Advances in Colloid and Interface Science

97 Ž2002. 63᎐89

Theoretical prediction of emulsion color

David Julian McClementsU
Biopolymers and Colloids Laboratory, Department of Food Science, Uni¨ ersity of Massachusetts,
Amherst, MA 01003, USA

Abstract

The perceived quality of many commercial products that are based on emulsions is
determined by their color. In this article, a theory is presented to relate the color of
emulsions to their composition and microstructure. First, the scattering characteristics Ž Qs
and g . of individual droplets are calculated using Mie Theory. Second, the scattering Ž S .
and absorption Ž K . coefficients of a concentrated emulsion are calculated using radiative
transfer theory. Third, the reflectance spectrum Ž R . of the emulsion is calculated using
Kubelka᎐Munk Theory. Finally, the tristimulus coordinates Ž XYZ, or LU aU bU . of the
emulsion are calculated using color theory. There is excellent agreement between theoreti-
cal predictions and experimental measurements of the influence of droplet and chro-
mophore characteristics on the tristimulus coordinates of concentrated oil-in-water emul-
sions. 䊚 2002 Elsevier Science B.V. All rights reserved.

Keywords: Emulsions; Optical properties; Color; Light scattering

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
2. Theoretical relationship between emulsion color and droplet characteristics . . . . . . . 65
2.1. Calculation of scattering characteristics of emulsion droplets . . . . . . . . . . . . 66
2.2. Calculation of spectral transmittance or reflectance of emulsions . . . . . . . . . . 67
2.3. Relationship of tristimulus coordinates to spectral reflectance and trans-
mittance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
2.4. Influence of polydispersity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
2.5. Sample calculation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
3. Numerical calculations of emulsion color . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72

U
Tel.: q1-413-545-1019; fax: q1-413-545-1262.
E-mail address: mcclements@foodsci.umass.edu ŽD.J. McClements..

0001-8686r02r$ - see front matter 䊚 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 0 0 1 - 8 6 8 6 Ž 0 1 . 0 0 0 4 7 - 1
64 D.J. McClements r Ad¨ ances in Colloid and Interface Science 97 (2002) 63᎐89

4. Comparison of theory with experimental measurements . . . . . . . . . . . . . . . . . . . . 78

4.1. Qualitative agreement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78
4.2. Quantitative agreement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
5. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
Appendices . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88

1. Introduction

The perceived quality of emulsion-based products, such as foods, pharmaceuti-

cals, petrochemicals, health care products and cosmetics, is determined by a
combination of physicochemical characteristics such as stability, rheology and
appearance w2᎐4,32,27x. A great deal of theoretical and experimental work has
been carried out to establish the factors that determine the stability and rheology
of emulsions w18᎐21,31,33x. On the other hand, there have been few studies on the
factors that determine the overall appearance of emulsions. This is surprising given
the obvious importance of optical properties in determining the perceived quality
of emulsion-based products. The appearance of an object is the first sensory
impression that a person normally experiences of its quality. If the appearance of
the product does not fall within the expected range it may be rejected. A better
understanding of the relationship between the appearance of emulsions and their
composition and microstructure would aid in the design of emulsion-based products
with improved quality.
The appearance of a material is determined by a combination of factors,
including the nature of the light source, the detector and the material w23,36x. A
change in the characteristics of any of these three factors alters the perceived
appearance of the material. For example, the appearance of a material is de-
termined by the intensity, wavelength and polarization of the electromagnetic
radiation generated by the light source; by the geometry, composition and mi-
crostructure of the material; by the sensitivity and specificity of the detector; and
by the relative location of the light source, material and detector. In this manuscript
we will focus primarily on the influence of the composition and microstructure of
the emulsion on its overall appearance. Even so, it must be stressed that the same
emulsion will appear differently when observed using different light sources or
detectors.
Before presenting a theory that can be used to predict the color of emulsions it
is useful to give a brief overview of the physical processes that occur when a light
wave encounters an emulsion. When a beam of white light is incident upon the
outer surface of an emulsion some of the light is transmitted and some of the light
is reflected w14,15,25,35x. The relative proportions of transmitted and reflected light
depend on the geometry, composition and microstructure of the emulsion, as well
as the nature of the container that holds it w6,24,25x. That part of the light that is
transmitted into the emulsion travels through the continuous phase and interacts
 D.J. McClements r Ad¨ ances in Colloid and Interface Science 97 (2002) 63᎐89 65

with the droplets. When chromophoric substances are present in either the
continuous or dispersed phases some of the light wave is absorbed. The extent of
absorption depends on the concentration and absorbtivity of the chromophores and
on the wavelength of the light used. Some wavelengths are absorbed more strongly
than others so that the color of the light emerging from the emulsion is no longer
white. For example, if light is absorbed strongly at the wavelengths corresponding
to yellow-to-indigo, then the emerging light would appear red w29x. When a light
wave that enters an emulsion encounters a droplet, part of the wave is transmitted
and part of the wave is scattered w6,24,34x. The fraction of the wave that is
scattered and the direction that the scattered waves travel depends on the refrac-
tive index of the droplets and continuous phase, as well as on the size of the
droplets relative to the wavelength of light. In a dilute emulsion, a light wave that
travels through the emulsion may only encounter a single droplet before emerging
Žsingle scattering .. In a concentrated emulsion, a light wave scattered from one
droplet may be scattered by a number of other droplets before it emerges from an
emulsion Žmultiple scattering . w1x. In a highly concentrated emulsion, a significant
fraction of the incident light may travel back to the surface of an emulsion through
multiple scattering events and emerge as diffusely reflected light w25x. The overall
appearance of an emulsion is therefore determined by a combination of light
scattering and absorption phenomena. Scattering is largely responsible for the
turbidity, opacity or lightness of an emulsion, whereas absorption is largely respon-
sible for the chromaticness Žblueness, greenness, redness, etc...

2. Theoretical relationship between emulsion color and droplet characteristics

Human beings have great difficulty in objectively quantifying the precise color of
objects, even though they can easily subjectively discriminate between objects of
similar color w22x. For this reason, the color of a material is normally quantified
instrumentally in terms of tristimulus coordinates, such as the XYZ or LU aU bU
systems specified by the Commission International de l’Eclairage ŽCIE. w23,36x.
The advantage of using a 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 pre-defined quality criteria in a quantita-
tive manner. For example, in the LU aU bU color space, LU represents the lightness
and aU and bU are color coordinates: where qaU is the red direction, yaU is the
green direction, qbU is the yellow direction and ybU is the blue direction w36x. In
this section, we describe a theoretical approach that can be used to relate the
tristimulus coordinates of emulsions to their composition and microstructure. The
various steps involved in this approach are shown schematically in Fig. 1 for both
dilute and concentrated emulsions. In this approach, we assume that the color of
dilute emulsions is determined mainly by the light that is transmitted through
them, whereas the color of concentrated emulsions is determined mainly by the
light that is reflected from their surface.
66 D.J. McClements r Ad¨ ances in Colloid and Interface Science 97 (2002) 63᎐89

Fig. 1. Schematic representation of the approaches used to predict the color of concentrated and
dilute emulsions.

