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Amine Titration
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Introduction
The aim of this experiment was to suggest an identity for an unknown R-group in a primary amine.
The experiment was split into two halves; the first to titrate a known concentration of Na 2CO3
against an unknown concentration of HCl, then using the known concentration of HCl to titrate
against an unknown amine to discover the MR value and identity. Titration is a simplistic technique
but has many applications in discovering the qualitative and quantitative value of unknown
substances within forensics. Notable examples include testing tampered whiskey crossing the
Brazilian border1 and verifying the authorship of artwork, protecting cultural heritage and preventing
art fraud, by testing the oil make-up in painting fibres. 2 Titration is often overlooked in pursuit of
chromatography but as a low cost, time efficient and mobile test it is beginning to be recognised for
its many merits in field testing.

Method
First, a known concentration solution of Na2CO3 was made by dissolving a known mass of solids into
distilled water using a volumetric flask. A burette was then rinsed and filled with HCl acid of an
unknown concentration and titrated into 25cm 3 of Na2CO3 using methyl orange as an indicator to
determine the end point. The colour change watched for was green to grey. A purple colour
indicated that the titration had gone too far. After concordant titre results were obtained, the
molarity of the HCl acid was calculated using the following equation

Na 2 CO 3 +2 HCl → 2 NaCl+CO 2+ H 2 O

The same HCl acid solution was used in titration against an amine of known mass diluted with
ethanol as the mass was very small and the colour change would’ve been very difficult to notice.
Again, methyl orange indicator was used, and the same colour change was observed. Using the
−¿¿
chemical equation C 6 H 5 CH ( R ) N H 2+ HCl → C6 H 5 CH ( R ) N H 3+Cl the molar value of the
amine was calculated and therefore the MR value. 3

Results and Calculations

Molarity of Na2CO3
1.3188 g
=0.01244 mol ( 4 d . p )
( ( 2∗23 )+12+ ( 3∗16 ) )
Table showing HCl volumes required to reach an end point in titration of 25cm3
Na2CO3
Run number Volume of HCl (cm3)
Titre 1 21.90
Titre 2 21.80
Titre 3 21.60
Titre 4 21.70

1
(Nogueria, et al., 2019)
2
(Costa, et al., 2020)
3
(Crowe & Bradshaw, 2021)

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Concordant titre 21.65

Molarity of HCl(aq)
0.01244 mol 3
=0.001244 mol∈25 c m of N a2 C O3
10
0.001244 mol × 2=0.002488 mol of HCl because N a2 C O3 reacts with HCl∈a 1:2 molar ratio

0.002488 mol /0.02165 d m3=0.1149 mo l−1 d m−3

Molar mass of unknown amine
Table showing mass of amine and corresponding HCl acid titre volumes required to reach end point

Amine mass (g) Volume HCl (cm3)

0.2773 15.10
0.3589 30.80

−1 −3 3
0.1149 mo l d m × 0.01510 d m =0.0017350 mol of HClrequired ¿ react withunknown amine
Amine and HCl react in a 1:1 ratio

0.2773 g −1 −3
=159.83 g mol
0.0017350 mol
0.3589 g −1 −3
=206.86 g mol
0.0017350 mol
−1 −3 −1 −3
159.83 g mo l +206.86 g mol −1 −3
=183.34 g mo l
2
−1 −3
7 ( 12.011 ) +8 ( 1.0079 )+ 14.007=106.1472 g mo l

R group=183.34 g−1 mol −3 −106.1472 g−1 mo l−3=77.1928 g−1 mol −3

Discussion
By searching a database4 for species by mean relative molecular mass (RMM) within a range of ±0.5,
a range of molecules could be candidates. Further testing would be required to include or exclude
certain species. There is such a numerous list that it is not worth mentioning them all by name.
Neither does searching for each individual amine’s RMM give a conclusive identity.

Where there is such a great range in the calculated molecular mass of the amine in both runs, it
would be best to repeat this experiment until results similar to the range of a concordant titre were
reached. Furthermore, the indicator used was quite difficult to see the end point as the colour
change was very subtle. A light detecting machine to determine colour would’ve been better than
the naked eye to determine end point. In contrast to a titration, mass spectrometry would be a
much more accurate way to determine the molecular mass of the unknown amine. This would be a
more efficient method as it wouldn’t rely on a two step method where there is more room for error.
Running both gas chromatography in conjunction with mass spectrometry would give both
quantitative and qualitative results about the unknown amine which could also be useful in

4
(National Institute of Standards and Technology, 2022)

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determining purity level.5 This is assumed as 100% in the titration which may not be true and would
also affect the accuracy of results.

To calculate the relative molecular mass of a diamine the chemical equation for step two of the
method would change and therefore the molar ratio and corresponding calculations would also
change. However, the titration method would stay the same. The new chemical equation would be

H2 N ¿

The molar ratio between the unknown amine and HCl acid would become 1:2, therefore the moles
of amine would halve to become 8.675x10 -4mol. This value would be carried froward in the following
calculations.

To dilute a 250cm3 HCl solution of 10mol dm-3 to 0.1mol dm-3 is a dilution of 100. Using a pipette
remove 2.5cm3 from the original solution into a clean volumetric flask and add distilled water to a
total of 250cm3.6
−3 3
10 mol dm ×0. 0025 dm =0.025 mo l HCl
0.025 mol −3
3
=0. 1 mol d m
0 .25 dm

Conclusion
In summary, this method does give a molecular mass value for the unknown amine, although it is
difficult to find a corresponding molecule because of the range of types of molecules. Further
qualitative chemical testing is required to find out more about the unknown R-group, such as what
different chemical groups are included. This could easily be achieved through Gas Chromatography,
which although more expensive and requiring more technical apparatus would give a more accurate
value excluding the risk of human error.

References
Costa, T. G. et al., 2020. Potentiometric titration of microhydrolysis products of oils: A new low-cost
methodology and investment for the analysis of oil binders present in works of art. Talanta, Volume
212, p. 120736.

Crowe, J. & Bradshaw, T., 2021. Chemistry for the biosciences: the essential concepts. 4 ed. Oxford:
Oxford Univeristy Press.

National Institute of Standards and Technology, 2022. Search for Species Data by Molecular Weight.
[Online]
Available at: https://webbook.nist.gov/chemistry/mw-ser/
[Accessed 14 March 2023].

Nogueria, S. A. et al., 2019. Redox titration on foldable paper-based analytical evices for the visual
determination of alcohol content in whiskey samples. The International Journal of Pure and Applied
Analytical Chemistry, Volume 194, pp. 363-369.

Valcarcel, M., Cardenas, S., Simonet, B. & Carillo-Carrion, C., 2007. Principles of qualitative analysis in
the chromotograpic context. Journal of Chromatography A, Volume 1158, pp. 234-240.

5
(Valcarcel, et al., 2007)
6
(Crowe & Bradshaw, 2021)

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