation and the

NET field at the nucleus that matters

The NET field is the sum of all incident

magnetic fields including those from

ndash The Giant Magnet (applied field)

ndash Diamagnetic Shielding field (electrons)

ndash Coupling (spin fields of adjacent nuclei)

ndash credit card strips earthrsquos field etchellip

Page 16: OC 2/e 12 - University of Texas at Austinwillson.cm.utexas.edu/Teaching/Chem328N/Files/Lecture 03... · 2016. 1. 29. · Born, 1856 in Smiljan, Lika (Austria-Hungary) Died 1943 in

Chemistry 328N

Nuclear Magnetic Resonance

If the nucleus is irradiated with radiation

having energy (E=h) that is exactly the

same as the difference between the nuclear

spin states

ndash energy is absorbed and

ndash the nuclear spin is flipped from spin state +12

(with the applied field) to -12 (against the

applied field)

Chemistry 328N

Nuclear Spin States

Spin quantum numbers and allowed nuclear

spin states for selected isotopes of elements

common to organic compounds

Element 1H 2H 12C 13C 14N 16O 31P

number of

spin states

12 1 0 0 0

32S

12 1

2 3 1 2 3 1

12

2 1

nuclear spin

quantum

number ( I )

Chemistry 328N

Serbian-American inventor electrical engineer and scientist

Born 1856 in Smiljan Lika (Austria-Hungary)

Died 1943 in New York City New York (USA)

Inventions a telephone repeater rotating magnetic field principle polyphase

alternating-current system induction motor alternating-current power

transmission Tesla coil transformer wireless communication radio

fluorescent lights and more than 700 other patents

Nikola Tesla

T (Tesla) = W (Weber)

m2

Chemistry 328N

Famous and Controversial picture of Tesla

httpwwwteslasocietycomindexhtml

Chemistry 328N

ldquoThe ray was described as the most important of all Teslarsquos inventions so far It was

said that IT COULD SEND CONSECRATED BEAMS OF PARTICLES THROUGH

FREE AIR and could cause armies of millions to drop dead in their tracks

Wardenclyffe Tower

if constructed would result in

An inexpensive instrument not

bigger than a watch will enable its

bearer to hear anywhere on sea or

land music or song the speech of a

political leader the address of an

eminent man of science or the

sermon of an eloquent clergyman

delivered in some other place

however distant In the same

manner any picture character

drawing or print can be transferred

from one to another place

Tesla ray gun

Chemistry 328N

)( 0BfhE == n

42

At B=10T

E = 4258MHz

Chemistry 328N

Nuclear Spins in B0

In an applied field strength of 705T (BIG)

E between nuclear spin states for

ndash 1H is approximately 00286 calmol which

corresponds to electromagnetic radiation of 300

MHz (300000000 Hz)

ndash 13C is approximately 000715 calmol which

corresponds to electromagnetic radiation of

75MHz (75000000 Hz)

ndash This E is quite smallhelliplow frequency

radiation induces ldquofliprdquo (resonance)

Chemistry 328N

ldquoResonancerdquo The transition from the lower state to the higher

occurs at unique combinations of magnetic field and frequency of electromagnetic radiation

When placed in a magnetic field of strength B a particle with a net spin can absorb a photon of frequency n The frequency n depends on the gyromagnetic ratio of the particle

n = B

For hydrogen = 4258 MHz Tesla

Allows you to calculate ldquospectrometer frequencyrdquo for 1H

This is the frequency at which ldquonakedrdquo 1H resonates in that machine

Chemistry 328N

Some Proportionality Constants

Gyromagnetic Ratio n = B

ndash For 1H = 4258 MHzT

Planckrsquos Constant E = h n

Speed of light n = c l or c = n l

Chemical Shift 119889(119901119901119898) =∆n

119878119901119890119888119905119903119900119898119890119905119890119903 119891119903119890119902119906119890119899119888119910

Chemistry 328N

NMR Spectrometer

Chemistry 328N

In principle we could hold field constant and scan frequency looking

for resonance but it is equally effective to scan field strength and hold

frequency constant

Chemistry 328N

500MHz 1H-nmr Spectrometer

Magnet

Chemistry 328N

httpwwwjeolusacomRESOURCESAnalyticalInstrumentsNMRMagnetDestructiontabid390Defaultaspx

Chemistry 328N

800 MHz machine at UH

Highest Frequency in 2013

The first Avance 1000 system was

delivered to the new lsquoCentre de RMN agrave

Tregraves Hauts Champsrsquo in Lyon France

1020 MHz nmr

June 2015

Weight 15 tons

Chemistry 328N

The 100MHz nmr Chart

1000 900 800 700 600 500 400 300 200 100 00

10

20

30

40

50

60

70

80

90

000

Si CH3

CH3

CH3

CH3

Frequency

field

The TMS resonance is defined as having ldquo0rdquo frequency

Chemistry 328N

100MHz Spectrum

450 400 350 300 250 200 150 100 50 00

5

10

15

20

Hz

CH3 Cl

325 320 315 310 305 300 295 290 285 2800

5

10

15

2030400

304 Hz

Chemistry 328N

100MHz nmr Spectrum

450 400 350 300 250 200 150 100 50 00

5

10

15

20

CH3 Br

275 270 265 260 2550

5

10

15

20

26850

Hz2685Hz

Chemistry 328N

Nuclear Magnetic Resonance

If we were dealing with 1H nuclei isolatedfrom all other atoms and electrons anycombination of applied field and radiation thatproduces a signal for one 1H would produce asignal for all 1H The same for 13C nuclei

But helliphydrogens in organic molecules are notisolated from all other atoms they aresurrounded by electrons which are caused tocirculate by the presence of the applied field

Chemistry 328N

Nuclear Magnetic Resonance

The circulation of electrons around anucleus in an applied field is calleddiamagnetic current

This current generates a field that opposesthe applied field diamagnetic nuclearshielding results Lenzrsquos Law

The difference in resonance frequenciesbetween the various hydrogen nuclei withina molecule is due to shieldingdeshielding isvery small but very important

Chemistry 328N

Lenzrsquos Law

Heinrich Lenz

1804-1865

Chemistry 328N

Conditions for Resonance

It is the frequency of the radiation and the

NET field at the nucleus that matters

The NET field is the sum of all incident

magnetic fields including those from

ndash The Giant Magnet (applied field)

ndash Diamagnetic Shielding field (electrons)

ndash Coupling (spin fields of adjacent nuclei)

ndash credit card strips earthrsquos field etchellip

Page 17: OC 2/e 12 - University of Texas at Austinwillson.cm.utexas.edu/Teaching/Chem328N/Files/Lecture 03... · 2016. 1. 29. · Born, 1856 in Smiljan, Lika (Austria-Hungary) Died 1943 in

Chemistry 328N

Nuclear Spin States

Spin quantum numbers and allowed nuclear

spin states for selected isotopes of elements

common to organic compounds

Element 1H 2H 12C 13C 14N 16O 31P

number of

spin states

12 1 0 0 0

32S

12 1

2 3 1 2 3 1

12

2 1

nuclear spin

quantum

number ( I )

Chemistry 328N

Serbian-American inventor electrical engineer and scientist

Born 1856 in Smiljan Lika (Austria-Hungary)

Died 1943 in New York City New York (USA)

Inventions a telephone repeater rotating magnetic field principle polyphase

alternating-current system induction motor alternating-current power

transmission Tesla coil transformer wireless communication radio

fluorescent lights and more than 700 other patents

Nikola Tesla

T (Tesla) = W (Weber)

m2

Chemistry 328N

Famous and Controversial picture of Tesla

httpwwwteslasocietycomindexhtml

Chemistry 328N

ldquoThe ray was described as the most important of all Teslarsquos inventions so far It was

said that IT COULD SEND CONSECRATED BEAMS OF PARTICLES THROUGH

FREE AIR and could cause armies of millions to drop dead in their tracks

Wardenclyffe Tower

if constructed would result in

An inexpensive instrument not

bigger than a watch will enable its

bearer to hear anywhere on sea or

land music or song the speech of a

political leader the address of an

eminent man of science or the

sermon of an eloquent clergyman

delivered in some other place

however distant In the same

manner any picture character

drawing or print can be transferred

from one to another place

Tesla ray gun

Chemistry 328N

)( 0BfhE == n

42

At B=10T

E = 4258MHz

Chemistry 328N

Nuclear Spins in B0

In an applied field strength of 705T (BIG)

