13.22 Mass Spectrometry. Atom or molecule is hit by high-energy electron Principles of...

13.2213.22

Mass SpectrometryMass Spectrometry

Atom or molecule is hit by high-energy electronAtom or molecule is hit by high-energy electron

Principles of Electron-Impact Mass SpectrometryPrinciples of Electron-Impact Mass Spectrometry

ee––


electron is deflected but transfers much of electron is deflected but transfers much of its energy to the moleculeits energy to the molecule

ee––



electron is deflected but transfers much of electron is deflected but transfers much of its energy to the moleculeits energy to the molecule

ee––


This energy-rich species ejects an electron.This energy-rich species ejects an electron.


This energy-rich species ejects an electron.This energy-rich species ejects an electron.


forming a positively charged, odd-electron forming a positively charged, odd-electron species called the species called the molecular ionmolecular ion

ee––++••

Molecular ion passes between poles of a Molecular ion passes between poles of a magnet and is deflected by magnetic fieldmagnet and is deflected by magnetic field

amount of amount of deflection depends deflection depends on mass-to-charge on mass-to-charge ratioratio

highest m/z highest m/z deflected leastdeflected least

lowest m/z lowest m/z deflected mostdeflected most


++••


If the only ion that is present is the molecular If the only ion that is present is the molecular ion, mass spectrometry provides a way to ion, mass spectrometry provides a way to measure the molecular weight of a compound measure the molecular weight of a compound and is often used for this purpose.and is often used for this purpose.

However, the molecular ion often fragments to However, the molecular ion often fragments to a mixture of species of lower m/z.a mixture of species of lower m/z.

The molecular ion dissociates to a cationThe molecular ion dissociates to a cationand a radical.and a radical.


++••

The molecular ion dissociates to a cationThe molecular ion dissociates to a cationand a radical.and a radical.


++ ••

Usually several fragmentation pathways are Usually several fragmentation pathways are available and a mixture of ions is produced.available and a mixture of ions is produced.

mixture of ions of mixture of ions of different mass different mass gives separate peak gives separate peak for each m/zfor each m/z

intensity of peak intensity of peak proportional to proportional to percentage of each percentage of each ion of different ion of different mass in mixturemass in mixture

separation of peaks separation of peaks depends on relative depends on relative massmass


++

++++

++

+

+

mixture of ions of mixture of ions of different mass different mass gives separate peak gives separate peak for each m/zfor each m/z

intensity of peak intensity of peak proportional to proportional to percentage of each percentage of each atom of different atom of different mass in mixturemass in mixture

separation of peaks separation of peaks depends on relative depends on relative massmass

++ ++ ++ ++

+ +


2020 4040 6060 8080 100100 120 120

m/zm/z

m/z m/z = 78= 78

100100

8080

6060

4040

2020

00

Relative Relative intensityintensity

Some molecules undergo very little Some molecules undergo very little fragmentationfragmentation

Benzene is an example. The major peak Benzene is an example. The major peak corresponds to the molecular ion.corresponds to the molecular ion.

HH

HH HH

HHHH

HH

HH

HH HH

HHHH

HH

HH

HH HH

HHHH

HH

all H are all H are 11H and all H and all C are C are 1212CC

one C is one C is 1313CC one H is one H is 22HH

Isotopic ClustersIsotopic Clusters

7878 7979 7979

93.4%93.4% 6.5%6.5% 0.1%0.1%

2020 4040 6060 8080 100100 120 120

m/zm/z

100100

8080

6060

4040

2020

00


112112

114114

Isotopic ClustersIsotopic Clustersin Chlorobenzenein Chlorobenzene

visible in peaks visible in peaks for molecular ionfor molecular ion

3535ClCl 3737ClCl

2020 4040 6060 8080 100100 120 120

m/zm/z


7777

Isotopic ClustersIsotopic Clustersin Chlorobenzenein Chlorobenzene

no no mm//zz 77, 79 77, 79 pair; therefore ion pair; therefore ion responsible forresponsible formm//zz 77 peak does 77 peak does not contain Clnot contain Cl

HH

HH

HH

HH

HH ++

100100

8080

6060

4040

2020

00

Alkanes undergo extensive fragmentationAlkanes undergo extensive fragmentation

m/zm/z

DecaneDecane

142142

4343

5757

7171

8585

9999

CHCH33—CH—CH22—CH—CH22—CH—CH22—CH—CH22—CH—CH22—CH—CH22—CH—CH22—CH—CH22—CH—CH33


100100

8080

6060

4040

2020

00

2020 4040 6060 8080 100100 120 120

Propylbenzene fragments mostlyPropylbenzene fragments mostlyat the benzylic positionat the benzylic position

2020 4040 6060 8080 100100 120 120

m/zm/z


120120

9191 CHCH22—CH—CH22CHCH33

100100

8080

6060

4040

2020

00

13.2313.23

Molecular FormulaMolecular Formula

as aas a

Clue to StructureClue to Structure

Molecular WeightsMolecular Weights

One of the first pieces of information we try to One of the first pieces of information we try to obtain when determining a molecular obtain when determining a molecular structure is the molecular formula.structure is the molecular formula.