2.1. Calculation of scattering characteristics of emulsion droplets

The first step in calculating the color of an emulsion is to calculate the scattering
efficiency Ž Qs . and the asymmetry factor Ž g . of the droplets over the visible
wavelength range Ž380᎐780 nm. ŽFig. 1..1 The scattering efficiency is a measure of
the fraction of the incident energy that is removed from the forward beam by
scattering, whereas the asymmetry factor is a measure of the angular distribution
of the energy scattered by a droplet w24x. Mathematically, the scattering efficiency
is the ratio of the scattering cross-section to the geometrical cross section, whereas
the asymmetry factor is the average cosine of the scattering angle w6x. As g tends
towards unity, the scattered light is directed more and more in the forward
direction. These two parameters can be calculated for droplets of arbitrary size
using the Mie Theory w13,37x:

1
In systems where the absorption coefficient of an emulsion is comparable to, or larger than, the
scattering coefficient it is not possible to uncouple absorption and scattering phenomenon Žas assumed
in this work.. Under these circumstances one should use the extinction efficiency Qext , rather than the
scattering efficiency Qs .
 D.J. McClements r Ad¨ ances in Colloid and Interface Science 97 (2002) 63᎐89 67

2 ⬁
Qs s Ý Ž 2 n q 1 . < an < 2 q < bn < 2 Ž1.
x2 ns1

4 ⬁ n Ž n q 2. 2n q 1
w f Ž an ,bn .x q w f ⬘ Ž an ,bn .x
gs 2
x Qs
Ý
ns1
½ nq1 n Ž n q 1. 5 Ž2.

where x s 2 ␲ rn1r␭, r is the droplet radius, ␭ is the wavelength, m is the ratio of

the complex refractive index of the droplets to that of the surrounding medium
Žs w n 2 y i k 2 xrw n1 y i k 1 x., n1 and n 2 are the refractive indices of the continuous
phase and dispersed phases, k 1 and k 2 are the absorptive indices of the continuous
phase and dispersed phases, f w a,b x and f ⬘w a,b x are functions of a and b ŽAppendix
A., and a and b are coefficients that depend on x and m. Recurrence relations are
available in the literature for calculating the a and b coefficients w6,37x. Under
certain conditions it is possible to use approximations for the above expressions.
For example, for small particles the Rayleigh᎐Gans᎐Debye Theory can be used, or
for particles with m close to unity the anomalous diffraction theory can be used
w24x. Nevertheless, with the widespread availability of sophisticated mathematical
software and rapid digital computers there is little reason for using these approxi-
mations rather than the full Mie Theory. Indeed, there are computer programs
available on the Internet for calculating Qs and g as a function of relative
refractive index, wavelength and droplet size w28x. Calculations of the dependence
of Qs and g on x are shown in Fig. 2 for a typical oil-in-water emulsion. The main
limitation of the Mie Theory is that it does not take into account mutual
polarization effects that become important when the droplets are in close prox-
imity, i.e. concentrated or flocculated emulsions w24x.

2.2. Calculation of spectral transmittance or reflectance of emulsions

The second step in calculating the color of an emulsion is to determine the

Fig. 2. Dependence of scattering characteristics of emulsion droplets Ž Qs and g . on the size parameter
Ž x . for 1-␮m radius oil droplets Ž n 2 s 1.43. dispersed in water Ž n1 s 1.33..
68 D.J. McClements r Ad¨ ances in Colloid and Interface Science 97 (2002) 63᎐89

spectral transmittance Žfor dilute emulsions. or spectral reflectance Žfor concen-

trated emulsions. ŽFig. 1..
Dilute Emulsions: In terms of its optical properties, an emulsion can be defined
as being ‘dilute’ when a light wave that propagates through it only encounters a
single droplet before emerging, i.e. no multiple scattering occurs w24x. In this
section, we assume that the appearance of a dilute emulsion is determined by the
light transmitted through it. In practice, the color of a dilute emulsion perceived by
an individual is a combination of reflected, scattered and transmitted light, which is
more difficult to quantify mathematically. Even so, transmission measurements on
dilute emulsions are extremely valuable for instrumentally quantifying their color.
The fraction of light transmitted through a dilute emulsion depends on the
scattering of light by the droplets and the absorption of light by any chromophores.
The overall amount of light transmitted through an emulsion can therefore be
characterized by the extinction coefficient, ␧, which depends on the turbidity Ž ␶ .
and the absorption coefficient Ž ␣ .:

I s I0 exp Ž y␧ x . Ž3.

␧s␶q␣ Ž4.

where, I is the intensity of light transmitted through the emulsion, I0 is the

intensity of the light transmitted through the continuous phase of the emulsion in
the absence of droplets and chromophores, and x is the emulsion path length. The
transmission coefficient of an emulsion is given by:

T s IrI0 s exp Ž y w ␶ q ␣ x x . Ž5.

The absorption coefficient spectra Ž ␣ Ž ␭ .. of an emulsion normally has to be

determined experimentally. The emulsion may contain chromophoric species in
both the oil and aqueous phases. To determine the overall absorption spectrum of
an emulsion it may therefore be necessary to measure the absorption spectra of the
oil and aqueous phases separately: ␣ E Ž ␭ . s ␾␣ D Ž ␭ . q Ž1 y ␾ . ␣ C Ž ␭ . where the
subscripts E, D and C refer to the emulsion, dispersed phase and continuous
phase, respectively and ␾ is the dispersed phase volume fraction. The turbidity of
an emulsion can be calculated from the scattering characteristics of its droplets
w24x:

3␾Qs
␶s Ž6.
4r
The transmission spectrum T Ž ␭ ., of a dilute emulsion can therefore be calculated
from the droplet size and concentration and the measured absorption spectrum by
combining Eq. Ž5. and Eq. Ž6..
Concentrated emulsions: In this section, we assume that a ‘concentrated’ emul-
sion is one in which the light waves propagate entirely by diffusion w30x however,
the droplets are not close enough together for mutual polarization effects to be
 D.J. McClements r Ad¨ ances in Colloid and Interface Science 97 (2002) 63᎐89 69

significant w24x. Most concentrated emulsions are optically opaque, and therefore
their color is determined by the reflection of light waves from Žor near to. their
surface, rather than by the transmission of light waves through them. The spectral
reflectance of an optically opaque emulsion can be related to its scattering and
absorption characteristics using the Kubelka᎐Munk Theory w25x:

K K K
Rs1q
S
y ( S S
q2 Ž7.

where, K and S are the absorption and scattering coefficients of the emulsion,
respectively. Note that R, K and S are all wavelength dependent. The
Kubelka᎐Munk Theory is based on a two-flux solution of the radiative transfer
theory, which mathematically describes the propagation of light waves through
media that both scatter and absorb radiation w30x. The K and S coefficients can be
related to the scattering and absorption characteristics of emulsion components
using the following equations which were established by empirically comparing the
predictions made using the two-flux-radiative-transfer theory to those made using a
more exact many-flux theory w30x:

K s 2␣E Ž8.