E between nuclear spin states for

ndash 1H is approximately 00286 calmol which

corresponds to electromagnetic radiation of 300

MHz (300000000 Hz)

ndash 13C is approximately 000715 calmol which

corresponds to electromagnetic radiation of

75MHz (75000000 Hz)

ndash This E is quite smallhelliplow frequency

radiation induces ldquofliprdquo (resonance)

Chemistry 328N

ldquoResonancerdquo The transition from the lower state to the higher

occurs at unique combinations of magnetic field and frequency of electromagnetic radiation

When placed in a magnetic field of strength B a particle with a net spin can absorb a photon of frequency n The frequency n depends on the gyromagnetic ratio of the particle

n = B

For hydrogen = 4258 MHz Tesla

Allows you to calculate ldquospectrometer frequencyrdquo for 1H

This is the frequency at which ldquonakedrdquo 1H resonates in that machine

Chemistry 328N

Some Proportionality Constants

Gyromagnetic Ratio n = B

ndash For 1H = 4258 MHzT

Planckrsquos Constant E = h n

Speed of light n = c l or c = n l

Chemical Shift 119889(119901119901119898) =∆n

119878119901119890119888119905119903119900119898119890119905119890119903 119891119903119890119902119906119890119899119888119910

Chemistry 328N

NMR Spectrometer

Chemistry 328N

In principle we could hold field constant and scan frequency looking

for resonance but it is equally effective to scan field strength and hold

frequency constant

Chemistry 328N

500MHz 1H-nmr Spectrometer

Magnet

Chemistry 328N

httpwwwjeolusacomRESOURCESAnalyticalInstrumentsNMRMagnetDestructiontabid390Defaultaspx

Chemistry 328N

800 MHz machine at UH

Highest Frequency in 2013

The first Avance 1000 system was

delivered to the new lsquoCentre de RMN agrave

Tregraves Hauts Champsrsquo in Lyon France

1020 MHz nmr

June 2015

Weight 15 tons

Chemistry 328N

The 100MHz nmr Chart

1000 900 800 700 600 500 400 300 200 100 00

10

20

30

40

50

60

70

80

90

000

Si CH3

CH3

CH3

CH3

Frequency

field

The TMS resonance is defined as having ldquo0rdquo frequency

Chemistry 328N

100MHz Spectrum

450 400 350 300 250 200 150 100 50 00

5

10

15

20

Hz

CH3 Cl

325 320 315 310 305 300 295 290 285 2800

5

10

15

2030400

304 Hz

Chemistry 328N

100MHz nmr Spectrum

450 400 350 300 250 200 150 100 50 00

5

10

15

20

CH3 Br

275 270 265 260 2550

5

10

15

20

26850

Hz2685Hz

Chemistry 328N

Nuclear Magnetic Resonance

If we were dealing with 1H nuclei isolatedfrom all other atoms and electrons anycombination of applied field and radiation thatproduces a signal for one 1H would produce asignal for all 1H The same for 13C nuclei

But helliphydrogens in organic molecules are notisolated from all other atoms they aresurrounded by electrons which are caused tocirculate by the presence of the applied field

Chemistry 328N

Nuclear Magnetic Resonance

The circulation of electrons around anucleus in an applied field is calleddiamagnetic current

This current generates a field that opposesthe applied field diamagnetic nuclearshielding results Lenzrsquos Law

The difference in resonance frequenciesbetween the various hydrogen nuclei withina molecule is due to shieldingdeshielding isvery small but very important

Chemistry 328N

Lenzrsquos Law

Heinrich Lenz

1804-1865

Chemistry 328N

Conditions for Resonance

It is the frequency of the radiation and the

NET field at the nucleus that matters

The NET field is the sum of all incident

magnetic fields including those from

ndash The Giant Magnet (applied field)

ndash Diamagnetic Shielding field (electrons)

ndash Coupling (spin fields of adjacent nuclei)

ndash credit card strips earthrsquos field etchellip

Page 18: OC 2/e 12 - University of Texas at Austinwillson.cm.utexas.edu/Teaching/Chem328N/Files/Lecture 03... · 2016. 1. 29. · Born, 1856 in Smiljan, Lika (Austria-Hungary) Died 1943 in

Chemistry 328N

Serbian-American inventor electrical engineer and scientist

Born 1856 in Smiljan Lika (Austria-Hungary)

Died 1943 in New York City New York (USA)

Inventions a telephone repeater rotating magnetic field principle polyphase

alternating-current system induction motor alternating-current power

transmission Tesla coil transformer wireless communication radio

fluorescent lights and more than 700 other patents

Nikola Tesla

T (Tesla) = W (Weber)

m2

Chemistry 328N

Famous and Controversial picture of Tesla

httpwwwteslasocietycomindexhtml

Chemistry 328N

ldquoThe ray was described as the most important of all Teslarsquos inventions so far It was

said that IT COULD SEND CONSECRATED BEAMS OF PARTICLES THROUGH

FREE AIR and could cause armies of millions to drop dead in their tracks

Wardenclyffe Tower

if constructed would result in

An inexpensive instrument not

bigger than a watch will enable its

bearer to hear anywhere on sea or

land music or song the speech of a

political leader the address of an

eminent man of science or the

sermon of an eloquent clergyman

delivered in some other place

however distant In the same

manner any picture character

drawing or print can be transferred

from one to another place

Tesla ray gun

Chemistry 328N

)( 0BfhE == n

42

At B=10T

E = 4258MHz

Chemistry 328N

Nuclear Spins in B0

In an applied field strength of 705T (BIG)

E between nuclear spin states for

ndash 1H is approximately 00286 calmol which

corresponds to electromagnetic radiation of 300

MHz (300000000 Hz)

ndash 13C is approximately 000715 calmol which

corresponds to electromagnetic radiation of

75MHz (75000000 Hz)

ndash This E is quite smallhelliplow frequency

radiation induces ldquofliprdquo (resonance)

Chemistry 328N

ldquoResonancerdquo The transition from the lower state to the higher

occurs at unique combinations of magnetic field and frequency of electromagnetic radiation

When placed in a magnetic field of strength B a particle with a net spin can absorb a photon of frequency n The frequency n depends on the gyromagnetic ratio of the particle

n = B

For hydrogen = 4258 MHz Tesla

Allows you to calculate ldquospectrometer frequencyrdquo for 1H

This is the frequency at which ldquonakedrdquo 1H resonates in that machine

Chemistry 328N

Some Proportionality Constants

Gyromagnetic Ratio n = B

ndash For 1H = 4258 MHzT

Planckrsquos Constant E = h n

Speed of light n = c l or c = n l

Chemical Shift 119889(119901119901119898) =∆n

119878119901119890119888119905119903119900119898119890119905119890119903 119891119903119890119902119906119890119899119888119910

Chemistry 328N

NMR Spectrometer

Chemistry 328N

In principle we could hold field constant and scan frequency looking

for resonance but it is equally effective to scan field strength and hold

frequency constant

Chemistry 328N

500MHz 1H-nmr Spectrometer

Magnet

Chemistry 328N

httpwwwjeolusacomRESOURCESAnalyticalInstrumentsNMRMagnetDestructiontabid390Defaultaspx

Chemistry 328N

800 MHz machine at UH

Highest Frequency in 2013

The first Avance 1000 system was

delivered to the new lsquoCentre de RMN agrave

Tregraves Hauts Champsrsquo in Lyon France

1020 MHz nmr

June 2015

Weight 15 tons

Chemistry 328N

The 100MHz nmr Chart

1000 900 800 700 600 500 400 300 200 100 00

10

20

30

40

50

60

70

80

90

000

Si CH3

CH3

CH3

CH3

Frequency

field

The TMS resonance is defined as having ldquo0rdquo frequency

Chemistry 328N

100MHz Spectrum

450 400 350 300 250 200 150 100 50 00

5

10

15

20

Hz

CH3 Cl

325 320 315 310 305 300 295 290 285 2800

5

10

15

2030400

304 Hz

Chemistry 328N

100MHz nmr Spectrum

450 400 350 300 250 200 150 100 50 00

5

10

15

20

CH3 Br

275 270 265 260 2550

5

10

15

20

26850

Hz2685Hz

Chemistry 328N

Nuclear Magnetic Resonance

If we were dealing with 1H nuclei isolatedfrom all other atoms and electrons anycombination of applied field and radiation thatproduces a signal for one 1H would produce asignal for all 1H The same for 13C nuclei

