F322 Modern Analytical Techniques

Instrumental methods of Chemical Analysis

Candidates should be able to: (a) state that absorption of infrared radiation causes covalent bonds to vibrate; (b) identify, using an infrared spectrum of an organic compound: (i) an alcohol from an absorption peak of the OH bond, (ii) an aldehyde or ketone from an absorption peak of the C=O bond, (iii) a carboxylic acid from an absorption peak of the C=O bond and a broad absorption peak of the OH bond; (c) state that modern breathalysers measure ethanol in the breath by analysis using infrared spectroscopy; (d) outline the use of mass spectrometry: (i) in the determination of relative isotopic masses, (ii) as a method for identifying elements, ie use in the Mars space probe and in monitoring levels of environmental pollution, such as lead; (e) interpret mass spectra of elements in terms of isotopic abundances; (f) use the molecular ion peak in a mass spectrum of an organic molecule to determine its molecular mass; (g) suggest the identity of the major fragment ions, ie m/z = 29 as CH3CH2+, in a given mass spectrum (limited to alkanes, alkenes and alcohols); (h) use molecular ion peaks and fragmentation peaks to identify structures (limited to unipositive ions); (i) explain that a mass spectrum is essentially a fingerprint for the molecule that can be identified by computer using a spectral database.

Infrared Spectroscopy
Used to identify rapidly and non-destructively the bonds present in a compound. This allows the functional groups to be identified. Principle: The absorption of infrared radiation causes bonds to vibrate. Depending on the masses of the bonded atoms, different frequencies of radiation are absorbed. Each specific bond has a characteristic frequency at which it absorbs infrared radiation. The infrared spectrum is therefore a plot of absorbance (y-axis) vs. frequency of the infrared absorbed. Chemists use the units WAVENUMBERS (cm-1) for this axis. This is the number of wavelengths per centimetre, so high wavenumbers correspond to high frequencies of vibration.

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F322 Modern Analytical Techniques Characteristic infrared absorptions: O-H in alcohols 3230 3550 cm-1 O-H in carboxylic acids 2500 3300 cm-1

strong and broad (due to H-bonding) strong and broad (due to H-bonding)

Note: These should not be confused with the sharp strong absorptions around 2900 3100cm-1 due to C-H vibrations. C=O in ketones, aldehydes, esters, carboxylic acids 1680 1750cm-1 strong

Note: The region from 1500cm-1 to 500cm-1 (the fingerprint region) contains a wealth of fine detail and is difficult to interpret other than by using a spectral matching database. C-O (in alcohols, esters and carboxylic acids) is often found as a medium-strong sharp absorption between 1000cm-1 and 1300cm-1, but beware as there are other bonds which absorb in this region too, so this can only be a "possibly C-O" assignment. N.B. Datasheets in the exam give these wavenumbers, so they don't need to be learned, but you must be able to use them correctly ! Applications: We can tell apart isomers with different functional groups e.g. CH3OCH3 (methyl methoxide) from CH3CH2OH (ethanol) We can tell determine whether the oxidation products of an alcohol are a aldehyde/ketone or a carboxylic acid, and hence whether it is a primary or secondary alcohol, or indeed if it was oxidised at all.

Industrial Uses: Modern breathalysers use IR to measure the alcohol content in breath, and the analysers used to measure the level of CO in car exhaust emissions (for the MOT test) use infrared sensors. Industries such as the pharmaceutical industry use infrared spectroscopy along with a variety of other techniques for product and raw material quality control. Interpreting an infrared spectrum Using the data sheet provided in the exam, identify the main absorptions present in the spectrum and label which bonds they represent. Also note where significant absorptions such as O-H are *not* present. Then use the information to help sort out what functional group(s) are present in the molecule, given the context information in the question

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F322 Modern Analytical Techniques Example: The infrared spectrum shows what was produced when butanol was oxidised by refluxing with excess aciified potassium dichromate. Identify the product, and hence decide whether the butanol was butan-1-ol or butan-2-ol.

no O-H absorptions

C-H

C=O

Interpretation: Having identified that there is C=O present, but not O-H the product is either an aldehyde or a ketone, but not a carboxylic acid. Butanal could be produced by oxidising butan-1-ol, but the conditions for this are wrong - heat, reflux and an excess of the oxidising agent indicate that any butanal formed would be further oxidised to butanoic acid. Butanone could be produced by oxidising butan-2-ol, and would not oxidise further, so it is likely that this is the product shown, and that the alcohol was BUTAN-2-OL. Check your understanding: i) Identify the main bonds which cause the labelled absorptions in the following infrared spectrum:

A B

ii) Decide whether this molecule is i) an alcohol; ii) a carboxylic acid or iii) a ketone, giving reasons.

