Answers 9 Spectroscopy and chromatography

Answers to Topic 9 Test yourself questions

1 Cl + Cl This is the first (initiation) step that produces the free radicals that start the chain reaction when chlorine reacts with an alkane. 2

3 The energy of microwave radiation is absorbed directly by the molecules in the reaction mixture. Unlike heating with a flame or electric mantle, microwave heating means that all the energy heats up the chemicals and none is wasted warming the apparatus and the surroundings. 4 The nucleus of a 1H atom is simply a proton. 5 a) atoms. b) In methyl ethanoate, CH3COOCH3, there are two different chemical environments for hydrogen The peak just above 2 is due to H3C CO , while the peak at 3.7 is due to O CH3

c) Both chemical environments have three H atoms so the step size in the integration trace is the same for both peaks giving a ratio of 1 : 1 a) There are two distinct chemical environments. b) The ratio is about 9 : 1 c) The peak at 8.4 is close to the range for CHO. The peak close to 1.0 is in the range for R CH3. Three methyl groups contain nine hydrogen atoms and these all have to be in the same chemical environment. A possible structure is (CH3)3CCHO. d) Any two of these tests: add a solution of 2,4-dinitrophenylhrazine formation of a bright orange precipitate confirms the presence of a carbonyl group. add fresh Tollens reagent and warm a silver mirror confirms the presence of an aldehyde group

add fresh Fehlings reagent and warm an orange-red precipitate confirms the presence of an aldehyde
7 group. a)

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Answers 9 Spectroscopy and chromatography

b)

8 First way: all three aligned with the field (one possibility). Second way: two aligned with the field and one against (three possibilities with three protons). Third way: one aligned with the field and two against (three possibilities with three protons). Fourth way: all three aligned against the field (one possibility). 9 C6H5CH2CH3. Five hydrogen atoms at a shift of just over 7 suggest the five hydrogen atoms of a benzene ring with one substituent. There are two hydrogen atoms with a chemical shift corresponding to hydrogen atoms bonded to a carbon atom which is attached to a benzene ring. There are three hydrogen atoms which might be part of a methyl group.

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Answers 9 Spectroscopy and chromatography

10 a)

b)

11 CH3CH2OH + D2O

CH3CH2OD + HDO

12 If there is a trace of water present, the labile hydrogen on the OH group do not couple with other protons to produce any splitting. So the OH peak at 2.6 is a singlet. The group of peaks with a chemical shift of 3.7 is due to the CH2 group. The three hydrogen atoms on the adjacent CH3 group split this into a quartet. The triplet with a chemical shift of 1.2 arises from the CH3 group being split by coupling with the adjacent CH2 group. 13 There are three hydrogen atoms with a chemical shift value consistent with RCH3. The peak is a triplet so these hydrogens are next to a carbon atom with two hydrogen atoms. There are two hydrogen atoms with a chemical shift consistent with CH2 next to COOH. The peak is a quartet and so these hydrogen atoms are next to a carbon atom with four hydrogen atoms. There is one hydrogen atom attached to oxygen in a carboxylic acid group that is not split by hydrogens on the neighbouring carbon atom. CH3CH2COOH 14 The public is generally nervous of nuclear technologies because of the bad press associated with nuclear power. 15

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Answers 9 Spectroscopy and chromatography

16 m/e = 136: the parent ion [C6H5COOCH3]+ m/e = 105: [C6H5CO]+ m/e = 77: [C6H5]+ m/e = 51: [C4H3]+ this is one of the characteristic fragments from phenyl groups. 17 a) Chlorine consists of two isotopes: chlorine-35 and chlorine-37, with abundances in the ratio 3:1. In a molecular ion of C2H2Cl2 with two chlorine atoms the possibilities are: most likely two atoms of chlorine-35 (96); next one of chlorine-35 and one of chlorine-37 (98); and least likely two atoms of chlorine37 (100). The adjacent peaks differ by two mass units and the expected ratio is 9 : 6 : 1 b) These two peaks are fragments formed by the loss of one chlorine atom leaving a single chlorine atom in the fragment, so the ratio of abundances corresponds to the ratio of the abundance of the isotopes. 18 Left spectrum: chloroethane. Molecular ion peaks at 64 and 66 are in the ratio 3 : 1 suggesting that a single chlorine atom is present with chlorine-35 and chlorine-37 present in this ratio. The same ratio of peak heights is seen for CH2Cl+ at 49 and 51. The peak at 29 corresponds to C2H5+. Loss of further hydrogen atoms gives the peaks at 28, 27 and 26. Right spectrum: bromomethane. Peaks at 94 and 96 are the molecular ion peaks with two isotopes of bromine which occur which roughly equal abundance: bromine-79 and bromine-81. The peak at 15 is CH3+. The peaks at 79 and 81 correspond to the isotopic free bromine atoms. 19 a) Peak A: N H stretch; peaks B and C: C=O stretch b) Left spectrum: ethanamide; right spectrum: ethyl ethanoate 20 a) P: C6H5CHO; Q: C6H5COOH b) Benzaldehyde gives an orange precipitate with 2,4-dinitrophenylhydrazine. Benzoic acid is soluble in hot water to give an acidic solution which releases carbon dioxide when mixed with sodium carbonate. a) Powdered chalk b) 22 a) b) Hydrocarbon solvent Green Yellow

21

23 Two possibilities: measure the melting temperatures of solids

record IR spectra and compare with reference spectra.

24 Helium is a noble gas. It is very inert so there is no danger that it will react with the chemicals in the mixture being analysed. 25 a) There were 7 chemicals in the mixture. b) 60 seconds. Proportions of chemicals in the mixture are indicated by the areas under the peaks. If the peaks are narrow, the peak height can be taken as a measure of peak size. 26 The liquid of the stationary phase must not vaporise at the temperature of the column. The column is heated in an oven. 27 This means that it is not possible to identify compounds by the retention times, even if GC is carried out under carefully standardised conditions. 28 There is no data on the retention time of a new chemical when analysed by gas chromatography. This means

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Answers 9 Spectroscopy and chromatography

that GC cannot be used to identified a novel compound.

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