But helliphydrogens in organic molecules are notisolated from all other atoms they aresurrounded by electrons which are caused tocirculate by the presence of the applied field

Chemistry 328N

Nuclear Magnetic Resonance

The circulation of electrons around anucleus in an applied field is calleddiamagnetic current

This current generates a field that opposesthe applied field diamagnetic nuclearshielding results Lenzrsquos Law

The difference in resonance frequenciesbetween the various hydrogen nuclei withina molecule is due to shieldingdeshielding isvery small but very important

Chemistry 328N

Lenzrsquos Law

Heinrich Lenz

1804-1865

Chemistry 328N

Conditions for Resonance

It is the frequency of the radiation and the

NET field at the nucleus that matters

The NET field is the sum of all incident

magnetic fields including those from

ndash The Giant Magnet (applied field)

ndash Diamagnetic Shielding field (electrons)

ndash Coupling (spin fields of adjacent nuclei)

ndash credit card strips earthrsquos field etchellip

Page 19: OC 2/e 12 - University of Texas at Austinwillson.cm.utexas.edu/Teaching/Chem328N/Files/Lecture 03... · 2016. 1. 29. · Born, 1856 in Smiljan, Lika (Austria-Hungary) Died 1943 in

Chemistry 328N

Famous and Controversial picture of Tesla

httpwwwteslasocietycomindexhtml

Chemistry 328N

ldquoThe ray was described as the most important of all Teslarsquos inventions so far It was

said that IT COULD SEND CONSECRATED BEAMS OF PARTICLES THROUGH

FREE AIR and could cause armies of millions to drop dead in their tracks

Wardenclyffe Tower

if constructed would result in

An inexpensive instrument not

bigger than a watch will enable its

bearer to hear anywhere on sea or

land music or song the speech of a

political leader the address of an

eminent man of science or the

sermon of an eloquent clergyman

delivered in some other place

however distant In the same

manner any picture character

drawing or print can be transferred

from one to another place

Tesla ray gun

Chemistry 328N

)( 0BfhE == n

42

At B=10T

E = 4258MHz

Chemistry 328N

Nuclear Spins in B0

In an applied field strength of 705T (BIG)

E between nuclear spin states for

ndash 1H is approximately 00286 calmol which

corresponds to electromagnetic radiation of 300

MHz (300000000 Hz)

ndash 13C is approximately 000715 calmol which

corresponds to electromagnetic radiation of

75MHz (75000000 Hz)

ndash This E is quite smallhelliplow frequency

radiation induces ldquofliprdquo (resonance)

Chemistry 328N

ldquoResonancerdquo The transition from the lower state to the higher

occurs at unique combinations of magnetic field and frequency of electromagnetic radiation

When placed in a magnetic field of strength B a particle with a net spin can absorb a photon of frequency n The frequency n depends on the gyromagnetic ratio of the particle

n = B

For hydrogen = 4258 MHz Tesla

Allows you to calculate ldquospectrometer frequencyrdquo for 1H

This is the frequency at which ldquonakedrdquo 1H resonates in that machine

Chemistry 328N

Some Proportionality Constants

Gyromagnetic Ratio n = B

ndash For 1H = 4258 MHzT

Planckrsquos Constant E = h n

Speed of light n = c l or c = n l

Chemical Shift 119889(119901119901119898) =∆n

119878119901119890119888119905119903119900119898119890119905119890119903 119891119903119890119902119906119890119899119888119910

Chemistry 328N

NMR Spectrometer

Chemistry 328N

In principle we could hold field constant and scan frequency looking

for resonance but it is equally effective to scan field strength and hold

frequency constant

Chemistry 328N

500MHz 1H-nmr Spectrometer

Magnet

Chemistry 328N

httpwwwjeolusacomRESOURCESAnalyticalInstrumentsNMRMagnetDestructiontabid390Defaultaspx

Chemistry 328N

800 MHz machine at UH

Highest Frequency in 2013

The first Avance 1000 system was

delivered to the new lsquoCentre de RMN agrave

Tregraves Hauts Champsrsquo in Lyon France

1020 MHz nmr

June 2015

Weight 15 tons

Chemistry 328N

The 100MHz nmr Chart

1000 900 800 700 600 500 400 300 200 100 00

10

20

30

40

50

60

70

80

90

000

Si CH3

CH3

CH3

CH3

Frequency

field

The TMS resonance is defined as having ldquo0rdquo frequency

Chemistry 328N

100MHz Spectrum

450 400 350 300 250 200 150 100 50 00

5

10

15

20

Hz

CH3 Cl

325 320 315 310 305 300 295 290 285 2800

5

10

15

2030400

304 Hz

Chemistry 328N

100MHz nmr Spectrum

450 400 350 300 250 200 150 100 50 00

5

10

15

20

CH3 Br

275 270 265 260 2550

5

10

15

20

26850

Hz2685Hz

Chemistry 328N

Nuclear Magnetic Resonance

If we were dealing with 1H nuclei isolatedfrom all other atoms and electrons anycombination of applied field and radiation thatproduces a signal for one 1H would produce asignal for all 1H The same for 13C nuclei

But helliphydrogens in organic molecules are notisolated from all other atoms they aresurrounded by electrons which are caused tocirculate by the presence of the applied field

Chemistry 328N

Nuclear Magnetic Resonance

The circulation of electrons around anucleus in an applied field is calleddiamagnetic current

This current generates a field that opposesthe applied field diamagnetic nuclearshielding results Lenzrsquos Law

The difference in resonance frequenciesbetween the various hydrogen nuclei withina molecule is due to shieldingdeshielding isvery small but very important

Chemistry 328N

Lenzrsquos Law

Heinrich Lenz

1804-1865

Chemistry 328N

Conditions for Resonance

It is the frequency of the radiation and the

NET field at the nucleus that matters

The NET field is the sum of all incident

magnetic fields including those from

ndash The Giant Magnet (applied field)

ndash Diamagnetic Shielding field (electrons)

ndash Coupling (spin fields of adjacent nuclei)

ndash credit card strips earthrsquos field etchellip

Page 20: OC 2/e 12 - University of Texas at Austinwillson.cm.utexas.edu/Teaching/Chem328N/Files/Lecture 03... · 2016. 1. 29. · Born, 1856 in Smiljan, Lika (Austria-Hungary) Died 1943 in

Chemistry 328N

ldquoThe ray was described as the most important of all Teslarsquos inventions so far It was

said that IT COULD SEND CONSECRATED BEAMS OF PARTICLES THROUGH

FREE AIR and could cause armies of millions to drop dead in their tracks

Wardenclyffe Tower

if constructed would result in

An inexpensive instrument not

bigger than a watch will enable its

bearer to hear anywhere on sea or

land music or song the speech of a

political leader the address of an

eminent man of science or the

sermon of an eloquent clergyman

delivered in some other place

however distant In the same

manner any picture character

drawing or print can be transferred

from one to another place

Tesla ray gun

Chemistry 328N

)( 0BfhE == n

42

At B=10T

E = 4258MHz

Chemistry 328N

Nuclear Spins in B0

In an applied field strength of 705T (BIG)

E between nuclear spin states for

ndash 1H is approximately 00286 calmol which

corresponds to electromagnetic radiation of 300

MHz (300000000 Hz)

ndash 13C is approximately 000715 calmol which

corresponds to electromagnetic radiation of

75MHz (75000000 Hz)

ndash This E is quite smallhelliplow frequency

radiation induces ldquofliprdquo (resonance)

Chemistry 328N

ldquoResonancerdquo The transition from the lower state to the higher

occurs at unique combinations of magnetic field and frequency of electromagnetic radiation

When placed in a magnetic field of strength B a particle with a net spin can absorb a photon of frequency n The frequency n depends on the gyromagnetic ratio of the particle

n = B

For hydrogen = 4258 MHz Tesla

Allows you to calculate ldquospectrometer frequencyrdquo for 1H

This is the frequency at which ldquonakedrdquo 1H resonates in that machine

Chemistry 328N

Some Proportionality Constants

Gyromagnetic Ratio n = B

ndash For 1H = 4258 MHzT

Planckrsquos Constant E = h n

Speed of light n = c l or c = n l

Chemical Shift 119889(119901119901119898) =∆n

119878119901119890119888119905119903119900119898119890119905119890119903 119891119903119890119902119906119890119899119888119910