S s 34 ␲ r 2 Qs w 1 y g x y 14 ␣ E Ž9.

As mentioned earlier, these equations are based on the assumption that the
propagation of light through an emulsion is entirely diffuse. In practice, light may
pass through a material by both diffuse and non-diffuse processes and therefore
the equations must be modified. These modifications become increasingly impor-
tant as the droplet concentration or scattering efficiency decreases w17,30x. A
mathematical model has been developed to account for this effect in emulsions
where the Rayleigh᎐Gans᎐Debye Theory is valid w16x. The above equations are
also invalid at high droplet concentrations because of mutual polarization effects,
i.e. the polarization field of one droplet may interfere with that of another droplet
w24x. This effect usually occurs when the droplets are closer than a few diameters
from one another, for example in concentrated or flocculated systems. Another
limitation of the above theory is that it assumes that the reflection occurs from a
boundary between a pure continuous phase and a semi-infinite emulsion w25x. In
reality, an emulsion is usually contained in an optically transparent container, Že.g.
a plastic, glass or quartz bottle or cuvette. and so the reflection occurs from an
air-wall-emulsion-wall arrangement ŽFig. 3.. Methods of taking into account the
influence of the optical measurement arrangement on emulsion color are described
in a later section. Other limitations of the Kubelka᎐Munk Theory and methods of
overcoming them have been reviewed by w17x.
70 D.J. McClements r Ad¨ ances in Colloid and Interface Science 97 (2002) 63᎐89

Fig. 3. Comparison of reflection from a planar continuous phase᎐emulsion boundary Žassumed in the
Kubelka᎐Munk Theory. with reflection from an air᎐wall᎐emulsion᎐wall interface Žexperimental situa-
tion..

2.3. Relationship of tristimulus coordinates to spectral reflectance and transmittance

The third step in calculating the color of an emulsion is to calculate the

tristimulus coordinates of the emulsion from its spectral transmittance Ždilute
emulsions. or spectral reflectance Žconcentrated emulsions. ŽFig. 1.. The X, Y, Z
tristimulus coordinates are related to the spectral reflectance by the following
equations w36x:

770nm
Xsk Ý SŽ␭ . x Ž␭ . RŽ␭ . Ž 10.
380nm

770nm
Ysk Ý SŽ␭ . y Ž␭ . RŽ␭ . Ž 11 .
380nm

770nm
Zsk Ý SŽ␭ . z Ž␭ . RŽ␭ . Ž 12 .
380nm

100
ks 770nm
Ž 13.
Ý SŽ␭. yŽ␭.
380nm
 D.J. McClements r Ad¨ ances in Colloid and Interface Science 97 (2002) 63᎐89 71

where SŽ ␭ . is the spectral distribution of the standard illuminant at wavelength ␭,

x Ž ␭ ., y Ž ␭ ., z Ž ␭ . are the human response functions of the CIE color system and
RŽ ␭ . is the spectral reflectance of the material. The above equations highlight the
fact that the appearance of an emulsion depends on the nature of the light source
Ž SŽ ␭ .., the observer Ž x Ž ␭ ., y Ž ␭ ., z Ž ␭ .. and the material ŽT Ž ␭ . or RŽ ␭ ... It is
particularly important to use values of SŽ ␭ . that are applicable to the light source
used in an experiment when comparing theoretically and experimentally de-
termined tristimulus coordinates. The same approach can be used to calculate the
X, Y, Z values of a dilute emulsion, but in this case the transmittance spectrum
ŽT Ž ␭ .., rather than the reflectance spectrum Ž RŽ ␭ .., is used in Eqs. Ž10. ᎐ Ž13..
The X, Y and Z coordinates are not easily interpreted in terms that are used by
human beings to describe color w22x. Consequently, a variety of other color scales
have been developed that use coordinates that are more closely related to quanti-
ties associated with human perception of color w36x. One of the most widely used is
the CIE 1976 LU aU bU color scale, which is calculated from the X, Y, Z values
using published formulas w36x:

3
LU s 116 YrYn y 16
' Ž 14.

3
aU s 500 'XrX n '3
y YrYn Ž 15.

3 3
bU s 200 'YrY n y ZrZn
' Ž 16.

These equations are only applicable when XrXn , YrYn , or ZrZn are greater than
0.01, and must be corrected otherwise w22x. The X n , Yn and Zn values are
calculated using Eqs. Ž10. ᎐ Ž12., but with RŽ ␭ . Žfor concentrated emulsions. or
T Ž ␭ . Žfor dilute emulsions. equal to unity. The color of an emulsion can therefore
be predicted based on its spectral reflectance or transmittance.

2.4. Influence of polydispersity

The theory described above assumes that the droplets in the emulsion are all of
the same size, i.e. they are monodisperse. In reality, emulsions normally contain a
range of different droplet sizes and the light waves are scattered differently by the
droplets in each size class w6x. In this section, we show how polydispersity can be
incorporated into the equations for calculating the transmission and reflection
coefficients of emulsions. For dilute emulsions, the turbidity given by Eq. Ž6.
should be replaced by the following expression:

3 N ␾ i Qs,i
␶s Ý Ž 17.
4 is1 ri
72 D.J. McClements r Ad¨ ances in Colloid and Interface Science 97 (2002) 63᎐89

where, ␾ i , r i and Qs,i are the volume fraction, radius and scattering efficiency of
the droplets in the ith size class, and N is the total number of size classes. The
transmittance spectrum and tristimulus coordinates can then be calculated as
described above. For concentrated emulsions, the scattering coefficient given by
Eq. Ž9. should be replaced with the following expression:

3 N 1
Ss ␲ Ý r i2 Qs,i w 1 y g i x y ␣E Ž 18.
4 is1 4

where, ⌺s,i , and g i are the scattering cross-section and asymmetry factor of the
droplets in the ith size class. The reflectance spectrum and tristimulus coordinates
can then be calculated as described above. When an emulsion contains a range of
different droplet sizes the undulations in the optical properties, Že.g. Qs . with
droplet radius that are observed in a monodisperse emulsion are smoothed out
w24x. Incidentally, Eqs. Ž17. and Ž18. can also be used to calculate the transmission
and reflection spectra of emulsions containing droplets consisting of different types
of material.

