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Background
Mass spectrometry (Mass Spec or MS) uses high energy electrons to break a molecule into fragments. Separation and analysis of the fragments provides information about: Molecular weight Structure
Background
The impact of a stream of high energy electrons causes the molecule to lose an electron forming a radical cation. A species with a positive charge and one unpaired electron
H H C H H + e
-
H H C H H
+ 2e
Background
The impact of the stream of high energy electrons can also break the molecule or the radical cation into fragments.
H H H H H H H C C H H H + e
-
H C C H
m/z = 15
H C H
Background
Molecular ion (parent ion): The radical cation corresponding to the mass of the original molecule
H H C H H
H H H C C H H H
The molecular ion is usually the highest mass in the spectrum Some exceptions w/specific isotopes Some molecular ion peaks are absent.
Background
Mass spectrum of ethanol (MW = 46)
M+
SDBSWeb : http://riodb01.ibase.aist.go.jp/sdbs/ (National Institute of Advanced Industrial Science and Technology, 11/1/09)
Background
The cations that are formed are separated by magnetic deflection.
Background
Only cations are detected. Radicals are invisible in MS. The amount of deflection observed depends on the mass to charge ratio (m/z). Most cations formed have a charge of +1 so the amount of deflection observed is usually dependent on the mass of the ion.
Background
The resulting mass spectrum is a graph of the mass of each cation vs. its relative abundance. The peaks are assigned an abundance as a percentage of the base peak. the most intense peak in the spectrum The base peak is not necessarily the same as the parent ion peak.
Background
The mass spectrum of ethanol
base peak
M+
SDBSWeb : http://riodb01.ibase.aist.go.jp/sdbs/ (National Institute of Advanced Industrial Science and Technology, 11/1/09)
Background
Most elements occur naturally as a mixture of isotopes. The presence of significant amounts of heavier isotopes leads to small peaks that have masses that are higher than the parent ion peak. M+1 = a peak that is one mass unit higher than M+ M+2 = a peak that is two mass units higher than M+
Isotopes: present in their usual abundance. Hydrocarbons contain 1.1% C-13, so there will be a small M+1 peak. If Br is present, M+2 is equal to M+. If Cl is present, M+2 is one-third of M+. If iodine is present, peak at 127, large gap. If N is present, M+ will be an odd number. If S is present, M+2 will be 4% of M+. =>
SDBSWeb : http://riodb01.ibase.aist.go.jp/sdbs/ (National Institute of Advanced Industrial Science and Technology, 11/2/09)
2-bromopropane
M+ ~ M+2
SDBSWeb : http://riodb01.ibase.aist.go.jp/sdbs/ (National Institute of Advanced Industrial Science and Technology, 11/1/09)
M+ M+2
SDBSWeb : http://riodb01.ibase.aist.go.jp/sdbs/ (National Institute of Advanced Industrial Science and Technology, 11/2/09)
SDBSWeb : http://riodb01.ibase.aist.go.jp/sdbs/ (National Institute of Advanced Industrial Science and Technology, 11/1/09)
ICH2CN
I+
SDBSWeb : http://riodb01.ibase.aist.go.jp/sdbs/ (National Institute of Advanced Industrial Science and Technology, 11/2/09)
Fragmentation Patterns
The impact of the stream of high energy electrons often breaks the molecule into fragments, commonly a cation and a radical. Bonds break to give the most stable cation. Stability of the radical is less important.
Fragmentation Patterns
Alkanes Fragmentation often alkyl groups: Loss of methyl Loss of ethyl Loss of propyl Loss of butyl
Fragmentation Patterns
Mass spectrum of 2-methylpentane
Fragmentation Patterns
Alkenes: Fragmentation typically forms resonance stabilized allylic carbocations
Fragmentation Patterns
Aromatics: Fragment at the benzylic carbon, forming a resonance stabilized benzylic carbocation (which rearranges to the tropylium ion)
H H C Br H H C
H H C or
M+
Fragmentation Patterns
Aromatics may also have a peak at m/z = 77 for the benzene ring.