Chemistry 328N

NMR Spectrometer

Chemistry 328N

In principle we could hold field constant and scan frequency looking

for resonance but it is equally effective to scan field strength and hold

frequency constant

Chemistry 328N

500MHz 1H-nmr Spectrometer

Magnet

Chemistry 328N

httpwwwjeolusacomRESOURCESAnalyticalInstrumentsNMRMagnetDestructiontabid390Defaultaspx

Chemistry 328N

800 MHz machine at UH

Highest Frequency in 2013

The first Avance 1000 system was

delivered to the new lsquoCentre de RMN agrave

Tregraves Hauts Champsrsquo in Lyon France

1020 MHz nmr

June 2015

Weight 15 tons

Chemistry 328N

The 100MHz nmr Chart

1000 900 800 700 600 500 400 300 200 100 00

10

20

30

40

50

60

70

80

90

000

Si CH3

CH3

CH3

CH3

Frequency

field

The TMS resonance is defined as having ldquo0rdquo frequency

Chemistry 328N

100MHz Spectrum

450 400 350 300 250 200 150 100 50 00

5

10

15

20

Hz

CH3 Cl

325 320 315 310 305 300 295 290 285 2800

5

10

15

2030400

304 Hz

Chemistry 328N

100MHz nmr Spectrum

450 400 350 300 250 200 150 100 50 00

5

10

15

20

CH3 Br

275 270 265 260 2550

5

10

15

20

26850

Hz2685Hz

Chemistry 328N

Nuclear Magnetic Resonance

If we were dealing with 1H nuclei isolatedfrom all other atoms and electrons anycombination of applied field and radiation thatproduces a signal for one 1H would produce asignal for all 1H The same for 13C nuclei

But helliphydrogens in organic molecules are notisolated from all other atoms they aresurrounded by electrons which are caused tocirculate by the presence of the applied field

Chemistry 328N

Nuclear Magnetic Resonance

The circulation of electrons around anucleus in an applied field is calleddiamagnetic current

This current generates a field that opposesthe applied field diamagnetic nuclearshielding results Lenzrsquos Law

The difference in resonance frequenciesbetween the various hydrogen nuclei withina molecule is due to shieldingdeshielding isvery small but very important

Chemistry 328N

Lenzrsquos Law

Heinrich Lenz

1804-1865

Chemistry 328N

Conditions for Resonance

It is the frequency of the radiation and the

NET field at the nucleus that matters

The NET field is the sum of all incident

magnetic fields including those from

ndash The Giant Magnet (applied field)

ndash Diamagnetic Shielding field (electrons)

ndash Coupling (spin fields of adjacent nuclei)

ndash credit card strips earthrsquos field etchellip

Page 21: OC 2/e 12 - University of Texas at Austinwillson.cm.utexas.edu/Teaching/Chem328N/Files/Lecture 03... · 2016. 1. 29. · Born, 1856 in Smiljan, Lika (Austria-Hungary) Died 1943 in

Chemistry 328N

)( 0BfhE == n

42

At B=10T

E = 4258MHz

Chemistry 328N

Nuclear Spins in B0

In an applied field strength of 705T (BIG)

E between nuclear spin states for

ndash 1H is approximately 00286 calmol which

corresponds to electromagnetic radiation of 300

MHz (300000000 Hz)

ndash 13C is approximately 000715 calmol which

corresponds to electromagnetic radiation of

75MHz (75000000 Hz)

ndash This E is quite smallhelliplow frequency

radiation induces ldquofliprdquo (resonance)

Chemistry 328N

ldquoResonancerdquo The transition from the lower state to the higher

occurs at unique combinations of magnetic field and frequency of electromagnetic radiation

When placed in a magnetic field of strength B a particle with a net spin can absorb a photon of frequency n The frequency n depends on the gyromagnetic ratio of the particle

n = B

For hydrogen = 4258 MHz Tesla

Allows you to calculate ldquospectrometer frequencyrdquo for 1H

This is the frequency at which ldquonakedrdquo 1H resonates in that machine

Chemistry 328N

Some Proportionality Constants

Gyromagnetic Ratio n = B

ndash For 1H = 4258 MHzT

Planckrsquos Constant E = h n

Speed of light n = c l or c = n l

Chemical Shift 119889(119901119901119898) =∆n

119878119901119890119888119905119903119900119898119890119905119890119903 119891119903119890119902119906119890119899119888119910

Chemistry 328N

NMR Spectrometer

Chemistry 328N

In principle we could hold field constant and scan frequency looking

for resonance but it is equally effective to scan field strength and hold

frequency constant

Chemistry 328N

500MHz 1H-nmr Spectrometer

Magnet

Chemistry 328N

httpwwwjeolusacomRESOURCESAnalyticalInstrumentsNMRMagnetDestructiontabid390Defaultaspx

Chemistry 328N

800 MHz machine at UH

Highest Frequency in 2013

The first Avance 1000 system was

delivered to the new lsquoCentre de RMN agrave

Tregraves Hauts Champsrsquo in Lyon France

1020 MHz nmr

June 2015

Weight 15 tons

Chemistry 328N

The 100MHz nmr Chart

1000 900 800 700 600 500 400 300 200 100 00

10

20

30

40

50

60

70

80

90

000

Si CH3

CH3

CH3

CH3

Frequency

field

The TMS resonance is defined as having ldquo0rdquo frequency

Chemistry 328N

100MHz Spectrum

450 400 350 300 250 200 150 100 50 00

5

10

15

20

Hz

CH3 Cl

325 320 315 310 305 300 295 290 285 2800

5

10

15

2030400

304 Hz

Chemistry 328N

100MHz nmr Spectrum

450 400 350 300 250 200 150 100 50 00

5

10

15

20

CH3 Br

275 270 265 260 2550

5

10

15

20

26850

Hz2685Hz

Chemistry 328N

Nuclear Magnetic Resonance

If we were dealing with 1H nuclei isolatedfrom all other atoms and electrons anycombination of applied field and radiation thatproduces a signal for one 1H would produce asignal for all 1H The same for 13C nuclei

But helliphydrogens in organic molecules are notisolated from all other atoms they aresurrounded by electrons which are caused tocirculate by the presence of the applied field

Chemistry 328N

Nuclear Magnetic Resonance

The circulation of electrons around anucleus in an applied field is calleddiamagnetic current

This current generates a field that opposesthe applied field diamagnetic nuclearshielding results Lenzrsquos Law

The difference in resonance frequenciesbetween the various hydrogen nuclei withina molecule is due to shieldingdeshielding isvery small but very important

Chemistry 328N

Lenzrsquos Law

Heinrich Lenz

1804-1865

Chemistry 328N

Conditions for Resonance

It is the frequency of the radiation and the

NET field at the nucleus that matters

The NET field is the sum of all incident

magnetic fields including those from

ndash The Giant Magnet (applied field)

ndash Diamagnetic Shielding field (electrons)

ndash Coupling (spin fields of adjacent nuclei)

ndash credit card strips earthrsquos field etchellip

Page 22: OC 2/e 12 - University of Texas at Austinwillson.cm.utexas.edu/Teaching/Chem328N/Files/Lecture 03... · 2016. 1. 29. · Born, 1856 in Smiljan, Lika (Austria-Hungary) Died 1943 in

Chemistry 328N

Nuclear Spins in B0

In an applied field strength of 705T (BIG)

E between nuclear spin states for

ndash 1H is approximately 00286 calmol which

corresponds to electromagnetic radiation of 300

MHz (300000000 Hz)

ndash 13C is approximately 000715 calmol which

corresponds to electromagnetic radiation of

75MHz (75000000 Hz)

ndash This E is quite smallhelliplow frequency

radiation induces ldquofliprdquo (resonance)

Chemistry 328N

ldquoResonancerdquo The transition from the lower state to the higher

occurs at unique combinations of magnetic field and frequency of electromagnetic radiation

When placed in a magnetic field of strength B a particle with a net spin can absorb a photon of frequency n The frequency n depends on the gyromagnetic ratio of the particle

n = B

For hydrogen = 4258 MHz Tesla

Allows you to calculate ldquospectrometer frequencyrdquo for 1H

This is the frequency at which ldquonakedrdquo 1H resonates in that machine

Chemistry 328N

Some Proportionality Constants

Gyromagnetic Ratio n = B

ndash For 1H = 4258 MHzT

Planckrsquos Constant E = h n

Speed of light n = c l or c = n l

Chemical Shift 119889(119901119901119898) =∆n

119878119901119890119888119905119903119900119898119890119905119890119903 119891119903119890119902119906119890119899119888119910

