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Advanced Organic Chemistry: Mass spectrum of 1-bromobutane

Interpreting the mass spectrum of 1-bromobutane

Doc Brown's Chemistry Advanced Level Pre-University Chemistry Revision Study Notes for UK IB KS5 A/AS GCE advanced A level organic chemistry students US K12 grade 11 grade 12 organic chemistry courses involving molecular spectroscopy analysing mass spectra of 1-bromobutane

See also comparing infrared, mass, 1H NMR & 13C NMR spectra of 4 halogenoalkane isomers of C4H9Br

mass spectrum of 1-bromobutane C4H9Br CH3CH2CH2CH2Br fragmentation pattern of m/z m/e ions for analysis and identification of n-butyl iodide image diagram doc brown's advanced organic chemistry revision notes 

1-bromobutane, C4H9Br, CH3CH2CH2CH2Br, CH3-CH2-CH2-CH2-Br

Interpreting the fragmentation pattern of the mass spectrum of 1-bromobutane

[M]+ is the parent molecular ion peaks (M) with m/z values of 136 and 138 corresponding to [C4H9Br]+, the original 1-bromobutane molecule minus an electron, [CH3CH2CH2CH2Br]+.

There are two possibilities because bromine consists of two isotopes, 79Br and 81Br in the ratio ~1 : 1.

Therefore the molecular ion can be [CH3CH2CH2CH279Br]+ and [CH3CH2CH2CH281Br]+, which should, and does, show up as a double peak of ~equal heights (~equal abundance).

These are referred to as the M and M+2 peaks respectively, emphasising the two mass unit difference due to the bromine isotopes in the two molecular ions of 1-bromobutane.

The two bromine isotopes also account for the 'twin peaks' of m/z ions 93 & 95 and 107 & 109.

Bromine consists of two isotopes, 79Br and 81Br in roughly equal proportions, therefore any molecular ion or fragment containing a bromine atom will show up as a double peak of similar height (abundance) two mass units apart e.g. m/z ions 93 and 95, and 107 and 109, plus the molecular ion peaks of m/z values 136 and 138 (but still, all pairs of ~equal height!) in the mass spectrum of 1-bromobutane.

The very small small M+1 and M+3 peaks at m/z 137 and 139, corresponds to an ionised 1-bromobutane molecule with one 13C atom in it i.e. an ionised 1-bromobutane molecule of formula [13C12C3H9Br]+

Carbon-13 only accounts for ~1% of all carbon atoms (12C ~99%), but the more carbon atoms in the molecule, the greater the probability of observing this 13C M+1 peak.

1-bromobutane has 4 carbon atoms, so on average, ~1 in 25 molecules will contain a 13C atom.

The most abundant ion of the molecule under mass spectrometry investigation (1-bromobutane) is usually given an arbitrary abundance value of 100, called the base ion peak, and all other abundances ('intensities') are measured against it.

Identifying the species giving the most prominent peaks (apart from M) in the fragmentation pattern of 1-bromobutane.

Unless otherwise indicated, assume the carbon atoms in 1-bromobutane are the 12C isotope.

Some of the possible positive ions, [molecular fragment]+, formed in the mass spectrometry of 1-bromobutane.

The parent molecular ions of 1-bromobutane m/z 136: [C4H979Br]+  and  m/z 138  [C4H981Br]+

m/z value of [fragment]+ 138 136 109 107 95 93 58, with 13C atom 57, all 12C atoms
[molecular fragment]+ [C4H981Br]+ [C4H979Br]+ [C2H481Br]+ [C2H479Br]+ [CH281Br] [CH279Br] [C4H9]+ [C4H9]+
m/z value of [fragment]+ 56 55 79 80 81 82 m/z ions of 79 to 82 have a very low abundance, just tiny peaks in the mass spectrum of 1-bromobutane.
[molecular fragment]+ [C4H8]+ [C4H7]+ [79Br]+ [H79Br]+ [81Br]+ [H81Br]+
m/z value of [fragment]+ 43 42 41 40 39 29 28 27 26 15
[molecular fragment]+ [C3H7]+ [C3H6]+ [C3H5]+ [C3H2]+ [C3H3]+ [C2H5]+ [C2H4]+ [C2H3]+ [C2H2]+ [CH3]+

