Spectroscopic identication of organic compounds

[28 marks]

The structure of an unknown compound A with empirical formula CH2 can be determined using information from a
variety of analytical techniques.

The mass spectrum of A is shown below. [1 mark]

1a.

Deduce the formula of the molecular ion from the mass spectrum.

Markscheme
C4 H+
8 ;
Penalize missing charge only once in (i) and (ii).

Examiners report
This question focused on some of the fundamental spectroscopic techniques (MS, IR and 1 H NMR) used in analytical
chemistry. The better candidates did well on this question though few scored full marks. In (a), the most common
mistake was omission of the positive charge in (i). One G2 comment stated that isotopic effects in mass spectra with
regard to the determination of the molecular ion peak would confuse students. This generally was not the case and
although most got the C4 H8 formula a large majority of candidates simply did not read the question correctly which
specifically asked for the formula of the molecular ion. In (ii) the correct formulas of the fragments were usually given.
In (b), C=C was usually cited as the correct structural formula in (ii). The weaker candidates struggled with explaining
the doublet in (iii). Cyclobutane was obtained by a large number of candidates in (iv). In (c) (i), the better candidates
scored all three marks. In (ii), an understanding of the fingerprint region was poorly conveyed. There were two parts to
this question an outline of what happens on a molecular level when radiation in the fingerprint region is absorbed
and how this region is used in chemical analysis. One G2 comment referred to the fact that the fingerprint region is not
explicitly mentioned in the guide. Although this is true per se AS 3.2 does require a description of how the information
from an IR spectrum can be used to identify bonds, and it would be assumed that the fingerprint region would be
discussed in the context of teaching IR spectroscopy as part of the IB chemistry programme.
 The infrared (IR) spectrum of A is shown below.

1b. Explain the presence of a doublet in the high-resolution proton nuclear magnetic resonance (1H NMR) spectrum [3 marks]
of A.

Markscheme
produced by (Hs in) = CH2 group;

adjacent C has 1 H atom;

n + 1;
due to relative/(two) different orientations/alignment of spin of nuclei/protons/hydrogens (with applied/external
magnetic field);

Examiners report
This question focused on some of the fundamental spectroscopic techniques (MS, IR and 1 H NMR) used in analytical
chemistry. The better candidates did well on this question though few scored full marks. In (a), the most common
mistake was omission of the positive charge in (i). One G2 comment stated that isotopic effects in mass spectra with
regard to the determination of the molecular ion peak would confuse students. This generally was not the case and
although most got the C4 H8 formula a large majority of candidates simply did not read the question correctly which
specifically asked for the formula of the molecular ion. In (ii) the correct formulas of the fragments were usually given.
In (b), C=C was usually cited as the correct structural formula in (ii). The weaker candidates struggled with explaining
the doublet in (iii). Cyclobutane was obtained by a large number of candidates in (iv). In (c) (i), the better candidates
scored all three marks. In (ii), an understanding of the fingerprint region was poorly conveyed. There were two parts to
this question an outline of what happens on a molecular level when radiation in the fingerprint region is absorbed
and how this region is used in chemical analysis. One G2 comment referred to the fact that the fingerprint region is not
explicitly mentioned in the guide. Although this is true per se AS 3.2 does require a description of how the information
from an IR spectrum can be used to identify bonds, and it would be assumed that the fingerprint region would be
discussed in the context of teaching IR spectroscopy as part of the IB chemistry programme.
 1
1c. One isomer of A has only one signal in its H NMR spectrum. Deduce the structural formula of this isomer.
[1 mark]

Markscheme
;

Accept full or condensed structural formula.