Chemistry 328N

NMR Spectrometer

Chemistry 328N

In principle we could hold field constant and scan frequency looking

for resonance but it is equally effective to scan field strength and hold

frequency constant

Chemistry 328N

500MHz 1H-nmr Spectrometer

Magnet

Chemistry 328N

httpwwwjeolusacomRESOURCESAnalyticalInstrumentsNMRMagnetDestructiontabid390Defaultaspx

Chemistry 328N

800 MHz machine at UH

Highest Frequency in 2013

The first Avance 1000 system was

delivered to the new lsquoCentre de RMN agrave

Tregraves Hauts Champsrsquo in Lyon France

1020 MHz nmr

June 2015

Weight 15 tons

Chemistry 328N

The 100MHz nmr Chart

1000 900 800 700 600 500 400 300 200 100 00

10

20

30

40

50

60

70

80

90

000

Si CH3

CH3

CH3

CH3

Frequency

field

The TMS resonance is defined as having ldquo0rdquo frequency

Chemistry 328N

100MHz Spectrum

450 400 350 300 250 200 150 100 50 00

5

10

15

20

Hz

CH3 Cl

325 320 315 310 305 300 295 290 285 2800

5

10

15

2030400

304 Hz

Chemistry 328N

100MHz nmr Spectrum

450 400 350 300 250 200 150 100 50 00

5

10

15

20

CH3 Br

275 270 265 260 2550

5

10

15

20

26850

Hz2685Hz

Chemistry 328N

Nuclear Magnetic Resonance

If we were dealing with 1H nuclei isolatedfrom all other atoms and electrons anycombination of applied field and radiation thatproduces a signal for one 1H would produce asignal for all 1H The same for 13C nuclei

But helliphydrogens in organic molecules are notisolated from all other atoms they aresurrounded by electrons which are caused tocirculate by the presence of the applied field

Chemistry 328N

Nuclear Magnetic Resonance

The circulation of electrons around anucleus in an applied field is calleddiamagnetic current

This current generates a field that opposesthe applied field diamagnetic nuclearshielding results Lenzrsquos Law

The difference in resonance frequenciesbetween the various hydrogen nuclei withina molecule is due to shieldingdeshielding isvery small but very important

Chemistry 328N

Lenzrsquos Law

Heinrich Lenz

1804-1865

Chemistry 328N

Conditions for Resonance

It is the frequency of the radiation and the

NET field at the nucleus that matters

The NET field is the sum of all incident

magnetic fields including those from

ndash The Giant Magnet (applied field)

ndash Diamagnetic Shielding field (electrons)

ndash Coupling (spin fields of adjacent nuclei)

ndash credit card strips earthrsquos field etchellip

Page 23: OC 2/e 12 - University of Texas at Austinwillson.cm.utexas.edu/Teaching/Chem328N/Files/Lecture 03... · 2016. 1. 29. · Born, 1856 in Smiljan, Lika (Austria-Hungary) Died 1943 in

Chemistry 328N

ldquoResonancerdquo The transition from the lower state to the higher

occurs at unique combinations of magnetic field and frequency of electromagnetic radiation

When placed in a magnetic field of strength B a particle with a net spin can absorb a photon of frequency n The frequency n depends on the gyromagnetic ratio of the particle

n = B

For hydrogen = 4258 MHz Tesla

Allows you to calculate ldquospectrometer frequencyrdquo for 1H

This is the frequency at which ldquonakedrdquo 1H resonates in that machine

Chemistry 328N

Some Proportionality Constants

Gyromagnetic Ratio n = B

ndash For 1H = 4258 MHzT

Planckrsquos Constant E = h n

Speed of light n = c l or c = n l

Chemical Shift 119889(119901119901119898) =∆n

119878119901119890119888119905119903119900119898119890119905119890119903 119891119903119890119902119906119890119899119888119910

Chemistry 328N

NMR Spectrometer

Chemistry 328N

In principle we could hold field constant and scan frequency looking

for resonance but it is equally effective to scan field strength and hold

frequency constant

Chemistry 328N

500MHz 1H-nmr Spectrometer

Magnet

Chemistry 328N

httpwwwjeolusacomRESOURCESAnalyticalInstrumentsNMRMagnetDestructiontabid390Defaultaspx

Chemistry 328N

800 MHz machine at UH

Highest Frequency in 2013

The first Avance 1000 system was

delivered to the new lsquoCentre de RMN agrave

Tregraves Hauts Champsrsquo in Lyon France

1020 MHz nmr

June 2015

Weight 15 tons

Chemistry 328N

The 100MHz nmr Chart

1000 900 800 700 600 500 400 300 200 100 00

10

20

30

40

50

60

70

80

90

000

Si CH3

CH3

CH3

CH3

Frequency

field

The TMS resonance is defined as having ldquo0rdquo frequency

Chemistry 328N

100MHz Spectrum

450 400 350 300 250 200 150 100 50 00

5

10

15

20

Hz

CH3 Cl

325 320 315 310 305 300 295 290 285 2800

5

10

15

2030400

304 Hz

Chemistry 328N

100MHz nmr Spectrum

450 400 350 300 250 200 150 100 50 00

5

10

15

20

CH3 Br

275 270 265 260 2550

5

10

15

20

26850

Hz2685Hz

Chemistry 328N

Nuclear Magnetic Resonance

If we were dealing with 1H nuclei isolatedfrom all other atoms and electrons anycombination of applied field and radiation thatproduces a signal for one 1H would produce asignal for all 1H The same for 13C nuclei

But helliphydrogens in organic molecules are notisolated from all other atoms they aresurrounded by electrons which are caused tocirculate by the presence of the applied field

Chemistry 328N

Nuclear Magnetic Resonance

The circulation of electrons around anucleus in an applied field is calleddiamagnetic current

This current generates a field that opposesthe applied field diamagnetic nuclearshielding results Lenzrsquos Law

The difference in resonance frequenciesbetween the various hydrogen nuclei withina molecule is due to shieldingdeshielding isvery small but very important

Chemistry 328N

Lenzrsquos Law

Heinrich Lenz

1804-1865

Chemistry 328N

Conditions for Resonance

It is the frequency of the radiation and the

NET field at the nucleus that matters

The NET field is the sum of all incident

magnetic fields including those from

ndash The Giant Magnet (applied field)

ndash Diamagnetic Shielding field (electrons)

ndash Coupling (spin fields of adjacent nuclei)

ndash credit card strips earthrsquos field etchellip

Page 24: OC 2/e 12 - University of Texas at Austinwillson.cm.utexas.edu/Teaching/Chem328N/Files/Lecture 03... · 2016. 1. 29. · Born, 1856 in Smiljan, Lika (Austria-Hungary) Died 1943 in

Chemistry 328N

Some Proportionality Constants

Gyromagnetic Ratio n = B

ndash For 1H = 4258 MHzT

Planckrsquos Constant E = h n

Speed of light n = c l or c = n l

Chemical Shift 119889(119901119901119898) =∆n

119878119901119890119888119905119903119900119898119890119905119890119903 119891119903119890119902119906119890119899119888119910

Chemistry 328N

NMR Spectrometer

Chemistry 328N

In principle we could hold field constant and scan frequency looking

for resonance but it is equally effective to scan field strength and hold

frequency constant

Chemistry 328N

500MHz 1H-nmr Spectrometer

Magnet

Chemistry 328N

httpwwwjeolusacomRESOURCESAnalyticalInstrumentsNMRMagnetDestructiontabid390Defaultaspx

