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    Mass Spectrometry Part 1: Lecture Supplement: Take One Handout From The Stage

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    ravi_nyse
    Mass Spectrometry Part 1 1. Mass spectrometry is used to determine the molecular formula of an unknown substance by analyzing its mass spectrum. 2. The mass spectrum shows the relative abundances of molecular and fragment ions based on their mass-to-charge ratios. 3. Isotopic abundances reveal the elemental composition, while molecular and fragment ion peaks provide clues about functional groups and molecular structure. 4. Rules for interpreting mass spectra include using the relative intensity of M+1 peaks to determine carbon count, and looking for M+2 peaks indicating halogens. 5. Multiple candidate formulas can be generated and narrowed down using additional spectral data and rules about hydrogen counts, nitrogen parity, and pi bonds/rings.

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    Mass Spectrometry Part 1: Lecture Supplement: Take One Handout From The Stage

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    ravi_nyse
    29 views34 pages
    Mass Spectrometry Part 1 1. Mass spectrometry is used to determine the molecular formula of an unknown substance by analyzing its mass spectrum. 2. The mass spectrum shows the relative abundances of molecular and fragment ions based on their mass-to-charge ratios. 3. Isotopic abundances reveal the elemental composition, while molecular and fragment ion peaks provide clues about functional groups and molecular structure. 4. Rules for interpreting mass spectra include using the relative intensity of M+1 peaks to determine carbon count, and looking for M+2 peaks indicating halogens. 5. Multiple candidate formulas can be generated and narrowed down using additional spectral data and rules about hydrogen counts, nitrogen parity, and pi bonds/rings.

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    Mass Spectrometry Part 1 1. Mass spectrometry is used to determine the molecular formula of an unknown substance by analyzing its mass spectrum. 2. The mass spectrum shows the relative abundances of molecular and fragment ions based on their mass-to-charge ratios. 3. Isotopic abundances reveal the elemental composition, while molecular and fragment ion peaks provide clues about functional groups and molecular structure. 4. Rules for interpreting mass spectra include using the relative intensity of M+1 peaks to determine carbon count, and looking for M+2 peaks indicating halogens. 5. Multiple candidate formulas can be generated and narrowed down using additional spectral data and rules about hydrogen counts, nitrogen parity, and pi bonds/rings.

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    29 views34 pages

    Mass Spectrometry Part 1: Lecture Supplement: Take One Handout From The Stage

    Uploaded by

    ravi_nyse
    Mass Spectrometry Part 1 1. Mass spectrometry is used to determine the molecular formula of an unknown substance by analyzing its mass spectrum. 2. The mass spectrum shows the relative abundances of molecular and fragment ions based on their mass-to-charge ratios. 3. Isotopic abundances reveal the elemental composition, while molecular and fragment ion peaks provide clues about functional groups and molecular structure. 4. Rules for interpreting mass spectra include using the relative intensity of M+1 peaks to determine carbon count, and looking for M+2 peaks indicating halogens. 5. Multiple candidate formulas can be generated and narrowed down using additional spectral data and rules about hydrogen counts, nitrogen parity, and pi bonds/rings.

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    Mass Spectrometry Part 1

    Lecture Supplement: Take one handout from the stage

    Spectroscopy
    Why bother with spectroscopy? Determine structure of unknown substance

    erify purity!identity of known substance

    Spectroscopy
    What methods are commonly used?

    Mass spectrometry $MS%" molecular formula

    &nfrared spectroscopy $&'% functional groups

    #uclear magnetic resonance $#M'% C/H molecular skeleton


    "#ot rigorously a type of spectroscopy

    ()ray crystallography" spatial position of atoms

    Spectroscopy
    *+ample: unidentified white powder MS: ,1-.1/# &': ben0ene ring1 secondary amine $'2#.% #M': has ,.2),.),.3 ()ray: not necessary in this case
    . # ,.3 ,.3

    Mass Spectrometry
    The Mass Spectrometer Fundamental operating principle Determine mass by manipulating flight path of an ion in a magnetic field
    *lectron gun &oni0ation sample introduction 5 6ccelerator plates Detector fires Detector Detector 4uiet Detector 4uiet &oni0ation: ( 5 e) (58 5 2 e) Magnet m!0 m!0too too 7ust large small right Measure ion mass)to)charge ratio $m!0%

