Tutorial 5

1) Chromatography is a versatile technique that may be used to

separate and identify compounds.
(i) Name a type of chromatography that is used to separate and identify
dissolved substances.

Accept paper, column or thin-layer chromatography

(ii) State what quantitative value may be determined from the

chromatogram to identify the substances present in the solution.

The Rf value

(iii) Sketch a chromatogram to show how the value in (ii) is determined.

2) (a) Gas-liquid chromatography is used to separate and identify

gases and liquids.
(i) State what quantitative value is normally used to identify the components
in this type of chromatography.

Retention time

(ii) Sketch the chromatogram to show how the value in (i) is determined.

(b) State the physical process on which the separation used in gas-liquid
chromatography depends.

Partition

3) A mixture of tripeptides can be analysed by using gas

chromatography, coupled with mass spectrometry.
Summarise how each method contributes to the analysis.

gas/liquid chromatograph separates the tripeptides (1)

mass spectrometer produces a distinctive fragmentation pattern (1)
identification by computer using a spectral database (1)

4) In this question, one mark is available for the quality of use and
organisation of scientific terms.
The structural formulae of three isomers of C3H9NO are shown below.

Describe the similarities and differences you would expect to see when
comparing the
Infra-red spectrum of each isomer
Similarities

 Any 2 of the following three peaks (must give the quoted range)
peak corresponding to OH in all three(3230 3550 cm1)
peak corresponding to NH in all three(3100 3500 cm1)
peak corresponding to CO in all three (1000 1300 cm1)
Differences
only shown in the fingerprint region
Mass spectrum of each isomer.
Similarities
Mr (75)/ base peak will be the same
Differences
Fragmentation pattern may show differences between isomers /
specific example, eg CH3+ at m/e 15
5) In this question, one mark is available for the quality of the use
and organisation of scientific terms.
Describe and explain the different ways that a high resolution n.m.r.
spectrum can give information about a molecule.

value / chemical shift gives the type of proton / chemical environment

example quoted from data sheet

number of peaks gives the number of different types of proton / chemical

environments

relative / ratio of peak areas gives the number of protons (of each type)

splitting gives number of neighbouring / adjacent protons

description of n + 1 rule / example of doublet, triplet or quadruplet

showing 1, 2 and 3 protons neighbouring (carbon) atom

D2O can be used to identify OH groups

6) Unknown compounds are often identified by n.m.r. spectroscopy.

Part of the n.m.r. spectrum of butanone is shown on the axes below.

(i) State which part of the butanone molecule is responsible for peak A at _ =
2.1. Explain your reasoning.

the peak is due to the CH3CO- group

not split, so next to a C with no protons / has no neighbouring proton /
value is in the range 2.0 2.9

(ii) Explain why peak B is split into a quadruplet.

adjacent to a C with three protons / to a CH3

(iii) Predict the remainder of the n.m.r. spectrum of butanone by sketching it

on the axes above.
(iv) Write the relative peak area above each of the peaks on the completed
spectrum of butanone.

7) Lactic acid produces an n.m.r. spectrum in D2O with peaks at

chemical shift values of 1.4 ppm and 4.3 ppm.
(i) On the axes below, sketch the high resolution n.m.r. spectrum of lactic
acid in D2O. Show any splitting patterns and state the relative areas of the
two peaks.

Answers

splitting:
doublet
quartet
(ignore any other peak)

position:
doublet peak is at ~1.4 and
quartet peak is at ~4.3

areas:

1 and 3 on the correct peaks

(or either way round as ecf if any errors above)
(ii) How many peaks would you expect if the n.m.r. spectrum of lactic acid
was run in an inert solvent rather than in D2O? Explain your answer.

4 because OH/labile protons now visible

8)Thua nao is a traditional sauce made in Northern Thailand by

fermenting cooked soybeans. Its unique flavour is due to a range of
volatile compounds formed during the fermentation.
One of these volatile compounds is 3-hydroxybutanone.

(a) State the meaning of the term volatile.

low boiling point / easily turns to a gas

(b) Several hydroxyketones with similar boiling points can be separated from
the fermentation mixture. Describe a method, which does not involve
spectroscopy, that could be used to distinguish 3-hydroxybutanone from the
other hydroxyketones.

2,4-dinitrophenylhydrozine / 2,4-DNP(H) / Bradys reagent

purify/recrystallise the product/solid (derivative)
measure the melting point /mp
compare the result with data book/known values

9) a) Low resolution mass spectrometry identified the molecular ion

peak of an organic molecule as 86. Suggest three possible molecular
formulae for the molecule.
C3H2O3, C5H10O, C6H14

b) High resolution mass spectrometry identified the molecular ion peak of

the organic molecule as 85.998. Deduce the molecular formula of the
molecule, given the following relative isotopic masses:

Answers
C3H2O3

10) Identify the bonds responsible for all the peaks in the nonfingerprint region of the following infra-red spectra, and hence state
the functional group present:

Answers
a) O-H (alcohol)
b) C=O (carbonyl)
c) C=O and O-H (acid) so carboxylic acid
d) C=O (carbonyl)
11) Three compounds A, B and C, all with molecular formula C 4H8O2,
are found to have very different infra-red spectra. All three spectra
contain a sharp peak at 1700 cm-1, but the infra-red spectrum of A
contains a broad peak at 2500 3000 cm-1, the infra-red spectrum of
B contains no broad peaks, and the infra-red spectrum of C contains
a broad peak at 3000 3300 cm-1. Suggest possible structures for A,
B and C.

All have a carbonyl group (1700)

A is a carboxylic acid (2500 3000 broad) butanoic or
methylpropanoic acid.
B has no broad peaks so is either a carbonyl ether or an ester
C is an alcohol (3000 3000 broad) so is a carbonyl alcohol

12) Suggest how infra-red spectroscopy could be used to determine

the exact structure of a molecule containing only C-H absorptions
and a C=O absorption in the region 1500 3500 cm-1.

The fingerprint region (1500 3500 cm-1) is different for every

molecule
So compare the fingerprint region of the molecule with a database of
IR spectra of known carbonyl molecules until an exact match is found.