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SPECTROSCOPY - COMBINED TECHNIQUES

SPECTROSCOPY - COMBINED TECHNIQUES

Objectives:
Identify functional groups from IR spectra
Deduce formula mass from molecular ion peaks and parts of structures from fragmentation data

Use chemical, IR, MS and NMR data to deduce structures

Infra-red - The basics:
Different bonds in a molecule absorb IR and vibrate at different frequencies Infra-red spectra are complex due to the many different vibrations taking place in each molecule.

O-H in alcohol BUT… bonds such as O-H and C=O can be confirmed because they have peaks in identifiable parts of the spectrum.

INFRA RED SPECTRA .INTERPRETATION Vertical axis Horizontal axis Absorbance Frequency the stronger the absorbance the larger the peak wavenumber (waves per centimetre) / cm-1 .

FINGERPRINT REGION – the messy bit • organic molecules have a lot of C-C and C-H bonds within their structure • spectra obtained will have peaks in the 1400 cm-1 to 800 cm-1 range • this is referred to as the “fingerprint” region and unique to a molecule .

IR SPECTRUM OF A CARBONYL COMPOUND • carbonyl compounds show a sharp. strong absorption between 1700 and 1760 cm-1 • this is due to the presence of the C=O bond .

IR SPECTRUM OF AN ALCOHOL • alcohols show a broad absorption between 3200 and 3600 cm-1 • this is due to the presence of the O-H bond .

IR SPECTRUM OF A CARBOXYLIC ACID • • • • carboxylic acids show a VERY broad absorption between 2500 and 3300 cm-1 this is due to the presence of the O-H bond they also show a strong absorption around 1700 cm-1 this is due to the presence of the C=O bond .

chemical .g.IR SPECTRUM OF AN ESTER • esters show a strong absorption between 1750 cm-1 and 1730 cm-1 • this is due to the presence of the C=O bond .Note this gives a similar result to ketones/aldehydes so you may need to use other evidence e.

note the “double trough” – can be distinguished from O-H in an alcohol] .IR SPECTRUM OF AN AMINE • amines show an strong absorption between 3200 and 3500 cm-1 • this is due to the presence of the N-H bond [ .

FUNCTIONAL GROUP? 95 90 85 80 75 70 65 60 %T 55 50 45 40 35 30 25 20 15 10 4000 3500 3000 2500 2000 1500 1000 500 Wavenumbers (cm-1) Peak at 3300 cm-1 due to O-H in alcohols .

3200 cm-1 due to O-H in carboxylic acids Peak at 1700cm-1 due to C=O Possibly -COOH .FUNCTIONAL GROUP? 95 90 85 80 75 70 65 60 %T 55 50 45 40 35 30 25 20 15 10 4000 3500 3000 2500 2000 1500 1000 500 Wavenumbers (cm-1) Very broad peak at 2800.

aldehyde or ester .FUNCTIONAL GROUP? 95 90 85 80 75 70 65 60 %T 55 50 45 40 35 30 25 20 15 10 4000 3500 3000 2500 2000 1500 1000 500 Wavenumbers (cm-1) Peak at 1700cm-1 due to C=O Could be ketone.

the basics: Molecules are bombarded with electrons This causes positive ions to form of different mass as the molecule fragments These are detected and a spectrum results based on the ions’ masses (given as an m/z value) .Mass spectroscopy .

RE-ARRANGEMENT FRAGMENTION . The rest of the spectrum provides information about the structure. The final peak (M+) shows the molecular ion (highest m/z value) and indicates the molecular mass.When a molecule is ionised it forms a MOLECULAR ION IONISATION MOLECULAR ION FRAGMENTION The molecular ion can fragment to produce particles of smaller mass.

58 • Other peaks due to molecular ion breaking into fragments 70 80 90 100 110 10 20 30 40 50 m/z 60 .butane C4H10  [C4H10]+. + e– m/z 58 CH3CH2CH2CH3 [CH3CH2CH2]+ 43 [C4H10]+.  [CH3CH2CH2]+ + .CH3 m/z 43 [C4H10]+.CH2CH3 m/z 29 • Peak with greatest m/z value = MOLECULAR ION [CH3CH2]+ 29 [C4H10]+.  [CH3CH2]+ + .

.Using the m/z value of the molecular ion The m/z value of the M+ ion = formula mass of the molecule For example…. .

a signal occurs at 114 due to the species C8H18+ The species due to the final signal is known as the molecular ion and gives the molecular mass of the compound Abundance % 60 80 100 40 molecular ion 114 20 0 .THE MASS SPECTRUM . 10 20 30 40 50 60 70 80 90 100 110 120 130 140 m/z .THE MOLECULAR ION In the spectrum of octane.

butanone CH3CH2COCH3 43 Mr = 72 29 72 57 10 20 30 40 50 m/z 60 70 80 90 100 110 .

methyl butanoate CH3CH2CH2COOCH3 43 Mr = 102 71 59 29 87 102 10 20 30 40 50 m/z 60 70 80 90 100 110 .

