Current Opinion in Colloid and Interface Science 7 (2002) 451–455

Colloidal basis of emulsion color

David Julian McClements*
Biopolymers and Colloids Laboratory, Department of Food Science, University of Massachusetts, Amherst, MA 01003, USA

Abstract

The perceived quality of many commercial products that are based on emulsions is determined by their color. Recent theoretical
and experimental research has focussed on determining the relationship between emulsion color and the colloidal characteristics
of the system, e.g. particle size, concentration, refractive index and aggregation. Appreciable progress has been made in
understanding the factors that determine emulsion color and in describing the optical properties of emulsions theoretically.
䊚 2002 Elsevier Science Ltd. All rights reserved.

Keywords: Emulsions; Optical properties; Color; Light scattering

1. Introduction wave by the emulsion. Light scattering and absorption

The perceived quality of emulsion-based food prod-
ucts, such as milk, cream, salad dressings, sauces and
beverages, is strongly influenced by their stability, rhe-
ology and appearance w1x. A great deal of theoretical
and experimental work has been carried out to establish
the colloidal basis of food emulsion stability and rheol-
ogy. On the other hand, until recently, few systematic
studies had been carried out to establish the colloidal
basis of food emulsion appearance. This is surprising
since the appearance of a food is the first sensory
impression that a person normally experiences of its
quality w2x. A better understanding of the colloidal basis
of emulsion appearance would aid in the design of
emulsion-based food products with improved quality.
This article focuses on recent advances in our under-
standing of the influence of colloidal characteristics on
the appearance of food emulsions. An understanding of
the colloidal basis of emulsion color depends on an
understanding of the physical processes that occur when
a light beam interacts with an emulsion and is subse-
quently detected by an eye or instrumental detector.
When a light beam is incident upon the surface of an
emulsion some of the light is transmitted and some of
the light is reflected. The relative proportions of light
transmitted and reflected at different wavelengths
depend on the scattering and adsorption of the light
*Tel.: q1-413-545-1019; fax: q1-413-545-1262.
E-mail address:
mcclements@foodsci.umass.edu (D.J. McClements).
depend on the size, concentration, refractive index and
spatial distribution of the droplets, as well as the
presence of any chromophoric materials (e.g. dyes).
Hence, the overall appearance of an emulsion is influ-
enced by its colloidal characteristics. Scattering is large-
ly responsible for the ‘turbidity’, ‘opacity’, or ‘lightness’
of an emulsion, whereas absorption is largely responsible
for ‘chromaticness’ (blueness, greenness, redness, etc.).
It should be stressed that the overall appearance of an
emulsion also depends on the nature of the light source
and detector used, but these effects will not be explicitly
covered here w3,4●,5x.
2. Theoretical prediction of emulsion color
Human beings have great difficulty objectively quan-
tifying the color of objects, so color is normally quan-
tified instrumentally in terms of ‘tristimulus
coordinates’, such as the L*a*b* system specified by
the Commission International de l’Eclairage (CIE) w5x.
The advantage of using a tristimulus coordinate system
is that the color of an object can be described in terms
of just three mathematical variables. It is then possible
to determine whether an object meets some predefined
quality criteria in a quantitative manner. For example,
in the L*a*b* color space, L* is lightness, and a* and
b* are color coordinates: where L*s0 is black, L*s
100 is white, qa* is the red direction, ya* is the green
direction, qb* is the yellow direction and yb* is the
blue direction w5x.

1359-0294/02/$ - see front matter 䊚 2002 Elsevier Science Ltd. All rights reserved.
PII: S 1 3 5 9 - 0 2 9 4 Ž 0 2 . 0 0 0 7 5 - 4
452 D.J. McClements / Current Opinion in Colloid and Interface Science 7 (2002) 451–455

the emulsion is calculated from the wavelength-depend-

ence of S and K, e.g. using Kubelka–Munk theory
w8●,9●,10●x. Finally, the tristimulus coordinates (L*a*b*)
of the emulsion are calculated from R(l) or T(l) using
color theory and tabulated information about the appro-
priate light source and observer w5x. The details of these
calculations have recently been given by w6x. It should
be noted that mathematical theories of varying degrees
of sophistication could be used in the general approach
described above to model the propagation of light waves
through an emulsion. For example, more sophisticated
theories have recently been developed to describe the
diffuse propagation of light waves through concentrated
particulate media of finite thickness w8●,9●,11●,12●,13x,
which could be utilized for describing the optical prop-
erties of food emulsions.