Chemistry 328N

800 MHz machine at UH

Highest Frequency in 2013

The first Avance 1000 system was

delivered to the new lsquoCentre de RMN agrave

Tregraves Hauts Champsrsquo in Lyon France

1020 MHz nmr

June 2015

Weight 15 tons

Chemistry 328N

The 100MHz nmr Chart

1000 900 800 700 600 500 400 300 200 100 00

10

20

30

40

50

60

70

80

90

000

Si CH3

CH3

CH3

CH3

Frequency

field

The TMS resonance is defined as having ldquo0rdquo frequency

Chemistry 328N

100MHz Spectrum

450 400 350 300 250 200 150 100 50 00

5

10

15

20

Hz

CH3 Cl

325 320 315 310 305 300 295 290 285 2800

5

10

15

2030400

304 Hz

Chemistry 328N

100MHz nmr Spectrum

450 400 350 300 250 200 150 100 50 00

5

10

15

20

CH3 Br

275 270 265 260 2550

5

10

15

20

26850

Hz2685Hz

Chemistry 328N

Nuclear Magnetic Resonance

If we were dealing with 1H nuclei isolatedfrom all other atoms and electrons anycombination of applied field and radiation thatproduces a signal for one 1H would produce asignal for all 1H The same for 13C nuclei

But helliphydrogens in organic molecules are notisolated from all other atoms they aresurrounded by electrons which are caused tocirculate by the presence of the applied field

Chemistry 328N

Nuclear Magnetic Resonance

The circulation of electrons around anucleus in an applied field is calleddiamagnetic current

This current generates a field that opposesthe applied field diamagnetic nuclearshielding results Lenzrsquos Law

The difference in resonance frequenciesbetween the various hydrogen nuclei withina molecule is due to shieldingdeshielding isvery small but very important

Chemistry 328N

Lenzrsquos Law

Heinrich Lenz

1804-1865

Chemistry 328N

Conditions for Resonance

It is the frequency of the radiation and the

NET field at the nucleus that matters

The NET field is the sum of all incident

magnetic fields including those from

ndash The Giant Magnet (applied field)

ndash Diamagnetic Shielding field (electrons)

ndash Coupling (spin fields of adjacent nuclei)

ndash credit card strips earthrsquos field etchellip

Page 25: OC 2/e 12 - University of Texas at Austinwillson.cm.utexas.edu/Teaching/Chem328N/Files/Lecture 03... · 2016. 1. 29. · Born, 1856 in Smiljan, Lika (Austria-Hungary) Died 1943 in

Chemistry 328N

NMR Spectrometer

Chemistry 328N

In principle we could hold field constant and scan frequency looking

for resonance but it is equally effective to scan field strength and hold

frequency constant

Chemistry 328N

500MHz 1H-nmr Spectrometer

Magnet

Chemistry 328N

httpwwwjeolusacomRESOURCESAnalyticalInstrumentsNMRMagnetDestructiontabid390Defaultaspx

Chemistry 328N

800 MHz machine at UH

Highest Frequency in 2013

The first Avance 1000 system was

delivered to the new lsquoCentre de RMN agrave

Tregraves Hauts Champsrsquo in Lyon France

1020 MHz nmr

June 2015

Weight 15 tons

Chemistry 328N

The 100MHz nmr Chart

1000 900 800 700 600 500 400 300 200 100 00

10

20

30

40

50

60

70

80

90

000

Si CH3

CH3

CH3

CH3

Frequency

field

The TMS resonance is defined as having ldquo0rdquo frequency

Chemistry 328N

100MHz Spectrum

450 400 350 300 250 200 150 100 50 00

5

10

15

20

Hz

CH3 Cl

325 320 315 310 305 300 295 290 285 2800

5

10

15

2030400

304 Hz

Chemistry 328N

100MHz nmr Spectrum

450 400 350 300 250 200 150 100 50 00

5

10

15

20

CH3 Br

275 270 265 260 2550

5

10

15

20

26850

Hz2685Hz

Chemistry 328N

Nuclear Magnetic Resonance

If we were dealing with 1H nuclei isolatedfrom all other atoms and electrons anycombination of applied field and radiation thatproduces a signal for one 1H would produce asignal for all 1H The same for 13C nuclei

But helliphydrogens in organic molecules are notisolated from all other atoms they aresurrounded by electrons which are caused tocirculate by the presence of the applied field

Chemistry 328N

Nuclear Magnetic Resonance

The circulation of electrons around anucleus in an applied field is calleddiamagnetic current

This current generates a field that opposesthe applied field diamagnetic nuclearshielding results Lenzrsquos Law

The difference in resonance frequenciesbetween the various hydrogen nuclei withina molecule is due to shieldingdeshielding isvery small but very important

Chemistry 328N

Lenzrsquos Law

Heinrich Lenz

1804-1865

Chemistry 328N

Conditions for Resonance

It is the frequency of the radiation and the

NET field at the nucleus that matters

The NET field is the sum of all incident

magnetic fields including those from

ndash The Giant Magnet (applied field)

ndash Diamagnetic Shielding field (electrons)

ndash Coupling (spin fields of adjacent nuclei)

ndash credit card strips earthrsquos field etchellip

Page 26: OC 2/e 12 - University of Texas at Austinwillson.cm.utexas.edu/Teaching/Chem328N/Files/Lecture 03... · 2016. 1. 29. · Born, 1856 in Smiljan, Lika (Austria-Hungary) Died 1943 in

Chemistry 328N

In principle we could hold field constant and scan frequency looking

for resonance but it is equally effective to scan field strength and hold

frequency constant

Chemistry 328N

500MHz 1H-nmr Spectrometer

Magnet

Chemistry 328N

httpwwwjeolusacomRESOURCESAnalyticalInstrumentsNMRMagnetDestructiontabid390Defaultaspx

Chemistry 328N

800 MHz machine at UH

Highest Frequency in 2013

The first Avance 1000 system was

delivered to the new lsquoCentre de RMN agrave

Tregraves Hauts Champsrsquo in Lyon France

1020 MHz nmr

June 2015

Weight 15 tons

Chemistry 328N

The 100MHz nmr Chart

1000 900 800 700 600 500 400 300 200 100 00

10

20

30

40

50

60

70

80

90

000

Si CH3

CH3

CH3

CH3

Frequency

field

The TMS resonance is defined as having ldquo0rdquo frequency

Chemistry 328N

100MHz Spectrum

450 400 350 300 250 200 150 100 50 00

5

10

15

20

Hz

CH3 Cl

325 320 315 310 305 300 295 290 285 2800

5

10

15

2030400

304 Hz

Chemistry 328N

100MHz nmr Spectrum

450 400 350 300 250 200 150 100 50 00

5

10

15

20

CH3 Br

275 270 265 260 2550

5

10

15

20

26850

Hz2685Hz

Chemistry 328N

Nuclear Magnetic Resonance

If we were dealing with 1H nuclei isolatedfrom all other atoms and electrons anycombination of applied field and radiation thatproduces a signal for one 1H would produce asignal for all 1H The same for 13C nuclei

But helliphydrogens in organic molecules are notisolated from all other atoms they aresurrounded by electrons which are caused tocirculate by the presence of the applied field

Chemistry 328N

Nuclear Magnetic Resonance

The circulation of electrons around anucleus in an applied field is calleddiamagnetic current

This current generates a field that opposesthe applied field diamagnetic nuclearshielding results Lenzrsquos Law

The difference in resonance frequenciesbetween the various hydrogen nuclei withina molecule is due to shieldingdeshielding isvery small but very important

Chemistry 328N

Lenzrsquos Law

Heinrich Lenz

1804-1865

Chemistry 328N

Conditions for Resonance

It is the frequency of the radiation and the

NET field at the nucleus that matters

The NET field is the sum of all incident

magnetic fields including those from

ndash The Giant Magnet (applied field)

ndash Diamagnetic Shielding field (electrons)

ndash Coupling (spin fields of adjacent nuclei)

ndash credit card strips earthrsquos field etchellip

Page 27: OC 2/e 12 - University of Texas at Austinwillson.cm.utexas.edu/Teaching/Chem328N/Files/Lecture 03... · 2016. 1. 29. · Born, 1856 in Smiljan, Lika (Austria-Hungary) Died 1943 in

Chemistry 328N

500MHz 1H-nmr Spectrometer

Magnet

Chemistry 328N

httpwwwjeolusacomRESOURCESAnalyticalInstrumentsNMRMagnetDestructiontabid390Defaultaspx