NO2 77
77
M+ = 123
Fragmentation Patterns
Alcohols
Fragment easily resulting in very small or missing parent ion peak May lose hydroxyl radical or water M+ - 17 or M+ - 18 Commonly lose an alkyl group attached to the carbinol carbon forming an oxonium ion. 1o alcohol usually has prominent peak at m/z = 31 corresponding to H2C=OH+
Fragmentation Patterns
MS for 1-propanol
CH3CH2CH2OH
H2C OH
M+-18
M+
SDBSWeb : http://riodb01.ibase.aist.go.jp/sdbs/ (National Institute of Advanced Industrial Science and Technology, 11/28/09)
Fragmentation Patterns
Amines Odd M+ (assuming an odd number of nitrogens are present) a-cleavage dominates forming an iminium ion
CH3CH2 CH2 N CH2 H CH2CH2CH3 CH3CH2CH2N CH2 H m/z =72
iminium ion
Fragmentation Patterns
86 CH3CH2 CH2 N CH2 H 72 CH2CH2CH3
Fragmentation Patterns
Ethers a-cleavage forming oxonium ion
Fragmentation Patterns
MS of diethylether (CH3CH2OCH2CH3)
H O CH2
H O CHCH3
CH3CH2O CH2
Fragmentation Patterns
Aldehydes (RCHO) Fragmentation may form acylium ion
RC O
Common fragments:
M+ - 1 for RC O M+ - 29 for R
(i.e. RCHO - CHO)
Fragmentation Patterns
MS for hydrocinnamaldehyde
105 H H O C C C H H H 133 91
91
M+ = 134
105
SDBSWeb : http://riodb01.ibase.aist.go.jp/sdbs/ (National Institute of Advanced Industrial Science and Technology, 11/28/09)
Fragmentation Patterns
O
Ketones RCR' Fragmentation leads to formation of acylium ion:
Loss of R forming R'C O Loss of R forming RC O
Fragmentation Patterns
MS for 2-pentanone
CH3C O
O CH3CCH2CH2CH3
CH3CH2CH2C O
M+
SDBSWeb : http://riodb01.ibase.aist.go.jp/sdbs/ (National Institute of Advanced Industrial Science and Technology, 11/28/09)
Fragmentation Patterns
Esters (RCO2R) Common fragmentation patterns include: Loss of OR peak at M+ - OR Loss of R peak at M+ - R
Frgamentation Patterns
77 O C O CH3 105
105
77 M+ = 136
SDBSWeb : http://riodb01.ibase.aist.go.jp/sdbs/ (National Institute of Advanced Industrial Science and Technology, 11/28/09)
Rule of Thirteen
The Rule of Thirteen can be used to identify possible molecular formulas for an unknown hydrocarbon, CnHm. Step 1: n = M+/13 (integer only, use remainder in step 2) Step 2: m = n + remainder from step 1
Rule of Thirteen
Example: The formula for a hydrocarbon with M+ =106 can be found: Step 1: n = 106/13 = 8 (R = 2) Step 2: m = 8 + 2 = 10 Formula: C8H10
Rule of Thirteen
Example: A compound with a molecular ion peak at m/z = 102 has a strong peak at 1739 cm-1 in its IR spectrum. Determine its molecular formula.
Spesies elektron genap lebih suka pecah menjadi ion lain dan molekul netral A+ B .+ + C . Genap genap genap
Ion radikal yaitu spesies elektron ganjil, dapat melepaskan molekul netral dan ion radikal sebagai hasil ikutan.
A .+ ganjil B .+ + C . ganjil genap
Ion radikal dapat pecah menjadi radikal dan ion A .+ B+ . + C+ Genap ganjil Atau A + B .+ C+ ganjil genap
Suatu senyawa yang hanya mengandung C,H, O memiliki berat molekul genap, atau jika senyawa tersebut mengandung atom nitrogen maka jumlah atom nitrogen haruslah genap. Sedangkan jika senyawa hanya mengandung C,H,N,O mempunyai berat molekul ganjil jika jumlah atom nitrogennya ganjil. Jika senyawa yang mengandung C,H,O kehilangan fragmen radikal (CH3, OCH3 dan yang lainnya) maka akan menghasilkan ion fragmen ganjil, tetapi yang dilepaskan molekul netral (H2O, HCN, olefin dan yang lainnya), maka ion fragmen yang dihasilkan adalah genap.
5. Adanya ikatan rangkap dua mendukung pemecahan alil dan memberikan karbokation alilik terstabilkan resonansi. Aturan ini tidak pada alkalena sederhana disebabkan mudahnya migrasi ikatan rangkap dua tetapi terjadi pada sikloalkana.
6.
Cincin jenuh cenderung melepaskan rantai samping alkil pada ikatan-. Muatan positif cenderung bertahan pada fragmen cincin.
9. Pelepasan sering diikuti dengan penghilangan molekul kecil yang netral seperti karbon monoksida, olefin, air, amonia, hidrogen sulfida, hidrogen sianida, merkaptan, ketena atau alkohol, juga sering diikuti dengan penataan ulang.
Agar berlangsungnya penataan ulang Mclafferty suatu molekul harus memiliki heteroatom yang terletak tertentu, sistem- (biasanya ikatan rangkap) dan atom hidrogen yang terletak terhadap sistem c=0. Penataan ulang menyebabkan menonjolnya puncak yang khas.