3. Numerical calculation of emulsion color

The influence of droplet size, concentration and

refractive index on the color of model oil-in-water food
emulsions predicted by light scattering theory is shown
in Figs. 1–3. In these examples, emulsion color is
represented by lightness (L*) and chroma wCs(a*2q
b*2)1y2x, where L* is a measure of lightnessydarkness
and C is a measure of color intensity. Emulsion lightness
Fig. 1. Theoretical prediction of the influence of droplet concentration
on the lightness (L) and chroma (C) of oil-in-water emulsions (n1s
1.33, n2s1.43) containing different droplet radii in micrometers (see
annotation box) but the same dye concentration (cdyes0.002 wt.%
red dye).

One of the major advances in recent years has been

the development of a theoretical approach to relate the
tristimulus color coordinates of emulsions to their com-
position (dye and droplet concentration) and microstruc-
ture (particle size distribution) w6●● x. In this approach,
it is assumed that the color of dilute emulsions is mainly
determined by the wavelength-dependence of light trans-
mitted through them, whereas the color of concentrated
emulsions is mainly determined by the wavelength-
dependence of light reflected from their surface. The
various steps involved in this approach are outlined here.
First, the scattering characteristics (Qs and g) of indi-
vidual droplets are calculated from knowledge of their
radius (r), their refractive index (n2) and the refractive
index (n1) of the surrounding medium, e.g. using Mie
theory w7●x. Second, the wavelength-dependence of the
scattering (S) and absorption (K) coefficients of an
emulsion are calculated in the visible region of the
electromagnetic spectrum (ls370–770 nm) from
knowledge of the droplet concentration (f) and scatter-
ing characteristics (Qs and g) using an appropriate
Fig. 2. Theoretical prediction of the influence of droplet radius on the
theory, e.g. radiative transport theory w8●,9●x. Third, the lightness (L) and chroma (C) of oil-in-water emulsions (n1s1.33,
reflectance spectrum R(l) (for concentrated systems) n2s1.43) containing the same droplet volume fraction (see annotation
or transmission spectrum T(l) (for dilute systems) of box) and dye concentration (cdyes0.002 wt.% red dye).
 D.J. McClements / Current Opinion in Colloid and Interface Science 7 (2002) 451–455
Fig. 3. Theoretical prediction of the influence of refractive index ratio
(n2yn1) on the lightness (L) and chroma (C) of oil-in-water emulsions
(n2s1.43) containing the same dye concentration (cdyes0.002 wt.%
red dye), droplet concentration (fs0.1) and droplet radius (rs1
mm).
increases steeply with droplet concentration up to a few
percent, after which it increases less steeply (Fig. 1).
Emulsion lightness (L*) increases with droplet radius
up to a maximum value for droplets of approximately
100 nm, after which it decreases (Fig. 2). Emulsion
lightness decreases to a minimum value and then
increases as the droplet refractive index moves from
below to above the continuous phase refractive index
(Fig. 3). The chroma of emulsions decreases with
increasing droplet concentration (Fig. 1), as droplet
radius moves away from 100 nm (Fig. 2) and as the
relative refractive index tends towards unity (Fig. 3),
which is to be expected because C is inversely related
to L* w6x. These numerical calculations demonstrate the
usefulness of light scattering theory as a means of
predicting the color of oil-in-water emulsions. Changes
in emulsion color resulting from alterations in compo-
sition or microstructure can be rapidly determined using
a personal computer, rather than having to carry out
time-consuming, costly and laborious experiments.
4. Relating experimental measurements of emulsion
color to theoretical predictions
One of the main problems that has been encountered
when trying to quantitatively relate the color of emul-
453
sions predicted by light scattering theory to the color of
emulsions measured by an analytical instrument is the
influence of the optical measurement system. The light
scattering theories that have been developed so far to
predict emulsion color assume that light waves are
reflected from a planar boundary between a continuous
phase and an emulsion, whereas in reality the reflection
occurs at an air-front plate-emulsion-back plate arrange-
ment. It is therefore necessary to develop methods of
correcting the light scattering theory so that it takes into
account the influence of the optical measurement system
w14●x. Three methods of carrying out this correction
procedure have been proposed w6x:
● Theoretical approach. This approach uses mathemat-
ical equations based on the fundamental physical
processes occurring to calculate the fraction of light
that is reflected or transmitted at the various bound-
aries within the optical measurement system
w13,14●,15x.
● Empirical calibration approach. This approach
involves establishing an empirical relationship
between the theoretically predicted reflectance or
transmittance and the experimentally measured value
using a series of emulsions of known composition
and microstructure w16●x.
● Optical system approach. This approach involves
redesigning the optical measurement system so that
it more closely corresponds to the assumptions made
in the light scattering theory w15x.
5. Experimental studies of emulsion color