However, we can gain some information even However, we can gain some information even from the molecular weight. Mass from the molecular weight. Mass spectrometry makes it relatively easy to spectrometry makes it relatively easy to determine molecular weights.determine molecular weights.

The Nitrogen RuleThe Nitrogen Rule

A molecule with an A molecule with an odd number of odd number of nitrogens has an odd nitrogens has an odd molecular weight.molecular weight.

A molecule that A molecule that contains only C, H, contains only C, H, and O or which has and O or which has an even number of an even number of nitrogens has an nitrogens has an even molecular even molecular weight.weight.

NNHH22 9393

138138

NNHH22OO22NN

183183

NNHH22OO22NN

NNOO22

Exact Molecular WeightsExact Molecular Weights

CHCH33(CH(CH22))55CHCH33

HeptaneHeptane

CHCH33COCO

OO Cyclopropyl acetateCyclopropyl acetate

Molecular formulaMolecular formula

Molecular weightMolecular weight

CC77HH1616 CC55HH88OO22

100100 100100

Exact massExact mass 100.1253100.1253 100.0524100.0524

Mass spectrometry can measure exact Mass spectrometry can measure exact masses. Therefore, mass spectrometry can masses. Therefore, mass spectrometry can give molecular formulas.give molecular formulas.

Molecular FormulasMolecular Formulas

Knowing that the molecular formula of a Knowing that the molecular formula of a substance is Csubstance is C77HH1616 tells us immediately that is tells us immediately that is

an alkane because it corresponds to Can alkane because it corresponds to CnnHH22nn+2+2

CC77HH1414 lacks two hydrogens of an alkane, lacks two hydrogens of an alkane,

therefore contains either a ring or a double therefore contains either a ring or a double bond bond

Index of Hydrogen DeficiencyIndex of Hydrogen Deficiency

relates molecular formulas to multiple bonds relates molecular formulas to multiple bonds and ringsand rings

index of hydrogen deficiency = index of hydrogen deficiency =

1122

(molecular formula of alkane –(molecular formula of alkane – molecular formula of compound) molecular formula of compound)

Example 1Example 1

index of hydrogen deficiency index of hydrogen deficiency

C7H14C7H14

1122

(molecular formula of alkane –(molecular formula of alkane – molecular formula of compound) molecular formula of compound)

==

1122

(C(C77HH1616 – C – C77HH1414))==

1122

(2) = 1(2) = 1==

Therefore, one ring or one double bond.Therefore, one ring or one double bond.

Example 2Example 2

C7H12C7H12

1122

(C(C77HH1616 – C – C77HH1212))==

1122

(4) = 2(4) = 2==

Therefore, two rings, one triple bond,Therefore, two rings, one triple bond,two double bonds, or one double bond + one ring.two double bonds, or one double bond + one ring.

Oxygen has no effectOxygen has no effect

CHCH33(CH(CH22))55CHCH22OH (1-heptanol, COH (1-heptanol, C77HH1616O) has O) has

same number of H atoms as heptanesame number of H atoms as heptane


1122

(C(C77HH1616 – C – C77HH1616O)O) = 0= 0

no rings or double bondsno rings or double bonds

Oxygen has no effectOxygen has no effect


1122

(C(C55HH1212 – C – C55HH88OO22)) = 2= 2

one ring plus one double bondone ring plus one double bond

CHCH33COCO

OO Cyclopropyl acetateCyclopropyl acetate

If halogen is presentIf halogen is present

Treat a halogen as if it were hydrogen.Treat a halogen as if it were hydrogen.

CC CC

CHCH33

ClClHH

HH

CC33HH55ClCl

same index of hydrogensame index of hydrogendeficiency as for Cdeficiency as for C33HH66

Rings versus Multiple BondsRings versus Multiple Bonds

Index of hydrogen deficiency tells us the sum ofIndex of hydrogen deficiency tells us the sum ofrings plus multiple bonds.rings plus multiple bonds.

Catalytic hydrogenation tells us how many Catalytic hydrogenation tells us how many multiple bonds there are.multiple bonds there are.

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13.22 Mass Spectrometry. Atom or molecule is hit by high-energy electron Principles of...

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