Answers to end-of-chapter questions

Chapter 29
Examiners tip
The Applications of chemistry section involves less knowledge to recall than the other sections of the syllabus, but it does contain ideas and skills that you must learn how to apply. Practise these questions, and the check-up questions in the text, until you are confident in applying ideas and skills. Questions 4, 5, 6 and 7 are good examples of this. You may not have encountered compounds B, C, D, and E before, and you are certainly not expected to recognise their mass spectra, or to be able to recall the answers to the questions here. But you should be able to use the ideas and skills that you have learned, in order to get the correct answers to the questions.

e anabolic steroids are non-polar compounds that are volatile; [1] the amounts present are small and gasliquid chromatography is very sensitive [1] f the compounds can be identified immediately by their fragmentation patterns; [1] compare results to database or there is no need for running standards in order to identify the unknowns [1] g they are large compounds with large relative molecular masses; [1] they have high boiling points and therefore are not volatile enough for separation using this method [1] Total = 21

1 a i due to CH3+ ii due to OH+ iii due to CH2OH+ iv due to CH3CO+ v due to CH3COCH2+ vi due to HOCH2CO+ b m/e = 74 2 a A = recorder response B = time of injection C = retention time b total area = (1 2 2 50) + (1 2 1 80) + (1 2 2 60) = 150 percentage of pentan-1-ol = 50 100% 150

[1] [1] [1] [1] [1] [1] [1] Total = 7 [1] [1] [1] [1] [1] [1] [1] [1] [1] [1] [1] [1] [1] [1] [1]

= 33.3% c the stationary phase is non-polar; the less polar compounds are adsorbed more strongly on the column and have longer retention times; octane has more electrons than pentane so stronger van der Waals forces between octane and column d i The order would be reversed/changed (and overall retention times would increase). ii The pentan-1-ol is the most polar molecule  and would be retained the longest.
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3 a The sample is spotted onto paper at the marked point and then placed in solvent 1 [1] and the chromatogram is run in solvent 1. [1] The paper is taken out and turned through 90 [1] and is then run again in solvent 2. [1] b C, D and E [1] A and G [1] c made visible by using ninhydrin spray [1] 2.7 d i Rf = = 0.75 [1] 3.6 0.9 ii Rf = = 0.225 [1] 4.0 e A and C [1] 3.0 f i Rf (X) = = 0.214 [1] 14.0 8.0  Rf (Y) = = 0.571 [1] 14.0 10.0  Rf (Z) = = 0.714 [1] 14.0 ii Mobile phase is solvent used; [1]  stationary phase is water between the cellulose fibres of the paper. [1]  The amino acids are partitioned between the stationary phase and the mobile phase. [1]  The more soluble the amino acid is in the mobile phase, the further up the paper it moves / the distance an amino acid moves up the paper depends on its relative solubility in the mobile and stationary phases. [1] Total = 17
Answers to end-of-chapter questions: Chapter 29

4 a Element Percentage Mass in 100g Number of moles Relative number of atoms

carbon 62.1 62.1 g 62.1 = 5.18 12.0 5.18 =3 1.73 [1] [1] [1] [1]

hydrogen 10.3 10.3 g 10.3 = 10.3 1.0 10.3 =6 1.73

oxygen 27.6 27.6 g 27.6 = 1.73 16.0 1.73 =1 1.73 [1]

empirical formula = C3H6O b molecular mass is 58 empirical formula mass = molecular mass, therefore the molecular formula = C3H6O c i H O H
H C H H H C H H C H C H C C H O propanal H propanone

b the m/e value for the penultimate peak on the mass spectrum = 106 [1] this is twice the empirical formula mass, so the molecular formula is C8H10 [1] c i H H H
H C H C H H H C HH H H C H