A number of systematic experimental studies have
recently been carried out to determine the influence of
composition and microstructure on the color of oil-in-
water emulsions w14●,16●,17●,18,19●,20,21x. These
measurements are in excellent qualitative agreement
with predictions made using the light scattering theory
mentioned above. However, the quantitative agreement
is still fairly poor, mainly because of problems associ-
ated with accounting for the optical measurement
system.
Systematic measurements of the influence of droplet
concentration and size on the color of oil-in-water
emulsions have been carried out w16●,17●,18x. These
studies have shown that emulsion lightness increased
and emulsion chroma decreased steeply as the droplet
concentration was increased from 0 to 5 wt.%, after
which they change less dramatically, as predicted by the
theory (Fig. 1). Experiments with polydisperse n-hex-
adecane oil-in-water emulsions have shown that emul-
sion lightness has a maximum value and emulsion
chroma has a minimum value for droplets with radii of
approximately 0.1 mm, and that L* increased and C
decreased as the droplet radius was increased from 0.1
to 15 mm w17●x, which is in qualitative agreement with
454 D.J. McClements / Current Opinion in Colloid and Interface Science 7 (2002) 451–455
theory (Fig. 2). The increase in emulsion lightness and
decrease in emulsion chroma with increasing droplet
concentration (from 0 to 20 wt.%) and decreasing
droplet radius (from 15 to 0.1 mm) was confirmed by
sensory analysis for emulsions containing blue dye
w17●x. The size of the particles in oil-in-water emulsions
may change appreciably over time due to coalescence,
Ostwald ripening, or flocculation w1x. A recent study
has shown that the color of an oil-in-water emulsion
may change appreciably over time due to droplet growth
caused by Ostwald ripening w22x. On the other hand,
there was little change in droplet color when the droplets
(rs0.18 mm) in soybean oil-in-water emulsions were
flocculated by a depletion or an electrostatic screening
mechanism w19●x. This suggests that emulsion color is
more sensitive to changes in particle size caused by the
growth of individual droplets, rather than by the for-
mation of clumps of droplets. The addition of dyes to
emulsions has been shown to decrease their lightness
because less light is reflected back to the detector, and
increase their chroma because more light is selectively
adsorbed w16●,17●,18x.
Recent studies have examined the influence of refrac-
tive index ratio (sn2 yn1) on the color of oil-in-water
emulsions by varying the refractive index of the aqueous
phase using water-soluble cosolvents, such as polyols or
sugars w20,23,24x. In one of these studies, the influence
of refractive index ratio on emulsion color was studied
using polydisperse n-hexadecane oil-in-water emulsions
(rs0.15 mm, n2s1.43) with different amounts of glyc-
erol added to the continuous phase to vary its refractive
index from 1.33 to 1.53 w20x. As expected from theory,
emulsion lightness was high when the refractive index
of the droplets was either much smaller or much greater
than the refractive index of the continuous phase, but
decreased as the refractive index ratio tended towards
unity (Fig. 3). In the region where n2fn1, however, the
lightness of the emulsions depended strongly on whether
the plate behind the emulsions was black or white.
When the plate was black there was a trough in the
lightness, but when it was white there was a peak. This
was because a significant fraction of the light waves
penetrated through the emulsions when n2fn1, and were
therefore reflected from the back plate. When the back
plate was black, only a small percentage of the light
waves were reflected back and, therefore, there was a
decrease in emulsion lightness as n2™n1. When the
back plate was white, a large percentage of the light
waves were reflected back to the detector and, therefore,
there was an increase in emulsion lightness as n2™n1.
This highlights the practical difficulty of measuring the
color of emulsions using reflectance techniques when
the overall scattering by the droplets is weak. In these
systems, it is better to use transmission measurements
to quantify emulsion color.
6. Conclusions
There have been significant advances in our quanti-
tative understanding of the factors that determine the
color of food emulsions in recent years. A theoretical
protocol has been described to relate the color of an
emulsion to its colloidal characteristics, i.e. droplet size,
concentration and refractive index. This theory could be
used to optimize product color without having to carry
out time-consuming and laborious experiments. Never-
theless, considerable improvement of the existing theory
is required to make it more accurately describe the color
of emulsions determined experimentally. In particular,
theoretical developments are required to account for the
influence of the optical measurement system and to
account for light propagation through highly concentrat-
ed and flocculated emulsions. From a practical stand-
point, it would be useful to apply the theory describing
the colloidal basis of food color to real food emulsions.
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● of special interest
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