2.5. Sample calculation

In this section we carry out a sample calculation in order to demonstrate how the
above theory can be used to predict the color of an emulsion. We assume that we
would like to know the LU , aU , bU values of a 10 vol% oil-in-water emulsion that
contains spherical monodisperse droplets with a radius of 1-␮m. The oil phase is
taken to have a refractive index of 1.434 and the aqueous phase is taken to have a
refractive index of 1.330. The emulsion is assumed to contain a known concentra-
tion of water-soluble red dye, the absorption spectra of which in pure water has
been measured experimentally. The first step is to calculate the scattering charac-
teristics of the droplets Ž Qs and g . as a function of wavelength in the visible region
of the electromagnetic spectrum wEqs. Ž1. and Ž2.x. The second step is to calculate
the scattering and absorption coefficients Ž S and K . of the emulsion as a function
of wavelength wEqs. Ž8. and Ž9.x, and then use these values to calculate the spectral
reflectance Ž R . ŽEq. Ž7... Finally, the LU Žs 93.2. , aU Žs 13.1. and bU Žs 3.2.
values are calculated from the spectral reflectance wEqs. Ž10. ᎐ Ž16.x. The informa-
tion used to calculate these tristimulus coordinates are tabulated in Appendix B. It
should be noted that these calculations assume that the reflection occurs at a
water-emulsion boundary ŽFig. 3..

3. Numerical calculations of emulsion color

The light scattering theory described above provides manufacturers of

emulsion-based products with a powerful tool for predicting the influence of
composition and microstructure on the optical properties of their products. The
theory could be used to optimize product color without having to carry out
 D.J. McClements r Ad¨ ances in Colloid and Interface Science 97 (2002) 63᎐89 73

time-consuming and laborious experiments. In this section the theory is used to

investigate some of the major factors that influence the color of concentrated
oil-in-water emulsions: droplet concentration; droplet radius; refractive index ratio;
dye concentration. Absorption spectra of the red dye used in the theoretical
calculations were determined experimentally Žsee ␣ column in Appendix B.. In all
of the numerical calculations reported here it is assumed that light reflection
occurs from a planar boundary between the pure continuous phase and an
emulsion ŽFig. 3., i.e. the influence of the optical measurement system is ignored
Žsee later.. Numerical calculations of the color of dilute emulsions have recently
been carried out and compared with experimental measurements w7x, so we will
only focus on the factors that influence the color of concentrated emulsions here.
The influence of droplet concentration Ž ␾ s 0᎐0.2. and droplet radius Ž r s
0.1᎐20 ␮m. on the color of monodisperse oil-in-water emulsions Ž n1 s 1.33,
n 2 s 1.43. was calculated ŽFigs. 4 and 5.. The dependence of the LU aU bU values on
droplet concentration for emulsions with the same droplet radius Ž r s 0.1, 1 or 10
␮m. is shown in Fig. 4. Emulsion lightness Ž LU . increased with increasing droplet
concentration because more light was multiply scattered backwards by the droplets.
The lightness increased steeply as the droplet volume fraction increased from
0᎐0.05 and then increased less steeply at higher droplet concentrations ŽFig. 4a..
This has important consequences for the development of emulsion-based products
with reduced droplet concentrations, Že.g. low fat salad dressings.. When the
droplet concentration is decreased below a certain level the product appearance
changes dramatically, which may have an adverse impact on perceived quality.2
The chromaticness of the emulsions decreased with increasing droplet concentra-
tion, Ži.e. < aU < and < bU < tended toward zero., which is to be expected because the
magnitudes of aU and bU are approximately proportional to the reciprocal of the
lightness w5x so that an increase in lightness tends to cause a decrease in chromatic-
ness. From a sensory perspective, this means that the color of the emulsions
becomes more faded as the droplet concentration is increased w8x.
The dependence of emulsion color on droplet concentration is strongly affected
by droplet size ŽFig. 4.. The LU value increased and the chromaticness decreased
as the droplet radius decreased from 10 to 0.1 ␮m. The full dependence of the
color coordinates on droplet radius is shown in Fig. 5 for emulsions with the same
droplet concentration Ž ␾ s 0.1.. The lightness has a maximum value in emulsions
containing 0.1-␮m radius droplets, and decreases for smaller or larger droplet
sizes. In contrast, the turbidity of dilute emulsions containing the same kind of
aqueous and oil phases has a maximum radius value for droplets of approximately
1.3-␮m w7x. The differences in the dependence of lightness and turbidity on the
radius can be attributed to the fact that the turbidity depends only on the fraction
of light removed from the forward beam by scattering, Ži.e. Qs ᎏ Eq. Ž6.., whereas
the lightness also depends on the direction that the light is scattered, Ži.e. Qs and g
ᎏ Eq. Ž9... As the droplet radius increases, more of the light is scattered in the

2
The reason that skim milk appears watery, whereas full fat milk appears creamy, is that skim milk
has a much lower droplet content Žf 0.1%. than full fat milk Žf 4%..
74 D.J. McClements r Ad¨ ances in Colloid and Interface Science 97 (2002) 63᎐89

Fig. 4. Theoretical prediction of the influence of droplet concentration on the color coordinates of
oil-in-water emulsions Ž n1 s 1.33, n 2 s 1.43. containing different droplet radii Žsee annotation box., but
the same dye concentration Ž cdye s 0.002 wt.% red dye..

forward direction Ž g ª 1, Fig. 2., and therefore a smaller fraction of light is

scattered backwards and detected as diffusely reflected light. As expected, the aU
and bU coordinates of the emulsions exhibit minimum values at the droplet size
where the lightness exhibits its maximum value.
The influence of refractive index on the color of emulsions is shown in Fig. 6.
These calculations were carried out assuming that the droplet radius Ž r s 1 ␮m.,
droplet concentration Ž ␾ s 0.1. and refractive index of the droplets Ž n 2 s 1.43.
remained constant however, the refractive index of the continuous phase varied
Ž n 2 s 1.33᎐1.53.. In practice, this kind of situation could be achieved by adding a
water-soluble solute to the aqueous phase of an oil-in-water emulsion, e.g. salt or
sugar. The lightness decreased and the chromaticness increased as the refractive
index of the droplets tended towards that of the continuous phase ŽFig. 6.. This is
because the scattering efficiency of the droplets decreases as the refractive index
 D.J. McClements r Ad¨ ances in Colloid and Interface Science 97 (2002) 63᎐89 75

Fig. 5. Theoretical prediction of the influence of droplet radius on the color coordinates of oil-in-water
emulsions Ž n1 s 1.33, n 2 s 1.43. containing the same droplet concentration Ž ␾ s 0.1. and dye concen-
tration Ž cdye s 0.002 wt.% red dye..