Analysing and explaining the principal ions in the fragmentation pattern of the mass spectrum of 1-bromobutane

Atomic masses: H = 1;  C = 12;  Br = 79 or 81 (1:1 isotope abundance ratio)

Bond enthalpies = kJ/mol: C-C = 348;  C-H = 412; C-Br 276

Possible equations to explain some of the most abundant ion peaks of 1-bromobutane (tabulated above)

Formation of m/z 107 and 109 ions:

[CH3CH2CH2CH2Br]+  ===>  [C2H4Br]+  +  C2H5

C-C bond scission in the parent molecular ion, mass change 136/138 - 29 = 107/109.

Note the twin ~1:1 peaks due to the two bromine isotopes.

The C-Br bond is the weakest bond in the molecule, hence the most likely bond scission is C-Br with 1-bromobutane (see below m/z 57 ion).

Formation of m/z 93 and 95 ions:

[CH3CH2CH2CH2Br]+  ===>  [CH2Br]+  +  C3H7

C-C bond scission in the parent molecular ion, mass change 136/138 - 43 = 93/95.

Note the twin ~1:1 peaks due to the two bromine isotopes.

The C-Br bond is the weakest bond in the molecule, hence the most likely bond scission is C-Br with 1-bromobutane (see below m/z 57 ion).

Formation of m/z 57 ion:

[CH3CH2CH2CH2Br]+  ===>  [C4H9]+  +  Br

This alternative ionisation compared to above is much more likely, C-Br bond (weakest) scission in the parent molecular ion, mass change 136/138 - 79/81 = 57.

The m/z 57 ion is the base peak ion, the most abundant and 'stable' ion fragment.

The m/z 58 ion is likely to be [13C12C3H9]+  i.e. as above but with a 13C atom in the hydrocarbon fragment.

The m/z 57 ion can lose a hydrogen atom/molecule to give m/z ions 56 and 55.

There is a low probability that the bromine atom can also be ionised to give m/z 79 and 81 ions - you can just about make out the tiny twin peaks.

Formation of m/z 56 ion:

[CH3CH2CH2CH2Br]+  ===>  [C4H8]+  +  HBr

Elimination of hydrogen bromide from the parent molecular ion can also give the m/z 56 ion.

Mass change 136/138 - 80/82 = 56.

There is a low probability that the hydrogen bromide molecule can also be ionised to give m/z 80 and 82 ions - you can just about make out the tiny twin peaks.

Formation of m/z 41 and 39 ions:

Possible reactions include:

m/z 41: [C4H8]+  ===>  [C3H5]+  +  CH3

m/z 39: [C3H5]+  ===>  [C3H3]+  +  H2

Formation of m/z 29, 28 and 27 ions:

Possible reactions include:

[CH3CH2CH2CH2Br]+  ===>  [C2H5]+  +  CH2CH2Br

From bond scission in the parent molecular ion.

m/z 27: [C4H8]+  ===>  [C2H3]+  +  C2H5

m/z 28: [C4H8]+  ===>  [C2H4]+  +  C2H4

m/z 29: [C4H8]+  ===>  [C2H5]+  +  C2H3

Comparing the infrared, mass, 1H NMR and 13C NMR spectra of the 4 halogenoalkane isomers of C4H9Br

NOTE: The images are linked to their original detailed spectral analysis pages AND can be doubled in size with touch screens to increase the definition to the original 1-bromobutane, 2-bromobutane, 1-bromo-2-methylpropane and 2-bromo-2-methylpropane image sizes.  These four molecules are structural isomers of molecular formula C4H9Br and exemplify the infrared, mass, 1H NMR and 13C NMR spectra of lower aliphatic halogenoalkanes (haloalkanes, alkyl halides, bromoalkanes, alkyl bromides).

INFRARED SPECTRA (above): Apart from the significant differences in the fingerprint region at wavenumbers 1500 to 400 cm-1, there are no other great striking differences, but each could be identified from its infrared spectrum.