Chemistry 328N

800 MHz machine at UH

Highest Frequency in 2013

The first Avance 1000 system was

delivered to the new lsquoCentre de RMN agrave

Tregraves Hauts Champsrsquo in Lyon France

1020 MHz nmr

June 2015

Weight 15 tons

Chemistry 328N

The 100MHz nmr Chart

1000 900 800 700 600 500 400 300 200 100 00

10

20

30

40

50

60

70

80

90

000

Si CH3

CH3

CH3

CH3

Frequency

field

The TMS resonance is defined as having ldquo0rdquo frequency

Chemistry 328N

100MHz Spectrum

450 400 350 300 250 200 150 100 50 00

5

10

15

20

Hz

CH3 Cl

325 320 315 310 305 300 295 290 285 2800

5

10

15

2030400

304 Hz

Chemistry 328N

100MHz nmr Spectrum

450 400 350 300 250 200 150 100 50 00

5

10

15

20

CH3 Br

275 270 265 260 2550

5

10

15

20

26850

Hz2685Hz

Chemistry 328N

Nuclear Magnetic Resonance

If we were dealing with 1H nuclei isolatedfrom all other atoms and electrons anycombination of applied field and radiation thatproduces a signal for one 1H would produce asignal for all 1H The same for 13C nuclei

But helliphydrogens in organic molecules are notisolated from all other atoms they aresurrounded by electrons which are caused tocirculate by the presence of the applied field

Chemistry 328N

Nuclear Magnetic Resonance

The circulation of electrons around anucleus in an applied field is calleddiamagnetic current

This current generates a field that opposesthe applied field diamagnetic nuclearshielding results Lenzrsquos Law

The difference in resonance frequenciesbetween the various hydrogen nuclei withina molecule is due to shieldingdeshielding isvery small but very important

Chemistry 328N

Lenzrsquos Law

Heinrich Lenz

1804-1865

Chemistry 328N

Conditions for Resonance

It is the frequency of the radiation and the

NET field at the nucleus that matters

The NET field is the sum of all incident

magnetic fields including those from

ndash The Giant Magnet (applied field)

ndash Diamagnetic Shielding field (electrons)

ndash Coupling (spin fields of adjacent nuclei)

ndash credit card strips earthrsquos field etchellip

Page 28: OC 2/e 12 - University of Texas at Austinwillson.cm.utexas.edu/Teaching/Chem328N/Files/Lecture 03... · 2016. 1. 29. · Born, 1856 in Smiljan, Lika (Austria-Hungary) Died 1943 in

Chemistry 328N

httpwwwjeolusacomRESOURCESAnalyticalInstrumentsNMRMagnetDestructiontabid390Defaultaspx

Chemistry 328N

800 MHz machine at UH

Highest Frequency in 2013

The first Avance 1000 system was

delivered to the new lsquoCentre de RMN agrave

Tregraves Hauts Champsrsquo in Lyon France

1020 MHz nmr

June 2015

Weight 15 tons

Chemistry 328N

The 100MHz nmr Chart

1000 900 800 700 600 500 400 300 200 100 00

10

20

30

40

50

60

70

80

90

000

Si CH3

CH3

CH3

CH3

Frequency

field

The TMS resonance is defined as having ldquo0rdquo frequency

Chemistry 328N

100MHz Spectrum

450 400 350 300 250 200 150 100 50 00

5

10

15

20

Hz

CH3 Cl

325 320 315 310 305 300 295 290 285 2800

5

10

15

2030400

304 Hz

Chemistry 328N

100MHz nmr Spectrum

450 400 350 300 250 200 150 100 50 00

5

10

15

20

CH3 Br

275 270 265 260 2550

5

10

15

20

26850

Hz2685Hz

Chemistry 328N

Nuclear Magnetic Resonance

If we were dealing with 1H nuclei isolatedfrom all other atoms and electrons anycombination of applied field and radiation thatproduces a signal for one 1H would produce asignal for all 1H The same for 13C nuclei

But helliphydrogens in organic molecules are notisolated from all other atoms they aresurrounded by electrons which are caused tocirculate by the presence of the applied field

Chemistry 328N

Nuclear Magnetic Resonance

The circulation of electrons around anucleus in an applied field is calleddiamagnetic current

This current generates a field that opposesthe applied field diamagnetic nuclearshielding results Lenzrsquos Law

The difference in resonance frequenciesbetween the various hydrogen nuclei withina molecule is due to shieldingdeshielding isvery small but very important

Chemistry 328N

Lenzrsquos Law

Heinrich Lenz

1804-1865

Chemistry 328N

Conditions for Resonance

It is the frequency of the radiation and the

NET field at the nucleus that matters

The NET field is the sum of all incident

magnetic fields including those from

ndash The Giant Magnet (applied field)

ndash Diamagnetic Shielding field (electrons)

ndash Coupling (spin fields of adjacent nuclei)

ndash credit card strips earthrsquos field etchellip

Page 29: OC 2/e 12 - University of Texas at Austinwillson.cm.utexas.edu/Teaching/Chem328N/Files/Lecture 03... · 2016. 1. 29. · Born, 1856 in Smiljan, Lika (Austria-Hungary) Died 1943 in

Chemistry 328N

800 MHz machine at UH

Highest Frequency in 2013

The first Avance 1000 system was

delivered to the new lsquoCentre de RMN agrave

Tregraves Hauts Champsrsquo in Lyon France

1020 MHz nmr

June 2015

Weight 15 tons

Chemistry 328N

The 100MHz nmr Chart

1000 900 800 700 600 500 400 300 200 100 00

10

20

30

40

50

60

70

80

90

000

Si CH3

CH3

CH3

CH3

Frequency

field

The TMS resonance is defined as having ldquo0rdquo frequency

Chemistry 328N

100MHz Spectrum

450 400 350 300 250 200 150 100 50 00

5

10

15

20

Hz

CH3 Cl

325 320 315 310 305 300 295 290 285 2800

5

10

15

2030400

304 Hz

Chemistry 328N

100MHz nmr Spectrum

450 400 350 300 250 200 150 100 50 00

5

10

15

20

CH3 Br

275 270 265 260 2550

5

10

15

20

26850

Hz2685Hz

Chemistry 328N

Nuclear Magnetic Resonance

If we were dealing with 1H nuclei isolatedfrom all other atoms and electrons anycombination of applied field and radiation thatproduces a signal for one 1H would produce asignal for all 1H The same for 13C nuclei

But helliphydrogens in organic molecules are notisolated from all other atoms they aresurrounded by electrons which are caused tocirculate by the presence of the applied field

Chemistry 328N

Nuclear Magnetic Resonance

The circulation of electrons around anucleus in an applied field is calleddiamagnetic current

This current generates a field that opposesthe applied field diamagnetic nuclearshielding results Lenzrsquos Law

The difference in resonance frequenciesbetween the various hydrogen nuclei withina molecule is due to shieldingdeshielding isvery small but very important

Chemistry 328N

Lenzrsquos Law

Heinrich Lenz

1804-1865

Chemistry 328N

Conditions for Resonance

It is the frequency of the radiation and the

NET field at the nucleus that matters

The NET field is the sum of all incident

magnetic fields including those from

ndash The Giant Magnet (applied field)

ndash Diamagnetic Shielding field (electrons)

ndash Coupling (spin fields of adjacent nuclei)

ndash credit card strips earthrsquos field etchellip

Page 30: OC 2/e 12 - University of Texas at Austinwillson.cm.utexas.edu/Teaching/Chem328N/Files/Lecture 03... · 2016. 1. 29. · Born, 1856 in Smiljan, Lika (Austria-Hungary) Died 1943 in

Chemistry 328N

The 100MHz nmr Chart

1000 900 800 700 600 500 400 300 200 100 00

10

20

30

40

50

60

70

80

90

000

Si CH3

CH3

CH3

CH3

Frequency

field

The TMS resonance is defined as having ldquo0rdquo frequency

Chemistry 328N

100MHz Spectrum

450 400 350 300 250 200 150 100 50 00

5

10

15

20

Hz

CH3 Cl

325 320 315 310 305 300 295 290 285 2800

5

10

15

2030400

304 Hz

Chemistry 328N

100MHz nmr Spectrum

450 400 350 300 250 200 150 100 50 00

5

10

15

20

CH3 Br

275 270 265 260 2550

5

10

15

20

26850

Hz2685Hz

Chemistry 328N

Nuclear Magnetic Resonance

If we were dealing with 1H nuclei isolatedfrom all other atoms and electrons anycombination of applied field and radiation thatproduces a signal for one 1H would produce asignal for all 1H The same for 13C nuclei

But helliphydrogens in organic molecules are notisolated from all other atoms they aresurrounded by electrons which are caused tocirculate by the presence of the applied field