ratio Ž n 2rn1 . tends towards unity w24x and consequently a smaller fraction of light
is scattered in the backwards direction.
The influence of dye concentration on the color of emulsions is shown in Fig. 7.
Emulsion lightness decreased with increasing dye concentration because dye
molecules absorbed light and therefore less light was reflected back from the
emulsions. As would be expected, the presence of dye had a pronounced influence
on the chromaticness Ž aU and bU . of the emulsions. The presence of dye in an
emulsion changes its tristimulus coordinates because the selective absorption of
light at different wavelengths alters the relative magnitude of the color ratios used
in Eqs. Ž14. ᎐ Ž16. Ž X r X 0 , Y r Y0 , Z r Z0 .. In the absence of dye, the emulsions
became more red Žq⌬ aU . and more yellow Žq⌬ bU . with increasing droplet
concentration. This was because the scattering efficiency of 1-␮m-radius droplets
76 D.J. McClements r Ad¨ ances in Colloid and Interface Science 97 (2002) 63᎐89

Fig. 6. Theoretical prediction of the influence of aqueous phase refractive index ratio Ž n 2 rn1 . on the
color coordinates of oil-in-water emulsions Ž n 2 s 1.43. containing the same dye concentration Ž cdye s
0.002 wt.% red dye., droplet concentration Ž ␾ s 0.1. and droplet radius Ž r s 1 ␮m.. The refractive
index of the droplets was 1.43.

decreased with increasing wavelength Ž Qs column in Appendix B. so that red light

was less scattered than green light Žleading to an increase in redness; q⌬ a. and
yellow light was less scattered than blue light Žleading to an increase in yellowness;
q⌬ bU .. As expected, the presence of red dye in the emulsions caused them to
become redder Žq⌬ aU . ŽFig. 7b. because the dye molecules selectively absorbed a
smaller fraction of red light than green light, causing X r X 0 to decrease less than
Y r Y0 wEq. Ž15.x. The emulsions also became more yellow in the presence of dye
ŽFig. 7c. because the dye molecules selectively absorbed less yellow light than blue
light, causing Z r Z0 to decrease less than Y r Y0 . In the presence of dye, the
redness of the emulsions decreased Žy⌬ aU . with increasing droplet concentration.
This is because droplets scattered light more strongly in the red region of the
 D.J. McClements r Ad¨ ances in Colloid and Interface Science 97 (2002) 63᎐89 77

Fig. 7. Theoretical prediction of the influence of droplet concentration on the color coordinates of
oil-in-water emulsions Ž n1 s 1.33, n 2 s 1.43. containing different dye concentrations Žsee annotation
box., but the same droplet radius Ž r s 1 ␮m..

electromagnetic spectrum than in the green region, therefore the amount of red
light that was reflected from the emulsions increased, causing X r X 0 to decrease
more than Y r Y0 wEq. Ž15.x. The yellowness of the emulsions containing red dye
decreased Žy⌬ bU . with increasing droplet concentration because droplets scat-
tered light less strongly in the yellow region of the electromagnetic spectrum than
in the blue region.
The numerical calculations shown in Figs. 4᎐7 demonstrate the usefulness of the
light scattering theory as a means of predicting the color of concentrated oil-in-
water emulsions. Changes in emulsion color resulting from alterations in composi-
tion or microstructure can be rapidly determined using a personal computer, rather
than having to carry out time-consuming, costly and laborious experiments. In the
following section, the validity of the light scattering theory is established by
comparing theoretical predictions with experimental measurements of emulsion
color.
78 D.J. McClements r Ad¨ ances in Colloid and Interface Science 97 (2002) 63᎐89

4. Comparison of theory with experimental measurements

The experimental data presented in the following section are taken from recent
studies performed in our laboratory on the influence of composition and mi-
crostructure on emulsion color w8,9,26x.

4.1. Qualitati¨ e agreement

Predictions made using the light scattering theory presented above are in
excellent qualitative agreement with experimental measurements of the color of
concentrated emulsions with different droplet and dye characteristics ŽFigs. 8᎐11..
The impact of droplet size and concentration on the color coordinates of n-

Fig. 8. Experimental measurements of the influence of droplet concentration on the color coordinates
of n-hexadecane oil-in-water emulsions Ž r s 0.15 ␮m. containing either no dye or 0.002 wt.% red dye
w10x.
 D.J. McClements r Ad¨ ances in Colloid and Interface Science 97 (2002) 63᎐89 79

Fig. 9. Experimental measurements of the influence of droplet radius on the color coordinates of
n-hexadecane oil-in-water emulsions containing the same droplet concentration Ž ␾ s 0.1. and dye
concentration Ž cdye s 0 or 0.002 wt.% red dye. w10x.

hexadecane oil-in-water emulsions containing either no dye or a red dye are shown
in Figs. 8 and 9. Emulsion lightness increased and chromaticness decreased as the
droplet concentration increased ŽFig. 8., particularly between 0 and 5 wt.% oil, as
predicted by the theory ŽFig. 4.. Emulsion lightness decreased and chromaticness
increased as the droplet radius increased from 0.1 to 15 ␮m ŽFig. 9., again in
agreement with the theory ŽFig. 5.. The increase in emulsion lightness and
decrease in chromaticness with increasing droplet concentration and decreasing
droplet size has also been demonstrated by sensory analysis w11x.
The influence of refractive index ratio on emulsion color has been studied using
polydisperse n-hexadecane oil-in-water emulsions Ž r s 0.15 ␮m, n 2 s 1.43. with
different amounts of glycerol added to the continuous phase to vary its refractive
index from 1.33 to 1.53 w8x. As expected from the theory ŽFig. 6., emulsion lightness
was high when the refractive index of the droplets was either much smaller or
80 D.J. McClements r Ad¨ ances in Colloid and Interface Science 97 (2002) 63᎐89

Fig. 10. Experimental measurements of the influence of aqueous phase refractive index ratio Ž n 2 rn1 .
on the color coordinates of n-hexadecane oil-in-water emulsions containing the same dye concentration
Ž cdye s 0.002 wt.% red dye., droplet concentration Ž ␾ s 0.1. and droplet radius Ž r s 1 ␮m.. The
refractive index of the continuous phase was varied by adding glycerol w8x. The refractive index of the
droplets was 1.43.

much greater than the refractive index of the continuous phase, but decreased as
the refractive index ratio tended towards unity ŽFig. 11.. In the region where
n 2 f n1 however, the color 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
n 2 f n1 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 n 2 ª n1. When the back plate was
white a large percentage of the light waves were reflected back to the detector and
 D.J. McClements r Ad¨ ances in Colloid and Interface Science 97 (2002) 63᎐89 81

Fig. 11. Experimental measurements of the influence of droplet concentration on the color coordi-
nates of n-hexadecane oil-in-water emulsions containing different dye concentrations Žsee annotation
box., but the same droplet radius Ž r s 0.15 ␮m..

therefore there was an increase in emulsion lightness as n 2 ª 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.
The impact of dye concentration on the color coordinates of n-hexadecane
oil-in-water emulsions is shown in Fig. 11. As expected from the theory ŽFig. 7.,
emulsion lightness decreased and chromaticness increased as the dye concentration
increased because more of the light was absorbed by the chromophores in the dye.

