Chapter 18

Technical Aspects of Perfumery

Leslie C. Smith
Coty Inc., Morris Plains, New Jersey, USA

Introduction
Fragrance and odor have been a central part of communication, reproduction, and
civilization since the beginning of the human species. Throughout our evolution the
sense of smell has refined and attenuated. However, it still remains an integral sense
in our culture and is a major contributor in our choice of environment, mates, and
material items. The importance of perfume in consumer products is self-evident.
Despite emerging technologies, such products are often differentiated and preferred
only on the basis of perfume. In this case individuals in the fragrance industry some-
times claim (somewhat immodestly) that “fragrance drives market share.”
This chapter will focus on the technical aspects of successfully incorporating
fragrance into consumer products. The constraints that appear in any perfume pro-
ject can be classified as performance, technical, safety, and price. Although safety
and price are central to fragrance development, these are beyond the scope of this
chapter. This chapter will be concerned with the first two “Filters to Creativity,”
namely performance and technical aspects.

What Is a Fragrance?
Fragrances are hedonically pleasing (in principle at least), complex mixtures of
organic chemicals (esters, alcohols, aldehydes, essential oils, ketones, “aromatics,”
“heterocycles,” etc.), solvents (DPG and alcohol), and stabilizing materials
(“chelants” [EDTA] and antioxidants [BHT]).

Fragrance Performance
The performance of a fragrance can be related to parameters, such as threshold values,
that give a measure of “power” and relate to the lowest concentration at which a mate-
rial can be olfactorily detected; response curves, that relate to how people respond to
increases in concentration; diffusivity; substantivity; and the interaction between bases
and matrices in which they are applied. Some relative odor strengths are represented in
Table 18.1. These range from formic acid which has only a faint odor to the “rotten”
dimethyl sulfide which can be smelled at a concentration equivalent to one drop in an
Olympic-sized swimming pool.

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 TABLE 18.1
Relative Odor Strengths

Odor type Compound Concentration (ppm)

Ethereal Ethylene chloride 800
Camphoraceous 1,8 Cineole 10
Musky Pentadecalactone 1
Floral Phenylethylmethylethyl carbinol 300
Minty Menthone 6
Pungent Formic acid 50,000
Putrid Dimethyl sulfide 0.1

Over recent years, a veritable arsenal of tools has been brought to bear by the
fragrance industry to understand, optimize, and predict fragrance performance in
consumer products. Among these are gas chromatography (GC)/headspace/sniff-
ing, logP (octanol/water partition) calculations, analytical instrumentation, and fra-
grance engineering.

GC/Headspace/Sniffing
Headspace analysis allows clear qualification and quantification of organic materi-
als in the atmosphere. Typically vapors are trapped and then analyzed using
GC/MS techniques. A recent technique that has achieved widespread use in the
fragrance industry is known as solid phase micro extraction (SPME) (Fig. 18.1)
(1). Vapors are trapped on a fine fiber before being directly injected into GC/MS
for analysis. Some of the many uses of this technique are illustrated in Figure 18.2. In
addition to headspace analysis, state-of-the-art techniques are employed to identify
new fragrance chemicals and understand the fate of fragrances in the environment.
These techniques include HPLC–MS, high resolution NMR, many MS techniques,
vapor-phase FTIR, among others (Fig. 18.3). An attempt to predict fragrance per-
formance has been represented by a number of patents (2). These “logP patents”
characterize deposition of fragrances in relation to certain solubility parameters
(Fig. 18.4).

Fragrance Engineering: A New Creative Tool for Perfumery

Sophisticated computational techniques have been applied that use a solvation
model to calculate chemical ingredient charge distribution. Mathematical descrip-
tors can be used to model many aspects of fragrance performance that include the
effects of bases and the interaction of matrices such as fabric, skin, hair, and even
olfactive receptors (Fig. 18.5). These descriptors, so-called σ-moments, are calcu-
lated and provide key performance parameters for all fragrance chemicals to model
the effects of bases and the interaction on the following matrices: textiles, hair,
skin, and “clay” olfactive receptors.

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 Fig. 18.1. Solid phase micro extraction.

Fig. 18.2. GC/headspace in fragrance performance.

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 Fig. 18.3. State-of-the-art analytical capabilities used to trace the fate and life cycle of
fragrance chemicals in the environment and in an application.

These predictions are then inserted into a more intuitive chart for creative per-
fumers. One of the key performance parameters in consumer products is generally
known as substantivity. Substantivity is particularly important in rinse-off prod-
ucts, such as soaps, detergents, and shampoos, where as much as 90% of the fra-
grance can “go down the drain.” A popular way to characterize the optimal sub-
stantivity is “the right level of the right fragrance in the right place at the right

• LogP

— “The logarithm of
the octanol/water
partition coefficient”

— Measurement of the
polarity of the aroma
chemical.

CH3 LogP = 3.38

CH2 Values and calculations
COH as outlined by Howard
C=C and Meylan
C-C

Fig. 18.4. LogP and other physical chemical parameter calculations using structure
activity relationships (SAR).

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 H

Fig. 18.5. Prediction of fragrance performance in application through computational

techniques.

time” (and at the right price). This is a complex phenomenon and is best referred to
as “perceived substantivity” (Fig. 18.6). Perceived substantivity is what the con-
sumer actually smells during an application and is a synthesis of psychophysical,
chemical, and physical effects.