MASS SPECTRA (above): All four give the parent molecular ions of m/z 136 and 138, but it is only a relatively tiny peak for 2-bromobutane and 2-bromo-2-methylpropane. All four give the base ion peak of m/z 57. All four give prominent peaks for m/z ions 27, 29, 39 and 41 and all give a tiny peak from an ionised iodine atom at m/z 127. They look quite similar to me and lack a clear fingerprint fragmentation pattern. There are small differences in the relative abundances (peak heights) for pairs of ions involving 79Br/81Br isotopes e.g. m/z 93/95, 107/109 and 121/123. 1-bromo-2-methylpropane is the only one of the four to have a prominent peak for the m/z 43 ion.

1H NMR SPECTRA (above): The 1H NMR spectra of all four molecules give different integrated proton ratios i.e.1-bromobutane four peaks of ratio 3:2:2:2; 2-bromobutane four peaks of ratio 3:3:2:1, 1-bromo-2-methylpropane three peaks of ratio 6:2:1 and 2-bromo-2-methylpropane gives just one peak '1' (effectively no ratio involved), so all four molecular structures can be distinguished from each other by their 1H NMR spectra proton ratios, numbers of peaks and (n+1) rule splitting patterns.

13C NMR SPECTRA (above): The 13C NMR spectra of the four molecules show various numbers of carbon-13 chemical environments i.e 1-bromobutane and 2-bromobutane show four 13C NMR resonances, 1-bromo-2-methylpropane three 13C NMR resonances and 2-bromo-2-methylpropane only two 13C resonances. Therefore 1-bromo-2-methylpropane and 2-bromo-2-methylpropane can be distinguished from the other three by their number of resonances in their 13C NMR spectra, but 1-bromobutane and 2-bromobutane cannot be distinguished from each other from their number of 13C NMR resonance lines - other data would be required.

Key words & phrases: C4H9Br CH3CH2CH2CH2Br image diagram on how to interpret and explain the mass spectrum of 1-bromobutane m/z m/e base peaks, image and diagram of the mass spectrum of 1-bromobutane, details of the mass spectroscopy of 1-bromobutane,  low and high resolution mass spectrum of 1-bromobutane, prominent m/z peaks in the mass spectrum of 1-bromobutane, comparative mass spectra of 1-bromobutane, the molecular ion peak in the mass spectrum of 1-bromobutane, analysing and understanding the fragmentation pattern of the mass spectrum of 1-bromobutane, characteristic pattern of peaks in the mass spectrum of 1-bromobutane, relative abundance of mass ion peaks in the mass spectrum of 1-bromobutane, revising the mass spectrum of 1-bromobutane, revision of mass spectroscopy of 1-bromobutane, most abundant ions in the mass spectrum of 1-bromobutane, how to construct the mass spectrum diagram for abundance of fragmentation ions in the mass spectrum of 1-bromobutane, how to analyse the mass spectrum of 1-bromobutane, how to describe explain the formation of fragmented ions in the mass spectra of 1-bromobutane equations for explaining the formation of the positive ions in the fragmentation of the ionised molecule of 1-bromobutane recognising the base ion peak of 1-bromobutane interpreting interpretation the mass spectrum of 1-bromobutane  n-butyl iodide alkyl halide functional group haloalkane halogenoalkane bromoalkane

Stick diagram of the relative abundance of ionised fragments in the fingerprint pattern of the mass spectrum of 1-bromobutane (n-butyl bromide). Table of the m/e m/z values and formula of the ionised fragments in the mass spectrum of 1-bromobutane (n-butyl bromide). The m/e m/z value of the molecular ion peak in the mass spectrum of 1-bromobutane (n-butyl bromide).  The m/e m/z value of the base ion peak in the mass spectrum of 1-bromobutane (n-butyl bromide). Possible examples of equations showing the formation of the ionised fragments in 1-bromobutane (n-butyl bromide). Revision notes on the mass spectrum of 1-bromobutane (n-butyl bromide). Matching and deducing the structure of the 1-bromobutane (n-butyl bromide) molecule from its mass spectrum.


Links associated with 1-bromobutane

The chemistry of HALOGENOALKANES (haloalkanes) revision notes INDEX

The infrared spectrum of 1-bromobutane (n-butyl bromide)

The H-1 NMR spectrum of 1-bromobutane (n-butyl bromide)

The C-13 NMR spectrum of 1-bromobutane (n-butyl bromide)

Mass spectroscopy index

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