Chemistry 328N

Nuclear Magnetic Resonance

The circulation of electrons around anucleus in an applied field is calleddiamagnetic current

This current generates a field that opposesthe applied field diamagnetic nuclearshielding results Lenzrsquos Law

The difference in resonance frequenciesbetween the various hydrogen nuclei withina molecule is due to shieldingdeshielding isvery small but very important

Chemistry 328N

Lenzrsquos Law

Heinrich Lenz

1804-1865

Chemistry 328N

Conditions for Resonance

It is the frequency of the radiation and the

NET field at the nucleus that matters

The NET field is the sum of all incident

magnetic fields including those from

ndash The Giant Magnet (applied field)

ndash Diamagnetic Shielding field (electrons)

ndash Coupling (spin fields of adjacent nuclei)

ndash credit card strips earthrsquos field etchellip

Page 31: OC 2/e 12 - University of Texas at Austinwillson.cm.utexas.edu/Teaching/Chem328N/Files/Lecture 03... · 2016. 1. 29. · Born, 1856 in Smiljan, Lika (Austria-Hungary) Died 1943 in

Chemistry 328N

100MHz Spectrum

450 400 350 300 250 200 150 100 50 00

5

10

15

20

Hz

CH3 Cl

325 320 315 310 305 300 295 290 285 2800

5

10

15

2030400

304 Hz

Chemistry 328N

100MHz nmr Spectrum

450 400 350 300 250 200 150 100 50 00

5

10

15

20

CH3 Br

275 270 265 260 2550

5

10

15

20

26850

Hz2685Hz

Chemistry 328N

Nuclear Magnetic Resonance

If we were dealing with 1H nuclei isolatedfrom all other atoms and electrons anycombination of applied field and radiation thatproduces a signal for one 1H would produce asignal for all 1H The same for 13C nuclei

But helliphydrogens in organic molecules are notisolated from all other atoms they aresurrounded by electrons which are caused tocirculate by the presence of the applied field

Chemistry 328N

Nuclear Magnetic Resonance

The circulation of electrons around anucleus in an applied field is calleddiamagnetic current

This current generates a field that opposesthe applied field diamagnetic nuclearshielding results Lenzrsquos Law

The difference in resonance frequenciesbetween the various hydrogen nuclei withina molecule is due to shieldingdeshielding isvery small but very important

Chemistry 328N

Lenzrsquos Law

Heinrich Lenz

1804-1865

Chemistry 328N

Conditions for Resonance

It is the frequency of the radiation and the

NET field at the nucleus that matters

The NET field is the sum of all incident

magnetic fields including those from

ndash The Giant Magnet (applied field)

ndash Diamagnetic Shielding field (electrons)

ndash Coupling (spin fields of adjacent nuclei)

ndash credit card strips earthrsquos field etchellip

Page 32: OC 2/e 12 - University of Texas at Austinwillson.cm.utexas.edu/Teaching/Chem328N/Files/Lecture 03... · 2016. 1. 29. · Born, 1856 in Smiljan, Lika (Austria-Hungary) Died 1943 in

Chemistry 328N

100MHz nmr Spectrum

450 400 350 300 250 200 150 100 50 00

5

10

15

20

CH3 Br

275 270 265 260 2550

5

10

15

20

26850

Hz2685Hz

Chemistry 328N

Nuclear Magnetic Resonance

If we were dealing with 1H nuclei isolatedfrom all other atoms and electrons anycombination of applied field and radiation thatproduces a signal for one 1H would produce asignal for all 1H The same for 13C nuclei

But helliphydrogens in organic molecules are notisolated from all other atoms they aresurrounded by electrons which are caused tocirculate by the presence of the applied field

Chemistry 328N

Nuclear Magnetic Resonance

The circulation of electrons around anucleus in an applied field is calleddiamagnetic current

This current generates a field that opposesthe applied field diamagnetic nuclearshielding results Lenzrsquos Law

The difference in resonance frequenciesbetween the various hydrogen nuclei withina molecule is due to shieldingdeshielding isvery small but very important

Chemistry 328N

Lenzrsquos Law

Heinrich Lenz

1804-1865

Chemistry 328N

Conditions for Resonance

It is the frequency of the radiation and the

NET field at the nucleus that matters

The NET field is the sum of all incident

magnetic fields including those from

ndash The Giant Magnet (applied field)

ndash Diamagnetic Shielding field (electrons)

ndash Coupling (spin fields of adjacent nuclei)

ndash credit card strips earthrsquos field etchellip

Page 33: OC 2/e 12 - University of Texas at Austinwillson.cm.utexas.edu/Teaching/Chem328N/Files/Lecture 03... · 2016. 1. 29. · Born, 1856 in Smiljan, Lika (Austria-Hungary) Died 1943 in

Chemistry 328N

Nuclear Magnetic Resonance

If we were dealing with 1H nuclei isolatedfrom all other atoms and electrons anycombination of applied field and radiation thatproduces a signal for one 1H would produce asignal for all 1H The same for 13C nuclei

But helliphydrogens in organic molecules are notisolated from all other atoms they aresurrounded by electrons which are caused tocirculate by the presence of the applied field

Chemistry 328N

Nuclear Magnetic Resonance

The circulation of electrons around anucleus in an applied field is calleddiamagnetic current

This current generates a field that opposesthe applied field diamagnetic nuclearshielding results Lenzrsquos Law

The difference in resonance frequenciesbetween the various hydrogen nuclei withina molecule is due to shieldingdeshielding isvery small but very important

Chemistry 328N

Lenzrsquos Law

Heinrich Lenz

1804-1865

Chemistry 328N

Conditions for Resonance

It is the frequency of the radiation and the

NET field at the nucleus that matters

The NET field is the sum of all incident

magnetic fields including those from

ndash The Giant Magnet (applied field)

ndash Diamagnetic Shielding field (electrons)

ndash Coupling (spin fields of adjacent nuclei)

ndash credit card strips earthrsquos field etchellip

Page 34: OC 2/e 12 - University of Texas at Austinwillson.cm.utexas.edu/Teaching/Chem328N/Files/Lecture 03... · 2016. 1. 29. · Born, 1856 in Smiljan, Lika (Austria-Hungary) Died 1943 in

Chemistry 328N

Nuclear Magnetic Resonance

The circulation of electrons around anucleus in an applied field is calleddiamagnetic current

This current generates a field that opposesthe applied field diamagnetic nuclearshielding results Lenzrsquos Law

The difference in resonance frequenciesbetween the various hydrogen nuclei withina molecule is due to shieldingdeshielding isvery small but very important

Chemistry 328N

Lenzrsquos Law

Heinrich Lenz

1804-1865

Chemistry 328N

Conditions for Resonance

It is the frequency of the radiation and the

NET field at the nucleus that matters

The NET field is the sum of all incident

magnetic fields including those from

ndash The Giant Magnet (applied field)

ndash Diamagnetic Shielding field (electrons)

ndash Coupling (spin fields of adjacent nuclei)

ndash credit card strips earthrsquos field etchellip

Page 35: OC 2/e 12 - University of Texas at Austinwillson.cm.utexas.edu/Teaching/Chem328N/Files/Lecture 03... · 2016. 1. 29. · Born, 1856 in Smiljan, Lika (Austria-Hungary) Died 1943 in

Chemistry 328N

Lenzrsquos Law

Heinrich Lenz

1804-1865

Chemistry 328N

Conditions for Resonance

It is the frequency of the radiation and the

NET field at the nucleus that matters

The NET field is the sum of all incident

magnetic fields including those from

ndash The Giant Magnet (applied field)

ndash Diamagnetic Shielding field (electrons)

ndash Coupling (spin fields of adjacent nuclei)

ndash credit card strips earthrsquos field etchellip

Page 36: OC 2/e 12 - University of Texas at Austinwillson.cm.utexas.edu/Teaching/Chem328N/Files/Lecture 03... · 2016. 1. 29. · Born, 1856 in Smiljan, Lika (Austria-Hungary) Died 1943 in

Chemistry 328N

Conditions for Resonance

It is the frequency of the radiation and the

NET field at the nucleus that matters

The NET field is the sum of all incident

magnetic fields including those from

ndash The Giant Magnet (applied field)

ndash Diamagnetic Shielding field (electrons)

ndash Coupling (spin fields of adjacent nuclei)

ndash credit card strips earthrsquos field etchellip