Stability
Now that the performance of a fragrance in consumer products has been defined,
another critical topic to address is the creation of “winning fragrances.” Generally

Psychophysical

Perceived
Substantivity

Chemical Attach /Detach

effects effects (physical)
Fig. 18.6. Substantivity.

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 referred to as “stability,” this is best considered a synthesis of two areas, fragrance
integrity and product effects. Therefore, stability can be defined as “the integration
of a fragrance into a finished product providing ‘fragrance integrity’ and ‘product
integrity’ under conditions of storage and application of that product” (Fig. 18.7).
The first part of the stability issue relates to the effect of the product on the fra-
grance and is referred to as fragrance integrity. Once again there are three con-
tributing factors: chemical, physical, and base odor.

Chemical Stability
Fragrance degradation may occur as a function of oxidation. “Ariel oxidation” is a
relatively inefficient process and not therefore a major challenge. Chemical oxida-
tion is more important, and the low-temperature bleach-activated detergents with
perborate or percarbonate salts and bleach activators, such as tetra acetyl ethylene
diamine (TAED) or nonanoyl oxybenzene sulfonate (NOBS), are problematic.
This system eliminates a significant proportion of materials available to the per-
fumer. Other mechanisms of chemical decomposition include hydrolysis (pH), rad-
ical chain reactions (hypochlorite bleach), and reduction (inorganic bisulphite).
Figure 18.8 crudely represents the percentage of raw materials that are chemically
stable across a wide range of applications.

Physical Effects
These fall into two categories: absorption and adsorption. Absorption occurs into
liquid detergents, while adsorption occurs onto zeolites and bentonites. An exam-
ple is given on how adsorption onto different clays used in cat litter can dramati-
cally change the profile of a fragrance (Fig. 18.9).

Chemical

Fragrance
Integrity

Physical Base Odors

Fig. 18.7. The effect of a product on fragrance.

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 % Raw materials stable (2000)
100
80
60
(%)

40
20
0
Fine LDL/LDD HDD
Fragrance (Bleach)
“Problem areas”
Fig. 18.8. Chemical stability of fragrance ingredients.

Base Odors
This is often a major issue in providing an acceptable fragrance for consumer prod-
ucts. It can even become a contentious area between suppliers and their customers.
Two kinds of base odors should be considered, inherent and problem. Inherent
odors occur even with the use of good quality stable materials and include materi-
als, such as fats, sulfur compounds, and iso-propanol. Problem odors are related to
the use of poor quality or unstable raw materials. These could typically include
enzymes, and cationic surfactants. Base odor issues can be addressed by “cleaning
up” the base or by applying “odor management” techniques.
Product aspects are the second major component contributing to product
integrity. This represents the effect of a fragrance on the product. The product
aspects are classified as physical, chemical, and others. Physical effects can be rep-
resented by viscosity changes (attachment) in fabric softeners in which the fra-
grance can effect a change on the physical form of the product from vesicles (lipo-
somes) to liquid crystals and result in a catastrophic increase in viscosity.
Chemical effects can be represented by the effect of certain olfactorily stable fra-
grance chemicals that catalyze the decomposition of the hypochlorite in household
bleaches and lead to a loss of available chlorine. Other considerations can include
packaging and coloration issues. Examples of these are displayed in Figures 18.10
and 18.11. When any issues of fragrance integrity have been addressed, and when
product aspects are acceptable, the fragrance company or consumer product devel-
opers arrive at product integrity (Fig. 18.12).

Additional Benefits of Fragrance

Besides the key hedonic and consumer preference benefits that are delivered by
fragrances, certain additional benefits can also occur. “Perceived benefits” arise in

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 Fig. 18.9. Absorption profiles in cat litter.

consumer tests, where consumer product attributes can sometimes significantly

change from fragrance to fragrance. Thus certain fragrances can smell whiter, soft-
er, and fresher. These are psychological effects and are the subject of a large area
of fragrance research. Functional benefits are those cases in which a fragrance
actually performs a physically or olfactively measurable task. Such effects include
grease removal by orange terpenes, insect repellant, sunscreen, and deodorant. An
example of a typical underarm deodorant panel is given in Figure 18.13.

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 Fig. 18.10. The effect of
fragrance ingredients on
Vesicle Liquid concentrated fabric soft-
(Liposome) (X40,000) crystal ener.

Physical Chemical

Fig. 18.11. The effect of

“Others” fragrance on a product.

Fragrance
Integrity
Product
Integrity
Product
Aspects
Fig. 18.12. Aspects that
influence product
integrity.

Conclusion
At the end of this overview, here are a few words on fragrance trends. It has been
said that: “The only certain thing about the future is that it will surprise even those
who have seen into it.” Fragrance trends parallel social trends; the major trends can
be translated as: communication (Internet, media), demographics (singles, house-

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 Fig. 18.13. Deodorant panel.

holds, aging), environment (care for the planet, water, energy), leisure (health, self-
interest), mistrust of science, and consumption and waste. Where this will lead the
fragrance industry is anybody’s guess. What is certain is that in coming years there
will be a myriad of new consumer products whose success or failure will be driven
by technology, consumerism, and fragrances.

References
1. Mookherjee, B.D., A novel technology to study the emission of fragrance from skin,
Perfumer & Fragrance 23 (1998), pp. 1–23.
2. Procter & Gamble, Detergent Compositions Containing Enduring Perfume, U.S. Patent
6,491,728.

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