4.2. Quantitati¨ e agreement

To quantitatively compare the color of emulsions predicted by the light scatter-

82 D.J. McClements r Ad¨ ances in Colloid and Interface Science 97 (2002) 63᎐89

ing theory to the color of emulsions measured by an analytical instrument it is

necessary to account for the nature of the optical measurement system. As
mentioned previously, the light scattering theory assumes that the light waves are
reflected from a planar boundary between a continuous phase and an emulsion,
whereas in reality the reflection occurs at an air-wall-emulsion-wall arrangement
ŽFig. 3.. Experiments have shown that the reflectance of light from a micro-hetero-
geneous material is reduced appreciably when it is covered by a smooth layer of an
optically transparent material w12x. This reduction is a result of the reverberations
of light waves within the container: each time a light wave encounters the emulsion
it is partly transmitted and absorbed ŽFig. 3.. 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. Three methods of carrying out this
correction procedure are outlined below:
Theoretical approach: The first method involves theoretically accounting for the
influence of the optical measurement system on the fraction of light reflected from
a concentrated emulsion w26x. This approach uses mathematical equations to
calculate the fraction of light that is reflected or transmitted at the various
boundaries within the optical measurement system.
The first step is to relate the predicted reflection coefficient, R P , which is
calculated assuming that the reflection occurs from a continuous phase᎐emulsion
interface, to that at a container᎐emulsion interface, R CE w25x:
Ž 1 y R SCE .Ž 1 y R EC
D .
RP
R CE s Ž 19 .
1 y R EC
D
RP

where, R SCE is the specular reflectance at the container᎐emulsion boundary and

RD
EC is the diffuse reflectance of light traveling from within the emulsion at the
emulsion᎐container boundary:

n E y nC 2
S
R CE s ž / Ž 20 .
n E q nC

␲r2 sin 2 Ž ␣ y ␤ . tan 2 Ž ␣ y ␤ .

EC s q
RD H0 ž sin 2 Ž ␣ q ␤ . tan 2 Ž ␣ q ␤ . / sin␣cos␣ d␣ Ž 21 .

Here, n E and n C are the refractive indices of the emulsion and container, and ␣
and ␤ are the angles of incidence and refraction of the light beam at the
container᎐emulsion boundary.
The second step is to calculate the reflection coefficient from the air-container-
emulsion system taking into account the reverberations of the light beam within
the container walls w25x:
S D
TAC TCA R CE
R corrected s RAC
S
q Ž 22 .
1 y R CA
D
R CE
 D.J. McClements r Ad¨ ances in Colloid and Interface Science 97 (2002) 63᎐89 83

S S
where TAC and RAC are the specular transmittance and reflectance at the air᎐con-
tainer boundary Ž RACS
s 1 y TAC S . D
, and TAC D
and RAC are the diffuse transmittance
and reflectance at the container᎐air boundary Ž RAC s 1 y TAC
D S
rn2C s 1 y TCAD .
.
The main advantage of this method is that it can be used without having to carry
out any experiments. The color of an emulsion can be predicted from its composi-
tion and microstructure provided information about the optical measurement
system is known, e.g. the refractive index of the material making up the measure-
ment cell and the angle of incidence of the light beam.
Empirical calibration approach: The second method involves establishing an
empirical relationship between the theoretically predicted reflection coefficient
Ž R P . and the experimentally measured reflection coefficient Ž R M .. In a previous
study, we found that R P could be related to R M using the following empirically
determined correction factor:

RM
CŽ K , S. s Ž 23 .
RPŽ K , S.

Initially, a series of emulsions containing a wide range of droplet sizes, droplet

concentrations and dye concentrations are prepared and their reflectance Ž R M . is
measured over an appropriate wavelength range, Že.g. ␭ s 380᎐770 nm, in 10-nm
increments .. The absorption coefficient Ž K ., scattering coefficient Ž S . and pre-
dicted spectral reflectance Ž R P . are then calculated theoretically for the same
droplet characteristics, dye characteristics and wavelengths. The emulsions used in
the calibration experiments must cover the whole range of K and S values that will
be encountered in practice. The correction factor is determined at each wavelength
by dividing the measured spectral reflectance by the predicted one. An interpola-
tion technique is then used to calculate C(K, S) for any pair of K and S values.
The dependence of C(K, S) on the predicted scattering and absorption coefficients
is shown in Fig. 12 for a UV-visible spectrophotometer with an integrating sphere
used in our laboratory. As the scattering coefficient and absorption coefficient
decreased, the measured reflectance became appreciably smaller than the pre-
dicted value and so C(K, S) decreased. The correction factor is then stored in the
computer program used to calculate the spectral reflectance of the emulsions and
is applied to the predicted reflectance values in order to take into account
container effects.
The main disadvantage of this approach is that a large number of calibration
experiments have to be carried out for each optical measurement system using
emulsions of known composition and microstructure. Nevertheless, the empirical
calibration approach seems to be the most successful for obtaining good quantita-
tive agreement between theory and experiment Žsee below..
Optical system approach: Another method of improving the agreement between
theory and experiment is to use an optical measurement system that corresponds
more closely to the assumptions made in the light scattering theory ŽFig. 3.. Ideally
the emulsion should be contained in an optically transparent container with
84 D.J. McClements r Ad¨ ances in Colloid and Interface Science 97 (2002) 63᎐89

Fig. 12. Empirically determined correction factor that can be used to correct theoretically predicted
reflectance values for container effects.

parallel walls that is constructed from a material with the same refractive index as
the continuous phase of the emulsion. In addition, the sample container, optical
source and optical detector should be placed within a fluid that also has the same
refractive index as the emulsion continuous phase. The reflection of the light beam
will then occur from a boundary between a material with the same refractive index
as the emulsion continuous phase and the emulsion itself, as assumed in the
theory. This approach would be expected to greatly improve the agreement
between the theory and experiment, however, it may still be necessary to apply
some empirical correction to further improve the agreement because of the
practical difficulty in finding materials with appropriate refractive indices.
Comparison with theory: Theoretical predictions of the reflectance of 10 wt.%
n-hexadecane oil-in-water emulsions Ž r s 1 ␮m, n1 s 1.33, n 2 s 1.43. containing a
red dye are compared with experimental measurements ŽFig. 13.. The theoretical
predictions were either uncorrected for container effects or corrected using the
theoretical or empirical calibration approaches. There is a trough in the experi-
mental reflectance spectrum at wavelengths corresponding to the peak in the
absorption spectrum of the dye, i.e. 400 - ␭ - 600 nm. At other wavelengths there
is a high reflectance due to diffuse scattering of light by the concentrated emulsion.
Qualitatively, the uncorrected predicted reflectance Ž R P . spectrum agrees with the
experimental reflectance spectrum however, it is appreciably higher at all wave-
lengths because it does not take into account the optical measurement system.
There is an appreciable improvement in the agreement between prediction and
experiment when R P is corrected using the theoretical approach described above
wEqs. Ž19. ᎐ Ž22.x. Nevertheless, the agreement is still quantitatively poor in the
 D.J. McClements r Ad¨ ances in Colloid and Interface Science 97 (2002) 63᎐89 85

