Flavour Fragr J. 2019;34:63–69. wileyonlinelibrary.com/journal/ffj
|
63 © 2018 John Wiley & Sons, Ltd.
1 | INTRODUCTION
The flash-point temperature of fragrance and flavour oils is a prop-
erty of critical importance to regulatory compliance, particularly for
safety considerations concerning the handling, shipping, and stor-
age of potentially flammable products. By definition, the flash-point
temperature is the lowest temperature at which the vapour phase of
a liquid material will ignite in air in presence of a spark or a flame.
1,2
Perfumers and flavorists are required to finalize their formula-
tions with a flash-point measurement, which is time and resource
consuming, and slows down the creation process. Reliable flash-
point prediction for perfume and flavour oils is therefore a critical
business need in our industry. Yet, to our knowledge, the assessment
of flash-point predictions for complete perfumes and flavours, which
can easily encompass dozens or even hundreds of compounds with
diverse chemical functionalities, is not available in the current scien-
tific literature.
The flash point of a liquid mixture is dependent upon the flash
points of the individual ingredients, the vapour pressure–temperature
relationship for each ingredient, molecular interactions between
species in the mixture (captured via activity coefficients),
3,4
and the
homogeneity of the solution (miscibility gap).
5
Assuming that vapour
pressure–temperature relationships and flash points for individual
ingredients are available, the key to reliable flash-point prediction
is being able to capture molecular interactions in multi-component,
non-ideal solutions with reasonable accuracy.
6–9
In cases where the number of compounds in the mixture is lim-
ited (<10), two approaches have been reasonably successful in pre-
dicting the flash points of mixtures.
10
One approach is empirical,
based on the quantitative structure–property relationship (QSPR),
and is constructed from reliable experimental data (e.g. boiling point,
the composition range of flammable components in the mixture,
molecular descriptors, etc.), but depends on the quality of the avail-
able data and the quantity and type of molecular descriptors.
11,12
The other approach is drawn from thermodynamics, and combines
Le Chatelier's rule and a vapour–liquid equilibrium (VLE) model.
13–19
The latter approach is theoretically more reliable because every pa-
rameter in the model has a physical meaning, although it can also
Received: 22 June 2018
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Revised: 13 November 2018
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Accepted: 20 November 2018
DOI: 10.1002/ffj.3485
RESEARCH ARTICLE
Flash-point prediction of fragrances or flavours accounting for
non-ideality of the liquid phase
Denis Shcherbakov
1
| Silvère Massebeuf
2
| Valery Normand
1
1
Firmenich Inc., 250 Plainsboro Road,
Plainsboro, NJ 08536, USA
2
ProSim SA, Immeuble Stratège A, 51 rue
Ampère, 31670 Labège, France
Correspondence
Valery Normand, Firmenich Inc., 250
Plainsboro Road, Plainsboro, NJ 08536, USA.
Email: valery.normand@firmenich.com
Abstract
The flammability classifications of flavour and fragrance oils are determined from
their flash-point temperatures, which are of critical importance for safety and regula-
tory considerations. The reliable prediction of flash points for our products is a busi-
ness need challenged by the sheer number of ingredients present in a typical
formulation, ranging from dozens to hundreds of ingredients, and their chemical di-
versity. To assess the predictability of flash points for the complex mixtures relevant
to our industry, we consider five model mixtures of 15 perfume and flavour raw ma-
terials, with a variety of chemical functionalities, and apply Le Chatelier's rule to-
gether with vapour pressure curves from the Design Institute for Physical Properties
(DIPPR) database and activity coefficients predicted from the Modified UNIFAC
(Dortmund 1993) group contribution model. Flash-point temperatures of the
15-compound model mixtures were predicted with an accuracy of ±2°C, compared
with experimental data, when taking into account the non-ideality of the liquid phase.
KEYWORDS
flash-point temperature, ignition, lower flammable limit, mixtures, safety