    Isotopes
    &sotopes: atoms with same number of protons and same number of electrons but different numbers of neutrons 6ston mass spectrum of neon $1919% #e empirical atomic weight : 2-82 amu #e mass spectrum: predict single peak at m!0 : 2-82 'esults m!0 2-82 2-8228relati;e intensity no peak 9-< 1-<

    ,onclusions #eon is a mi+ture of isotopes =eighted a;erage: $9-< + 2-8- amu% 5 $1-8-< + 228- amu% : 2-82 amu #obel Pri0e in ,hemistry 1922 to 6ston for disco;ery of stable element isotopes

    The Mass Spectrum


    *+ample: methane ,.> 5 e) ,.>58 5 2 e) ?ase peak: most abundant ion 'elati;e ion abundance $<% m!0 : $1 + 12% 5 $> + 1% : 1@ , .

    mass)to)charge ratio $m!0%

    The Mass Spectrum


    6lternate data presentation888 m!0 $amu% 'elati;e abundance $<% 1A 1C 1@ 1/ 1> 13 12 B -8/ 181 1--8A/8982 3818M52 M51 M M). M ) 2. M ) 3. M ) >. ,1.> or 12,3.1.3 or888 13 1 , .> or 12,2.1.3 12 1 , .>
    1>

    Molecular ion $M%: intact ion of substance being analy0ed Dragment ion: formed by clea;age of one or more bonds on molecular ions

    The Mass Spectrum


    Origin of Relative Ion Abundances M contributors Isotope
    1

    M51 contributors Isotope


    2

    M52 contributors Isotope


    3

    Natural Abundance 9989A//< 9A8A93 998@3> 998C/9 1--89/8C/8CC /-8@9 1--8-

    Natural Abundance -8-1/< 181-C -83@@ -8-3C -8C@

    Natural Abundance ppm ppm -82-> >822 2>823 >9831

    . , # E D S

    . , # E S

    . ,

    12 1> 1@

    13 1/ 1C

    1>

    1A

    E S

    19 32 3/ C9

    33

    3> 3C A1

    ,l &

    ,l

    ?r

    ?r

    12C

    This table will be provided on an exam. Do not memorize it.

    The Mass Spectrum


    Relative Intensity of Molecular Ion ea!s &magine a sample containing 1-1--- methane molecules888 Molecule
    12

    F in sample 9AA9 11G1

    m!0 12 5 $> + 1% : 1@

    'elati;e abundance 1--<

    ,1.> ,1.> ,1.>

    13

    13 5 $> + 1% : 1C $11-!9AA9% + 1--< : 181<" 1> 5 $> + 1% : 1A $1!9AA9% + 1--< : B -81<"

    1>

    ",ontributions from ions with 2. are ignored because of its ;ery small natural abundance

    ,.> mass spectrum m!0 : 1@ $MH 1--<%1 m!0 : 1C $M51H 181<%1 m!0 : 1A $M52H B -81<%

    10

    Formula from Mass Spectrum


    M51 ,ontributors ,omparing many mass spectra re;eals M51 intensity G181< per , in formula *+amples: ,2.@ M : 1--<H M51 : G282< ,@.@ M : 1--<H M51 : G@8@< =orking backwards gi;es a useful obser;ation888 =hen relati;e contribution of M : 1--< then relati;e abundance of M51!181< gi;es the appro+imate number of carbon atoms in the molecular formula Ether M51 contributors 1/# $-83C<% and 33S $-8C@<% should be considered 2. $-8-1/<% and 1CE $-8-3C<% can be ignored

    11

    Formula from Mass Spectrum


    M52 ,ontributors 6nything useful from intensity of M52I &sotopes
    32

    #atural abundances 9/8- : >82 C/8A : 2>82 /-8C : >983

    &ntensity M : M52 1-- : >8> 1-- : 3189 1-- : 9C82

    S : 3>S

    3/

    ,l : 3C,l

    C9

    ?r : A1?r

    ,onclusion: Mass spectra of molecules with S, Cl, or Br have significant M+2 peaks

    12

    Formula from Mass Spectrum


    M52 ,ontributors
    ,.3 . , ,.3 ,l

    'elati;e abundance $<%

    ,3.C,l

    , . ,l M: 3@ 5 C 5 3/ : CA M52: 3@ 5 C 5 3C : ACA A-

    M:M52 abundance G3:1

    m!0

    13

    Formula from Mass Spectrum


    M52 ,ontributors ,3.C?r

    'elati;e abundance $<%

    ?r

    , . ?r M: 3@ 5 C 5 C9 : 122 M52: 3@ 5 C 5 A1 : 12> M:M52 abundance G1:1

    122

    12>

    m!0

    14

    Identifying the Molecular Ions


    Which pea!s are molecular ions? .ighest m!0 not always M M51 has m!0 one more than m!0 of M
    ?r