Fig. 13. Comparison of predicted and measured reflectance spectra for n-hexadecane oil-in-water
emulsions containing the same dye concentration Ž cdye s 0.002 wt.% red dye., droplet concentration
Ž ␾ s 0.1. and droplet radius Ž r s 1 ␮m..

regions where light absorption is low, Ži.e. low K value.. The best agreement
between the predicted and experimental reflectance spectrum was obtained using
the empirical correction approach ŽFig. 13.. Differences in the predicted re-
flectance spectra calculated using the different approaches led to differences in the
predicted tristimulus color coordinates ŽFig. 14.. Again we see that the best
agreement between predictions and measurements is obtained using the empirical
calibration approach, followed by the theoretical approach. The uncorrected ap-
proach gives good qualitative agreement, but poor quantitative agreement, as
would be expected because it does not take into account the optical measurement
system.

5. Conclusions

The tristimulus coordinates of emulsions can be predicted from a knowledge of

their composition and microstructure using the light scattering theory. The pre-
dicted dependence of emulsion color on droplet characteristics Žradius, concentra-
tion, refractive index. and chromophore characteristics Žabsorptivity, concentra-
tion. is in good qualitative agreement with experimental measurements. Excellent
quantitative agreement between predicted and measured emulsion color can be
86 D.J. McClements r Ad¨ ances in Colloid and Interface Science 97 (2002) 63᎐89

Fig. 14. Comparison of predicted and measured color coordinates for n-hexadecane oil-in-water
emulsions containing the same dye concentration Ž cdye s 0.002 wt.% red dye., droplet concentration
Ž ␾ s 0.1. and droplet radius Ž r s 1 ␮m..

obtained when the influence of the optical measurement system is taken into
account. The theory presented in this paper could be used by scientists to
investigate the influence of microstructure and composition on emulsion color.
Consequently, the need to carry out costly and time consuming experiments to
optimize the color of emulsion-based products could be eliminated.

Acknowledgements

The author thanks Prof. Clydesdale for many useful discussions and Drs Chana-
mai and Chantrapornchai for their excellent performance of the experimental
measurements reported in this manuscript.
 D.J. McClements r Ad¨ ances in Colloid and Interface Science 97 (2002) 63᎐89 87

Appendix A

Expression for calculating the asymmetry factor of emulsion droplets w37x

4 ⬁ n Ž n q 2.
w Re Ž an . Re Ž anq1 . q Im Ž an . Im Ž anq1 .
gs
x Qs2 Ý
ns1
½ nq1
qRe Ž bn . Re Ž bnq1 . q Im Ž bn . Im Ž bnq1 .x
2n q 1
w Re Ž an . Re Ž bn . q Im Ž an . Im Ž bn .x
q
n Ž n q 1. 5
Appendix B

Wavelength dependent optical characteristics needed to calculate the LU , aU and

U
b values of a 10 vol.% hexadecane oil-in-water emulsion with a 1-␮m droplet
radius The emulsion contained 0.002 wt.% of a water-soluble red dye, see text for
further details

␭ x Qs g ␣ S K R Sx Sy Sz
Žnm. Žmy1 .

380 21.99 3.211 0.9841 18.82 2858 37.64 0.8503 0.007 0 0.031
390 21.43 3.157 0.9841 22.02 2818 44.04 0.8381 0.022 0.001 0.104
400 20.89 3.1 0.9839 24.32 2793 48.63 0.83 0.112 0.003 0.532
410 20.38 3.041 0.9837 25.61 2775 51.21 0.8255 0.377 0.01 1.796
420 19.9 2.979 0.9835 26.93 2753 53.85 0.8208 1.189 0.035 5.711
430 19.43 2.916 0.9833 27.98 2725 55.97 0.8168 2.33 0.095 11.37
440 18.99 2.853 0.9832 30.09 2695 60.19 0.8098 3.458 0.228 17.34
450 18.57 2.789 0.9829 36.62 2671 73.25 0.7916 3.724 0.421 19.63
460 18.17 2.725 0.9826 47.36 2655 94.71 0.7662 3.243 0.669 18.61
470 17.78 2.661 0.9823 60.13 2635 120.3 0.7401 2.124 0.989 14
480 17.41 2.598 0.9821 73.37 2604 146.7 0.7159 1.048 1.524 8.915
490 17.05 2.536 0.9818 85.8 2572 171.6 0.6954 0.33 2.142 4.791
500 16.71 2.475 0.9815 91.58 2547 183.2 0.6859 0.051 3.343 2.815
510 16.39 2.415 0.9812 89.68 2531 179.4 0.6878 0.095 5.132 1.614
520 16.07 2.356 0.9808 84.23 2519 168.5 0.6951 0.628 7.041 0.775
530 15.77 2.298 0.9804 76.77 2509 153.5 0.7061 1.687 8.785 0.43
540 15.48 2.241 0.98 64.87 2499 129.7 0.7255 2.869 9.425 0.201
550 15.19 2.186 0.9797 46.21 2486 92.43 0.762 4.267 9.796 0.086
560 14.92 2.132 0.9794 26.44 2469 52.88 0.8133 5.625 9.415 0.037
570 14.66 2.08 0.979 12.2 2448 24.4 0.8684 6.947 8.678 0.019
580 14.41 2.029 0.9787 5.288 2428 10.58 0.9109 8.304 7.885 0.015
590 14.16 1.979 0.9783 2.347 2413 4.694 0.9395 8.612 6.352 0.009
600 13.93 1.931 0.9779 1.204 2403 2.408 0.9562 9.046 5.374 0.007
610 13.7 1.883 0.9774 0.849 2395 1.698 0.963 8.499 4.264 0.003
88 D.J. McClements r Ad¨ ances in Colloid and Interface Science 97 (2002) 63᎐89