[1] ii
H H C H H C H H C H H C H H

H C

H C H

ii it is propanal [1] iii There are three peaks present in the 1 H NMR spectrum; [1]  propanone has only one type of proton [1]  and therefore it would have only one peak. [1] d this is the peak for the CH3 protons; [1] it is split into a triplet because of the two chemically different (non-equivalent) protons on the adjacent carbon (by applying the n + 1 rule in which n = 2) [1] Total = 12 5 a Element Percentage Mass in 100g Number of moles in 100g carbon 90.6 90.6 g 90.6 = 7.55 12.0 hydrogen 9.4 9.4 g 9.4 = 9.4 1.0 9.4 = 1.25 7.55 5 [1] [1]

H H [1 mark for each structure] [4]

[1]

 This is because when chlorinated by electrophilic aromatic substitution it forms only the following compound:
H H C H Cl H C H H

[1]

Relative 7.55 =1 number of 7.55 atoms Whole 4 numbers empirical formula = C4H5

 The other possible isomers form several different compounds. [1]  The 1H NMR spectrum shows two peaks as C has only two different types of proton; [1]  the other possible isomers have larger numbers of different types of proton. [1] d The peak at = 7 ppm [1] is the peak from the benzene ring protons; [1] the peak at = 2.3 ppm [1] corresponds to the CH3 protons. [1] Total = 17

Answers to end-of-chapter questions: Chapter 29

AS and A Level Chemistry Cambridge University Press

6 a

Element Percentage Mass in 100g Number of moles in 100g Relative number of atoms

carbon 77.8 77.8 g 77.8 = 6.48 12.0 6.48 =7 0.925 [1] [1]

hydrogen 7.41 7.41 g 7.41 = 7.41 1.0 7.41 =8 0.925

oxygen 14.8 14.8 g 14.8 = 0.925 16.0 0.925 =1 0.925

[1]

empirical formula = C7H8O b The m/e value for the molecular-ion peak is 108; this corresponds to the mass of the empirical formula, so molecular formula = empirical formula = C7H8O. c i H
H H C H H H C H H H C O H H C H O O H O H H C H H O

[1]

d There are three peaks because of the three chemically different types of proton in D: [1] the peak for five protons at = 7.3 ppm is caused by the five benzene protons; [1] the peak given by two protons at = 4.6 ppm is caused by the CH2 protons; [1] the peak at = 2.4 ppm is caused by the OH proton. [1] Total = 17

ii
H C H O

H [1 mark for each structure] [5]

 H iii The relative area of the peak at = 7.3 ppm is 5, so there are five protons on the benzene ring; therefore D cannot be a di-substituted compound.  The other mono-substituted compound has only two types of proton  but the 1H NMR spectrum of D has three peaks, corresponding to the three different types of proton in D.

[1]

[1] [1] [1]

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Answers to end-of-chapter questions: Chapter 29

7 a

Element Percentage Mass in 100g Number of moles in 100g

carbon 69.8 69.8 g 69.8 = 5.82 12.0

hydrogen 11.6 11.6 g 11.6 = 11.6 1.0 11.6 = 10 1.16 [1]

oxygen 18.6 18.6 g 18.6 = 1.16 16.0 1.16 =1 1.16

Relative number of atoms 5.82 =5 1.16 empirical formula = C5H10O

[1]

b The m/e value for the molecular-ion peak is 86 so its relative molecular mass is 86; [1] this is the same as the empirical formula mass, so the molecular formula is also C5H10O. [1] c H H H H H H H
H H H C H C H C H C H C O H C H H H C C H H H H H C H H C H H C C O C H
O H H C H H C H C H C H H C H H H H C H H H C C O H

C C H

C H H

C O

d It is an aldehyde, because of the positive result from the silver mirror test. e on the 1H NMR spectrum there is an absorption at = 9.5 ppm, characteristic of the aldehyde CHO proton; it has only two distinct peaks and therefore only two types of proton; therefore E must be
H H H H C H H C H H C C O C H

[1] [1] [1]

H H C H

H C H H

H C O H

O H C H H C

H C H

H C H

H C H H

H  [1] There is no splitting of the peaks because there are no adjacent carbons with chemically different protons on them. [1] Total = 16

C
C H H H H

[1 mark for each structure] [7]

Answers to end-of-chapter questions: Chapter 29

AS and A Level Chemistry Cambridge University Press