    ,C.C?r M: m!0 : 1C-

    15

    Formula from Mass Spectrum


    "ummary of Information from Mass "pectrum M: 'e;eals mass of molecule composed of lowest mass isotopes M51: &ntensity of M51 ! 181< : number of carbons M52: &ntensity re;eals presence of sulfur1 chlorine1 and bromine

    #e+t lecture: procedure for deri;ing formula from mass spectrum

    16

    Mass Spectrometry Part 2


    Lecture Supplement: Take one handout from the stage

    17

    Summary of Part 1
    "pectroscopy: Study of the interaction of photons and matter Jseful to determine molecular structure Types: MS"1 &'1 #M'1 +)ray crystallography" "not really spectroscopy M" fundamental principle: Manipulate flight path of ion in magnetic field ,harge $0%1 magnetic field strength are knownH ion mass $m% is determined Isotopes: #atural abundance of isotopes controls relati;e abundance of ions Molecular ion #M$ M%&$ M%'$ etc()* &ntact ion of substance being analy0ed m!0 of M : molecular mass composed of lowest mass isotopes 1.1 12,1 3/,l1 etc8 'elati;e abundance of M51!181< gi;es appro+imate number of carbons M52 re;eals presence of sulfur1 chlorine1 or bromine +ragment ion* Drom decomposition of molecular ion before reaching detector 6nalysis of fragmentation patterns not important for ,hem 1>,

    18

    Mass Spectrum Dormula Structure


    ,ow do we derive structure from the mass spectrum?

    ,.3 . , ,.3 ,l

    #ot tri;ial to do this directly Structure comes from formulaH formula comes from mass spectrum
    ,.3

    ,3.C,l

    , ,.3

    ,l

    19

    Mass Spectrum Dormula Structure


    ,ow do we derive formula from the mass spectrum? m!0 and relati;e intensities of M1 M511 and M52

    M: m!0 : CA ,2.@E3 ,3.C,l ,/.># ,@.@ etc8

    6 few useful rules to narrow the choices

    20

    .ow Many #itrogen 6tomsI


    ,onsider these molecules:
    ,.3 E2# #E2 .3, # E ,.3 #

    #.3

    .2##.2
    E #E2

    # ,.3

    Dormula: m!0 $M%:

    #.3 1C

    #2 .> 32

    ,C./#3E@ 22C

    ,A.1-#>E2 19>

    ,onclusion =hen m!0 $M% : e;en1 number of # in formula is e;en -he Nitrogen Rule =hen m!0 $M% : odd1 number of # in formula is odd

    21

    .ow Many #itrogen 6tomsI


    A Nitrogen Rule ./ample *+ample: Dormula choices from pre;ious mass spectrum M: m!0 : CA ,2.@E3 ,3.C,l discarded ,/.># ,@.@ m!0 e;en e;en nitrogen count e;en nitrogen count odd nitrogen count e;en nitrogen count

    22

    .ow Many .ydrogen 6tomsI


    Ene pi bond Two pi bonds

    .,

    ,@.1> max H for 6 C

    ,@.12 H count max ! 2

    ,@.1H count max ! "

    ,onclusion: *ach pi bond reduces ma+ hydrogen count by two

    23

    .ow Many .ydrogen 6tomsI


    Ene ring Two rings

    ,@.1> max H for 6 C

    ,@.12 H count max ! 2

    ,@.1H count max ! "

    ,onclusion: *ach ring reduces ma+ hydrogen count by two

    24

    .ow Many .ydrogen 6tomsI


    Ene nitrogen Two nitrogens
    #.2 #.2

    #.2 # . 3,

    ,.3 # # ,.3 ,.3

    ,@.1> max H for 6 C

    ,@.1/# H count max + #

    ,@.1@#2 H count max + 2

    ,onclusion: *ach nitrogen increases ma+ . count by one Dor , carbons and # nitrogens1 ma+ number of . : 2, 5 # 5 2 -he ,ydrogen Rule

