Thermal Stability of Vitamin C: TGA & Use of Pyrogram

Mrta Juhsz1, Toshiya Sato1, Masamichi Tsukagoshi1, Toshihiro Fujii1*

Department of Chemistry, Meisei University

1.

Introduction
Evolved gas analysis (EGA) experiments were
conducted using the EGA/Ion Attachment MS systems.
Li+ ion attachment mass spectrometry has considerable
advantages in the study of products monitoring in the gas
phase in comparison with traditional EI mass
spectrometry. Unlike the traditional mass spectrometry,
employing ionization by high energy electrons, IAMS
much better preserves the profiles of product molecules,
allowing us to detect them as adduct ions without any
fragmentation. The fundamental mass spectra were
considered for EGA of vitamin C. The present work has
demonstrated that EGA/IAMS can be a valuable
technique for direct mass spectral analysis and kinetic
study of vitamin medicines. The thermal decomposition
kinetics of vitamin C was studied by non-isothermal
thermogravimetry as well.
2.

Experimental
Solid vitamin C (C6H8O6; M.W 176.12 g/mol; m.p
190-194C) was commercial product, newly purchased
from Sigma-Aldrich Co., Tokyo (purity 99.0%) and
was used without its any previously treatments.
Experiments were performed with the apparatus (Ion
attachment mass spectrometer, IA-Lab) manufactured by
the Canon ANELVA Technix Corp. for a quadrupole mass
spectrometer with a Li+ ion emitter and a direct inlet
probe (DIP). 1mg vitamin C was placed in a sample
holder and introduced to the mass spectrometric system
via DIP. In kinetic studies, DIP was heated according to a
temperature program.
Thermogravimetric analysis was conducted using a
Shimadzu DT-40 Thermal Analyzer both under nitrogen
and oxygen at a flow rate of 80 ml/min. The sample
weight used was 3mg. The heating rate was programmed
as 4C/min. The TG curves were recorded; using a
Shimadzu C-R6A data processing unit.
3.

Results and Discussion

Two methods, TGA and IAMS were used for
obtaining kinetic parameters and estimating lifetime for
vitamin C. The obtained thermogravimetry curve was
used for kinetic analysis in the TGA while the
ionchromatogram was used for kinetic analysis in the
IAMS.

In Figure 1 are reported the TG and DTG curves of

vitamin C obtained under nitrogen, showing that vitamin
C starts decomposing at about 200C and experiences the
maximum rate of decomposition temperature at about
225C. This maximum is followed by a less marked
decomposition step in the 260C400C temperature
range. After 450C, some residue was left.

In Figure 2 are reported the TIC (Total Ion Current)

and MIC (Mass Ion Current) curves of vitamin C
obtained under nitrogen by DIP-IAMS at the same
heating rate used for the TG experiments (4C/min up to
500C). The TIC curve corresponding to the vitamin C
sample closely reproduces the two maxima appearing in
the DTG curve which are due to the evolution of thermal
decomposition products of the vitamin C. However, in
the TIC curve, both peaks appear at lower temperature
ranges than the corresponding peaks on the DTG curve.
Its reason is that under DIP-IAMS, high vacuum was
applied, while the TGA measuring was carried out at
atmospheric pressure. Thermodynamic parameters
(activation energy, frequency factor) for decomposition
of vitamin C were calculated and lifetime estimation was
made.

The sum of the IAMS mass spectra recorded for the

peak within temperature range of 130 and 215C is
shown in Figure 3. The Li+ ion attachment mass
spectrometry technique provided mass spectra of
quasi-molecular ions formed by lithium ion attachment to
chemical species under vacuum. IAMS mass spectrum
contains the thermal decomposition products coming up
from vitamin C beside its evaporated molecular form.
The relative intensities of the mass peaks were
normalized to 100% for the main thermal decomposition
product peak among the species produced in the pyrolysis
process (Dehydro-L-ascorbic acid, m/z 181). The
monoisotopic mass peaks of the decomposition products
are numbered.
4.

Conclusions
Thermal decomposition of vitamin C was carried by
a temperature program of 4C/min heating rate from
room temperature up to 500C and thermal stability of
vitamin C was determined from the data recorded by both
the TGA and IAMS instrumental techniques.
References
[1]

[2]

T. Fujii, Ion Attachment Mass Spectrometry,

Encyclopedia of Mass Spectrometry: Ionization Methods,
vol. 6, p. 327, December 2006
S. Takahashi, Y. Kitahara, M. Nakamura, Y. Shiokawa, T.
Fujii, Temperature-resolved thermal analysis of cisplatin
by means of Li+ ion attachment mass spectrometry, Phys.
Chem. Chem. Phys., vol. 12, p. 3910, February 2010