Examiners report
This question focused on some of the fundamental spectroscopic techniques (MS, IR and 1 H NMR) used in analytical
chemistry. The better candidates did well on this question though few scored full marks. In (a), the most common
mistake was omission of the positive charge in (i). One G2 comment stated that isotopic effects in mass spectra with
regard to the determination of the molecular ion peak would confuse students. This generally was not the case and
although most got the C4 H8 formula a large majority of candidates simply did not read the question correctly which
specifically asked for the formula of the molecular ion. In (ii) the correct formulas of the fragments were usually given.
In (b), C=C was usually cited as the correct structural formula in (ii). The weaker candidates struggled with explaining
the doublet in (iii). Cyclobutane was obtained by a large number of candidates in (iv). In (c) (i), the better candidates
scored all three marks. In (ii), an understanding of the fingerprint region was poorly conveyed. There were two parts to
this question an outline of what happens on a molecular level when radiation in the fingerprint region is absorbed
and how this region is used in chemical analysis. One G2 comment referred to the fact that the fingerprint region is not
explicitly mentioned in the guide. Although this is true per se AS 3.2 does require a description of how the information
from an IR spectrum can be used to identify bonds, and it would be assumed that the fingerprint region would be
discussed in the context of teaching IR spectroscopy as part of the IB chemistry programme.
 The structure of an unknown compound A with empirical formula CH 2 can be determined using information from a
variety of analytical techniques.

The mass spectrum of A is shown below.

Determine the relative molecular mass of the compound from the mass spectrum and deduce the formula of the [2 marks]
2a.
molecular ion.

Markscheme
56;

C4 H+
8 ;
Penalize missing charge only once in (i) and (ii).

Examiners report
More than half of the candidates obtained the molecular mass from the spectrum. About a third of the candidates
identified C4 H8 as the molecular formula but only a few candidates remembered to include the positive charge on the
molecular ion and scored the second mark.

2b. Deduce the formulas of the fragments which give rise to peaks at m/z = 27 and 29. [1 mark]

m/z = 27:

m/z = 29:
 Markscheme
m/z = 27 : C2 H+ + + + +
3 /CH2 CH /CH2 =CH and m/z = 29 : C2 H5 /CH3 CH 2 ;
Penalize missing charge only once in (i) and (ii).

Examiners report
About a third of the candidates identified the correct fragments. It was disappointing to see candidates suggesting
fragments that did not match the masses of the peaks.

The infrared (IR) spectrum of A is shown below.

Identify the bond responsible for the IR absorption at B. [1 mark]

2c.

Markscheme
C=C/carboncarbon double bond;

Accept alkenyl/alkene.

Examiners report
Very well answered.
 Deduce a structural formula consistent with the data. [1 mark]
2d.

Markscheme
CH 3CH 2CH=CH 2;

Accept either a full or a condensed structural formula.

Examiners report
Only a few candidates deduced the correct structural formula consistent with the data.

Organic compound X is 68.11% carbon, 13.74% hydrogen and 18.15 % oxygen by mass.

3a. Show that the empirical formula of compound X is C5 H12 O. [1 mark]

Markscheme

/ OWTTE;

Accept mass of C5H 12O = 88.17 so % of C = ( 60.05

88.17
) 100 = 68.11,
% of H = ( 12.12
88.17
) 100 = 13.75 and % of O = ( 16.00
88.17
) 100 = 18.15.
Allow integer values for atomic masses.
Examiners report
The question on empirical formula in (a) posed no difficulty and even the weaker candidates scored the mark. In the
spectroscopy question in (b), some of the better candidates managed to score all 11 marks assigned to this extended
response type question. In the MS, + was often omitted. Many students could not distinguish between observed ions
and lost fragments. Only one candidate mentioned the "fingerprint" region of IR but did not refer to the need to
compare with library spectral data. For the IR the majority of candidates scored all three marks, though the weaker
candidates frequently suggested NH bonds and CF bonds even though neither nitrogen nor fluorine are part of the
empirical formula given in the stem of the question. Discussion of the 1 H NMR spectrum proved the most challenging
and many candidates did not relate the splitting pattern to the specific carbon fragments. It was disappointing at HL
seeing a number of candidates not including hydrogens in their final answer for the structural formula of 2-
methylbutan-2-ol.

1 H NMR
 1
3b. The mass spectrum, infrared spectrum and details of the H NMR spectrum of compound X are given below. [11 marks]

Mass spectrum:

Infrared spectrum:

1 H NMR spectrum:

Analyse these three spectra and, using relevant information, deduce the identity of the compound.

Mass spectrum:

Infrared spectrum:

1 H NMR spectrum:
Identity of X:
Markscheme
Mass spectrum:
+
molecular ion peak at 88/M = 88 shows molecular formula is C5 H12 O;
absorption at 73 due to (MCH 3)+ / X contains a methyl group as peak at M15 / OWTTE;

absorption at 59 due to (MC2H 5)+ / X contains an ethyl group as peak at M29;

Penalise once only if + charge omitted.

