QUESTION 1

Which of the following statements is true about the molecular ion of an analyte in the mass
spectrum?

A The molecular ion is the mass-to-charge ratio of the analyte minus an electron.
B The molecular ion is calculated using the average masses of each element.
C The molecular ion is always the most abundant peak in the mass spectrum.
D All of the above.

QUESTION 2
The correct order for the basic features of a mass spectrometer is...

A acceleration, deflection, detection, ionisation

B ionisation, acceleration, deflection, detection
C acceleration, ionisation, deflection, detection
D acceleration, deflection, ionisation, detection

QUESTION 3
Which one of the following statements about ionisation in a mass spectrometer is incorrect?

A Gaseous atoms are ionised by bombarding them with high energy electrons.
B Atoms are ionised so they can be accelerated.
C Atoms are ionised so they can be deflected.
D It doesn't matter how much energy you use to ionise the atoms.

QUESTION 4
The path of ions after deflection depends on...

A only the mass of the ion

B only the charge on the ion
C both the charge and the mass of the ion
D neither the charge nor the mass of the ion

QUESTION 5
Which of the following species will be deflected to the greatest extent?

A 37
Na +
B 35
Na +
37
C Na
D 35
Na 2+

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QUESTION 6
Which of the following statements regarding mass spectrometry is incorrect?

A In a normal mass spectrometer, electron impact causes a molecule to lose an electron

and become a molecular radical cation which decomposes into fragment cations and
radicals.

B Only cations can be detected by a normal mass spectrometer.

C A compound whose molecules contain just one bromine atom shows two molecular ion
peaks of similar intensity, one at +1 and one at -1 of the average m/z value.

D Molecular ion peaks always have even-numbered values of m/z.

QUESTION 7
Which of the following statements is incorrect?

A A conventional mass spectrometer employs high energy UV radiation.

B A conventional mass spectrometer does not employ a spectrophotometric detector.
C Conventional mass spectrometry does not always require samples of high purity.
D A mass spectrum does not show signals due to uncharged radicals.

QUESTION 8
Not only the molecular ion peak, but all peaks in the mass spectrum of chlorobenzene are
accompanied by a smaller peak one mass unit higher. This peak is due to which of the
following?

A Capture of an H atom
B Presence of a 13C
C Presence of a 36Cl
D Capture of a proton

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QUESTION 9
Consider the following mass spectrum:

(a) Which peak most likely represents the molecular ion?

(b) Which peak represents the base ion?

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QUESTION 10 (2 marks)
The mass spectrum of an organic compound is given below.

Use the fragments produced to draw the structural formula of the molecule that produced the
spectrum.

Solution

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QUESTION 11 (7 marks)
Below are the mass spectra of two structural isomers of hexane:

2-methylpentane
2,2-dimethylbutane

a. (i) How is the molecular ion formed in the mass spectrometer? (1 mark)

(ii) Account for the absence of the molecular ion in the second spectrum. (1 mark)

(iii) Which fragment in spectrum 1 has the greatest stability? (1 mark)

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b. (i) Write a semi structural equation for the formation of the fragment at m/z = 71 in the
mass spectrometer. (2 marks)

(ii) Which spectrum was produced by 2-methylpentane? Give a reason for your
answer. (2 marks)

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QUESTION 12 (6 marks)
An organic compound contains 48.6% carbon, 8.2% hydrogen and 43.2% oxygen by mass.
The mass spectrum and infrared spectrum of this compound are shown below.

(a) Calculate the empirical formula of this compound. (3 marks)

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(b) Hence find the molecular formula of compound X.

(c) Sketch a possible structure for compound X.

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QUESTION 1 Answer is A

QUESTION 2 Answer is B

QUESTION 3 Answer is D

QUESTION 4 Answer is C

QUESTION 5 Answer is D

35
Na 2+ has the smallest m/z value.

QUESTION 6 Answer is D

The molecular mass of a molecule containing one nitrogen atom, for example, is an odd
number of atomic mass units, so its molecular ion peak has an odd numbered m/z ratio;
statement (d) is wrong.

QUESTION 7 Answer is A

Since a conventional mass spectrometer detects positively charged species according to

their abundances, small amounts of impurities do not much affect the analysis of the main
compound.

QUESTION 8 Answer is B

QUESTION 9

(a) The peak at m/z = 100.

(b) The peak with the highest m/z value i.e. the ion at m/z = 43.

QUESTION 10

M + = CH 3CH 2CH 2OH +

Molecule is 1-propanol: CH 3CH 2CH 2OH

QUESTION 11

a. (i) When the vaporised organic sample passes into the ionisation chamber of a mass
spectrometer, it is bombarded by a stream of electrons. These electrons have a
high enough energy to knock an electron off an organic molecule to form a
positive ion. This ion is called the molecular ion.

(ii) The molecular ion is highly unstable and fragments into smaller units.

(iii) The peak with the highest m/z value i.e. the ion at m/z = 57.

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 +
b. (i) CH 3CH 2CH 2CH 2CH 2CH 3 → CH 3CH 2CH 2CH 2CH 2 + + CH 3
•

(ii) Spectrum 2 as 2-methylpentane produces a m/z = 71 fragment and

2,2-dimethylbutane does not.

QUESTION 12

(a) C : H : O

48.6 8.2 43.2

: :
12 1 16

3.833 : 8.2 : 2.7

1.42 : 3 : 1
3 : 6 : 2

Empirical formula is C3 H 6O2

(b) M ( C3 H 6O2 ) = 74 and the molecular ion in the mass spectrum has a m/z of 74, which
means that the molecular formula is the same as the empirical formula i.e. C3 H 6O2 .

(c) From the infrared spectrum, it is known that compound X has a C = O and O − H
functional group i.e. it is a carboxylic acid.

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