Using the m/z value of the molecular ion The m/z value of the molecular ion is useful for finding the molecular formula given empirical formulae data e.g. A compound has empirical formula of C2H4O The parent ion has an m/z value of 88 What is its molecular formula? Answer: C4H8O2 .

28 for CO). Peaks appear due to characteristic fragments (e. 100 43 Abundance % 60 80 29 57 71 85 114 20 40 0 . 10 20 30 40 50 60 70 80 90 100 110 120 130 140 m/z . 29 due to C2H5+) and differences between two peaks also indicates the loss of certain units (18 for H2O.THE MASS SPECTRUM .g.FRAGMENTATION The rest of the spectrum provides additional information of the molecule’s structure.

e. m/z 15 CH3+ 29 C2H5+ 43 C3H7+ 57 C4H9+ 71 C5H11+ 85 C6H13+ etc.FRAGMENTATION PATTERNS ALKANES The mass spectra of simple hydrocarbons have peaks at m/z values corresponding to the ions produced by breaking C-C bonds... more branches = greater stability) . Peaks can occur at . • the more stable the ion the higher the peak • the more alkyl groups attached to the ion the more stable it is (i.

CH2CH3 m/z 29 [CH3CH2]+ 29 [C4H10]+.  [CH3CH2CH2]+ + .butane C4H10  [C4H10]+. 58 10 20 30 40 50 m/z 60 70 80 90 100 110 .  [CH3CH2]+ + .CH3 m/z 43 [C4H10]+. + e– m/z 58 CH3CH2CH2CH3 [CH3CH2CH2]+ 43 [C4H10]+.

it will produce an m/z drop of 28 somewhere in the spectrum the more stable the acylium ion RCO+. A common fragment is carbon monoxide (CO) .FRAGMENTATION PATTERNS ALDEHYDES AND KETONES Breaking of bonds next to the carbonyl group (C=O) is a typical fragmentation of aldehydes and ketones. the taller its peak in the mass spectrum .

FRAGMENTATION PATTERNS Aldehydes and ketones The position of the carbonyl group influences the fragmentation pattern because the molecular ion fragments either side of the carbonyl group. O CH3 C •+ C4H9 MOLECULAR ION has m/z = 100 .

FRAGMENTATION PATTERNS Aldehydes and ketones The position of the carbonyl group influences the fragmentation pattern because the molecular ion fragments either side of the carbonyl group. Two peaks at m/z values 15 and 85 will appear in the mass spectrum. O CH3 C O C4H9 C+ m/z = 85 •+ C4H9 MOLECULAR ION has m/z = 100 CH3• Breaking the bond between the methyl group and the carbonyl group produces two possible ions. O C4H9 C• CH3+ m/z = 15 . depending on how the bond breaks.

FRAGMENTATION PATTERNS Aldehydes and ketones The position of the carbonyl group influences the fragmentation pattern because the molecular ion fragments either side of the carbonyl group. O CH3 C •+ C4H9 MOLECULAR ION has m/z = 100 O Breaking the bond between the butyl group and the carbonyl group produces two further ions. Two peaks at m/z values 43 and 57 will appear in the mass spectrum. CH3 C+ m/z = 43 C4H9• O CH3 C• C4H9+ m/z = 57 . depending on how the bond breaks.

FRAGMENTATION PATTERNS Aldehydes and ketones The position of the carbonyl group influences the fragmentation pattern because the molecular ion fragments either side of the carbonyl group. O CH3 C •+ C4H9 MOLECULAR ION has m/z = 100 O C4H9 C+ m/z = 85 O CH3• CH3 C+ m/z = 43 C4H9• O O CH3+ m/z = 15 C4H9 C• CH3 C• C4H9+ m/z = 57 A further peak occurs at m/z = 72 (100-28) due to loss of CO . Example.

butanone CH3CH2COCH3 43 29 72 57 10 20 30 40 50 m/z 60 70 80 90 100 110 .

Abundance % 80 100 105 77 51 120 43 40 60 20 28 0 m/z 10 20 30 40 50 60 70 80 90 100 110 120 130 140 C6H5COCH3 .

methyl butanoate CH3CH2CH2COOCH3 43 71 59 29 87 102 10 20 30 40 50 m/z 60 70 80 90 100 110 .

methyl butanoate CH3CH2CH2COOCH3 Which peaks would be absent if this was ethyl propanoate? 43 71 59 29 87 102 10 20 30 40 50 m/z 60 70 80 90 100 110 .

COMBINED TECHNIQUES Use I.R to find functional groups Use MS to find molecular formula with empirical formula data and clues about carbon skeleton Use C13 NMR for information on number and types of carbon environments Use proton NMR for information about numbers and types of proton and the environments they are in .