Accept that X contains a CHO group due to M29 but in fact it cannot as there are too many hydrogen atoms in the
compound for it to be an aldehyde.

Infrared spectrum:

peak in range at 32003600 cm1 shows it contains an OH group / OWTTE;

(sharp) peaks just below 3000 cm1 /in range 28503100 cm1 due to CH
absorptions;

lack of peak at approximately 1700 cm1 shows it does not contain C=O;

absorption between 1050 and 1410 cm1 due to CO;

Allow due to alcohol instead of due to CO.

Accept absorption between 1050 and 1410 cm 1 due to ether or ester although it cannot be either as there is only
one O atom and it has been identified as bonded to H.

fingerprint region specific to compound but needs to be compared with library / OWTTE;
1H NMR spectrum:

(12 protons are in) four different chemical environments (in the ratio 1:2:6:3);

singlet (with integration trace of 1) due to OH proton;

singlet (with integration trace of 6) suggests (two CH3 ) groups attached to a carbon atom with no Hs attached to it;
quartet (with integration trace of 2) due to CH2 next to CH3 ;
triplet (with integration trace of 3) due to CH3 next to CH2 ;
Reference must be made to the association of the splitting pattern (singlet, triplet etc.) to the specific carbon
fragments.

(X is) 2-methylbutan-2-ol/CH3 CH2 C(CH3 )2 OH;

No ECF throughout 2(b).

Examiners report
The question on empirical formula in (a) posed no difficulty and even the weaker candidates scored the mark. In the
spectroscopy question in (b), some of the better candidates managed to score all 11 marks assigned to this extended
response type question. In the MS, + was often omitted. Many students could not distinguish between observed ions
and lost fragments. Only one candidate mentioned the "fingerprint" region of IR but did not refer to the need to
compare with library spectral data. For the IR the majority of candidates scored all three marks, though the weaker
candidates frequently suggested NH bonds and CF bonds even though neither nitrogen nor fluorine are part of the
empirical formula given in the stem of the question. Discussion of the 1 H NMR spectrum proved the most challenging
and many candidates did not relate the splitting pattern to the specific carbon fragments. It was disappointing at HL
seeing a number of candidates not including hydrogens in their final answer for the structural formula of 2-
methylbutan-2-ol.

C H O
 Two students were provided with three different isomers of C3 H6 O2 . [6 marks]
4.

They were asked to suggest how the isomers could be distinguished and positively identified from each other using
spectroscopic techniques. Student A said that they could be positively identified just from their infrared spectra. Student B
said that they could be positively identified just from the number of peaks and the areas under each peak in their 1 H NMR
spectra.

Evaluate these two claims and suggest how any possible limitations could be overcome using the same spectroscopic
technique.

Student A / Infrared:

Student B / 1 H NMR:
Markscheme
Student A / Infrared

propanoic acid can be distinguished from the other two by the (broad) absorption at 25003300 cm1 /due to OH
absorption in carboxylic acids;

not easy to distinguish between methyl ethanoate and ethyl methanoate because all absorb at 17001750 cm1 /
C=O / 10501410 cm1 / CO / 28503100 cm1 / CH / because they have same functional groups;
can be distinguished from the pattern in the fingerprint region / by comparing with spectra of known samples;

Student B / 1H NMR

methyl ethanoate can be distinguished from the other two as it will have two peaks of equal area (due to the two CH 3
groups);

propanoic acid and ethyl methanoate cannot be distinguished as both have three peaks / peaks in the ratio of 1:2:3;

chemical shift is also required to distinguish them;

Absorption value or name of functional group required for M1 and M2.

Examiners report
This question proved to be very challenging for most candidates as majority were unable to evaluate the two claims.
Candidates appeared to have some general understanding but were often lacking depth in understanding of the two
analytical techniques. The answers were often too general and most did not suggest ways to overcome limitations
using the same spectroscopic techniques. Limited understanding of the directive term evaluate along with missing
the same spectroscopic technique in the question stem, penalized the most students from scoring even part marks.
 International Baccalaureate Organization 2017
International Baccalaureate - Baccalaurat International - Bachillerato Internacional

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