    25

    Mass Spectrum Dormula


    rocedure ,hem 1>, atoms: . , # E D S ,l ?r & M : molecular weight $lowest mass isotopes% M51: gi;es carbon count M52: presence of S1 ,l1 or ?r #o mass spec indicator for D1 & $ssume a%sent unless otherwise specifie& 6ccounts for all atoms e+cept E1 #1 and . M= ) mass due to ,1 S1 ,l1 ?r1 D1 and & : mass due to E1 #1 and . Systematically ;ary E and # to get formula candidates Trim candidate list with nitrogen rule and hydrogen rule

    26

    Mass Spectrum Dormula


    ./ample 0& m!0 Molecular ion 'elati;e abundance Li;en information 1-2 M 1--< ,onclusions Mass 'lowest isotopes( #)2 *ven num%er of nitrogens @89 ! 181 : @83 Six car%ons" + ", so no S, Cl, or Br -x.gen/

    1-3 1->

    M51 M52

    @89< -83A<

    "'ounding: @8-- to @833 : @H @83> to @8@@ : @ or CH @8@C to C8-- : C

    27

    Mass Spectrum Dormula


    ./ample 0& Mass $M% ) mass $,1 S1 ,l1 ?r1 D1 and &% : mass $#1 E1 and .% 1-2 ) ,@ : 1-2 ) $@ + 12% : 3- amu for #1 E1 and . E+ygens 1 2 #itrogens 2"
    "#itrogen ruleM

    3- ) E ) # : . 3- ) - ) - : 33- ) 1@ ) - : 1> 3- ) 32 ) - : )2 3- ) - ) 2A : 2

    Dormula ,@.3,@.1>E ,@.)2E2 ,@.2#2

    #otes iolates hydrogen rule 'easonable #ot possible 'easonable

    Ether data $functional groups from &'1 #M' integration1 etc8% further trims the list

    28

    Mass Spectrum Dormula


    ./ample 0' m!0 Molecular ion 'elati;e abundance 1/C M 1--< ,onclusions Mass 'lowest isotopes( #01 -&& num%er of nitrogens 9839 ! 181 : A8/ *ight or nine car%ons -ne Cl2 no S or Br

    1/A 1/9

    M51 M52

    9839< 3><

    29

    Mass Spectrum Dormula


    ./ample 0' Try eight carbons: M ) ,A ) ,l : 1/C ) $A + 12% ) 3/ : 2@ amu for E1 #1 and . E+ygens #itrogens 1"
    "#itrogen ruleM

    2@ ) E ) # : . 2@ ) - ) 1> : 12

    Dormula ,A.12,l#

    #otes 'easonable

    #ot enough amu a;ailable for one o+ygen!one nitrogen or no o+ygen!three nitrogens

    30

    Mass Spectrum Dormula


    ./ample 0' Try nine carbons: M ) ,9 ) ,l : 1/C ) $9 + 12% ) 3/ : 1> amu for E1 #1 and . E+ygens #itrogens 1"
    "#itrogen ruleM

    1> ) E ) # : . 1> ) - ) 1> : -

    Dormula ,9,l#

    #otes 'easonable

    #ot enough amu a;ailable for any other combination8

    31

    Dormula Structure
    What does the formula reveal about molecular structure? Dunctional groups 6bsent atoms may eliminate some functional groups *+ample: ,C.9# has no o+ygen)containing functional groups Pi bonds and rings 'ecall from pre;ious: one pi bond or one ring reduces ma+ . count by two *ach two . less than ma+ . count : double bond e4ui;alent $D?*% &f formula has less than full . count1 molecule must contain one pi bond or ring

    32

    1alculating D2. D?* may be calculated from molecular formula: h.&rogens an& halogens

    Dormula Structure
    nitrogens

    D?* : , ) . 5 # 5 1 2 2 car%ons Ene D?* : one ring or one pi bond Two D?* : two pi bonds1 two rings1 or one of each Dour D?* : possi%le ben0ene ring *+ample ,A.1-,l# D?* : , ) $.!2% 5 $#!2% 5 1 : A ) N$1-51%!2O 5 $1!2% 5 1 :> 3our pi %on&s an&/or ring 4ossi%le %en5ene ring

    33

    Dormula Structure
    1ommon Math .rrors "mall math errors can have devastating effects3 No calculators on exams 6;oid these common spectroscopy problem math errors: Di;ide by 181 di;ide by 18D?* cannot be a fraction D?* cannot be negati;e

    #e+t lecture: &nfrared spectroscopy part 1

    34

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