620 13.48 1.838 0.9769 0.639 2385 1.278 0.9678 7.089 3.161 0.002
630 13.26 1.793 0.9765 0.609 2372 1.218 0.9685 5.062 2.088 0
640 13.06 1.75 0.9761 0.599 2354 1.198 0.9686 3.547 1.386 0
650 12.86 1.708 0.9757 0.559 2334 1.118 0.9695 2.147 0.81 0
660 12.66 1.668 0.9753 0.6 2313 1.2 0.9683 1.252 0.463 0
670 12.47 1.628 0.9749 0.63 2295 1.26 0.9674 0.68 0.249 0
680 12.29 1.59 0.9745 0.65 2278 1.3 0.9668 0.347 0.126 0
690 12.11 1.553 0.9741 0.69 2263 1.38 0.9657 0.15 0.054 0
700 11.94 1.517 0.9736 0.8 2251 1.6 0.963 0.077 0.028 0
710 11.77 1.482 0.9731 0.979 2240 1.958 0.9591 0.041 0.015 0
720 11.61 1.448 0.9726 1.329 2232 2.658 0.9524 0.017 0.006 0
730 11.45 1.415 0.9721 1.959 2224 3.918 0.9424 0.009 0.003 0
740 11.29 1.383 0.9715 2.55 2218 5.1 0.9344 0.005 0.002 0
750 11.14 1.352 0.9709 2.62 2211 5.24 0.9335 0.002 0.001 0
760 11 1.322 0.9704 2.74 2203 5.48 0.9319 0.001 0 0
770 10.85 1.293 0.9698 2.66 2193 5.32 0.9327 0.001 0 0

References
w1x A.E. Bailey, D.S. Cannell, Practical method for calculation of multiple light scattering, Phys. Rev.
E50 Ž1994. 4853᎐4864.
w2x P. Becher, Encyclopedia of Emulsion Technology, vol. 4, Marcel Dekker, New York, 1996.
w3x P. Becher, Encyclopedia of Emulsion Technology, vol. 2, Marcel Dekker, New York, 1985.
w4x P. Becher, Encyclopedia of emulsion technology, Basic Theory, vol. 1, Marcel Dekker, New York,
1983.
w5x F.W. Billmayer, M Saltzman, Principles of Color Technology, 2nd ed, John Wiley and Sons, New
York, 1981.
w6x C.F. Bohren, D.R Huffman, Absorption and Scattering of Light by Small Particles, New York,
Wiley, 1983.
w7x R. Chanamai, D.J. McClements, Prediction of emulsion color from droplet characteristics: dilute
monodisperse oil-in-water emulsions. Food Hydrocoll. 2000 Žin press..
w8x W. Chantrapornchai, D.J. McClements, Influence of refractive index on the color of concentrated
oil-in-water emulsions. J. Food Sci. 2001 ŽSubmitted..
w9x W. Chantrapornchai, F. Clydesdale, D.J. McClements, Theoretical and experimental study of
spectra reflectance and color of concentrated oil-in-water emulsions, J. Colloids Int. Sci. 218
Ž1999a. 324᎐330.
w10x W. Chantrapornchai, F. Clydesdale, D.J. McClements, Influence of droplet characteristics on the
optical properties of colored oil-in-water emulsions, Colloids Surf. A155 Ž1999b. 373᎐382.
w11x W. Chantrapornchai, F. Clydesdale, D.J. McClements, Influence of droplet size and concentration
on the color of oil-in-water emulsions, J. Agric. Food Chem. 46 Ž1998. 2914᎐2920.
w12x H.W. Chatfield, The Science of Surface Coatings, Ernest Benn Ltd, London, 1962 Žp. 347..
w13x J.V. Dave, Scattering of electromagnetic radiation by a large, absorbing sphere, IBM J. Res. Dev.
13 Ž1969. 302᎐313.
w14x R.W. Frei, J.D. MacNeil, Diffuse Reflectance Spectrocopy in Environmental Problem-Solving,
CRC Press, Cleveland, Ohio, 1973.
w15x R.W. Frei, M.M. Frodyma, V.T. Lieu, Diffuse reflectance spectroscopy, in: G. Svehla ŽEd..,
Comprehensive Analytical Chemistry, Ch. 3, Elsevier Scientific, Amsterdam, 1975.
w16x R. Graaf, J.G. Aarnoudse, F.F.M. de Mul, H.W. Jentink, Light propagation parameters for
anisotropically scattering media based on a rigorous solution of the transport equation, Appl. Opt.
28 Ž1989. 2273᎐2279.
w17x B. Hapke, Theory of Reflectance and Emittance Spectroscopy, Cambridge University Press,
Cambridge, 1993.
 D.J. McClements r Ad¨ ances in Colloid and Interface Science 97 (2002) 63᎐89 89

w18x P.C. Hiemenz, R. Rajagopalan, Principles of Colloid and Surface Science, Marcel Dekker, New
York, 1997.
w19x R.J. Hunter, Introduction to Modern Colloid Science, Oxford University Press, Oxford, 1993.
w20x R.J. Hunter, Foundations of Colloid Science, vol. 2, Oxford University Press, Oxford, 1989.
w21x R.J. Hunter, Foundations of Colloid Science, vol. 1, Oxford University Press, Oxford, 1986.
w22x R.S. Hunter, R.W Harold, The Measurement of Appearance, 2nd ed, Wiley Interscience, New
York, 1987.
w23x D.B. Judd, G. Wyszecki, Color in Business, Science, and Industry, 2nd ed, New York, Wiley, 1963.
w24x M. Kerker, The Scattering of Light, Academic Press, New York, 1969.
w25x G. Kortum, Reflectance Spectroscopy: Principles, Methods, Applications, Springer-Verlag, New
York, 1969.
w26x D.J. McClements, W. Chantrapornchai, F. Clydesdale, Prediction of food emulsion color using
light scattering theory, J. Food Sci. 63 Ž1998. 935᎐939.
w27x D.J. McClements, Food Emulsions: Principles, Practice and Techniques, CRC Press, Boca Raton,
FL, 1999.
w28x B. Michel, Optics of Small Particles and Inhomogeneous Materials. Žwww.unternehmen.
comrBernhard᎐Michelreindex.html. 2000.
w29x F. Miller, College Physics, 4th ed, Harcourt Brace Jovanovich Inc, New York, 1977, p. 556.
w30x P.S. Mudget, L.W. Richards, Multiple scattering calculations for technology, Appl. Opt. 10 Ž1971.
1485᎐1502.
w31x Th.F. Tadros, Correlation of viscoelastic properties of stable and flocculated suspensions with
their interparticle interactions, Adv. Colloid Interface Sci. 68 Ž97. Ž1996..
w32x L.L. Schramm, Emulsions: Fundamentals and Applications in the Petroleum Industry, ch 3,
American Chemical Society, Washington, D.C, 1992.
w33x T.F Tadros, Fundamental principles of emulsion rheology and their applications, Colloid Surf. 91
Ž30. Ž1994..
w34x H.C. van de Hulst, Light Scattering by Small Particles, John Wiley and Sons, New York, 1957.
w35x W.W. Wendlandt, Modern Aspects of Reflectance Spectroscopy, Plenum Press, New York, 1968.
w36x G. Wyszecki, W.S. Stiles, Color science: Concepts and Methods, Quantitative Data and Formulae,
2nd ed, Wiley, New York, 1982.
w37x N.C. Wickramasinghe, Light Scattering Functions for Small Particles, John Wiley and Sons, New
York, 1973.