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F322 Modern Analytical Techniques

Mass Spectrometry
Used to identify the mass of atoms and groups of atoms present in compounds and mixtures. High resolution mass spectroscopy can measure masses sufficiently accurately to identify the different isotopes of atoms present. Principle: The gaseous sample is smashed into individual atoms and groups of atoms (fragments) by a high energy electron beam which also removes an electron to leave each atom or fragment positively charged. These positively charged ions are accelerated in an electric field, then deflected by a magnetic field at right-angles to their flight path. The lighter they are, the more they are deflected, so the mass spectrometer separates the ions on the basis of their mass. A detector is then used to measure the relative abundance of ions of each different mass. Units: The x-axis is labelled m/z, (or m/e) which means mass/charge. The ions all have +1 charge, so this is effectively a mass axis. The mass spectrometer is calibrated so that the carbon-12 isotope is given an m/z of exactly 12, so the mass spectrometer measures the relative isotopic/formula mass of the ions it detects. The y-axis is relative abundance, showing the proportion of the ions which have each different mass. Applications 1- determining relative isotopic masses The mass spectrum of an element contains one line for each isotope. We can use the results to work out the relative abundance of each isotope, or to work out the relative atomic mass of the element (the average mass of an atom over all the naturally-occuring isotopes, on the scale where 12C weighs 12.) 20 Ne = 90% 22 Ne = 10%

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F322 Modern Analytical Techniques The method for working out Ar values is: Isotope 20 Ne 22 Ne relative abundance mass x relative abundance 0.9 20 x 0.90 = 18.0 0.1 22 x 0.10 = 2.2 Ar = 20.2 1. divide %abundance by 100 to get relative abundance 2. multiply each relative abundance by the mass of that isotope 3. add the results of these multiplications to get the relative atomic mass % abundance 90.0 10.0

2 determining elements present in an unknown substance Having split the sample up into its component atoms and removed an electron from each atom to form positive ions, the mass of each ion shows the atoms present in a sample, and the relative amounts of each. Lightweight miniature spectrometers have been used e.g. in the Mars space probe to analyse rock/soil samples, and are used to monitor environmental pollutants e.g. Pb in the atmosphere, or in drinking water. 3- determining the structure of organic compounds based on their fragments Splitting an organic molecule into fragments allows the structure to be worked out by identifying which atoms are bonded to each other in each fragment. The masses of each fragment are characteristic: e.g. CH3+ m/z = 15 (CH3)2CH+ m/z = 43 + CH3CH2 m/z = 29 OH+ m/z = 17 + + CH3CH2CH2 m/z = 43 CH2OH m/z = 31 The peak furthest to the right (at highest m/z) is usually not the strongest peak, but always corresponds to the unfragmented molecule, with one electron removed to make it an ion. This is called the molecular ion peak, and tells you Mr for the molecule. N.B. You may well see a VERY SMALL peak at m/z = Mr+ 1. This is due to the fact that carbon-13 is present in all natural organic materials at about 1.1% abundance. Do not mistake this for the molecular ion peak ! The peaks all taken together constitute a fingerprint for the molecule, and are usually matched to mass spectral databases using a computer. This technique is used e.g. for identifying traces of drugs or explosives in forensics and security work. Check your understanding: iii) Suggest identities for the fragments giving rise to the following peaks in this mass spectrum of butanone m/e = 15 m/e = 29 m/e = 43 m/e = 57 m/e = 72

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F322 Modern Analytical Techniques

Answers to Check your Understanding questions:

i) Identify the main bonds which cause the labelled absorptions in the following infrared spectrum: A - strong broad absorption at 3100cm-1 is O-H in an carboxylic acid (if it were O-H in an alcohol it would be at higher wavenumbers) B strong sharp absorption at 1720cm-1 is C=O C the medium absorption at 1300cm-1 may possibly be a C-O ii) Decide whether this molecule is i) an alcohol; ii) a carboxylic acid or iii) a ketone, giving reasons.
O

The evidence suggests a carboxylic acid functional group:

C O H

iii) Suggest identities for the fragments giving rise to the following peaks in this mass spectrum of butanone. m/e = 15 m/e = 29 m/e = 43 m/e = 57 m/e = 72 this is likely to be CH3+ this is likely to be CH3CH2+ this is likely to be CH3CO+ (since butanone doesn't have CH3CH2CH2- in it) this is likely to be CH3CH2CO+ this is the molecular ion CH3CH2COCH3+

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