J. Soc. Cosmetic Chemists,19, 649-667 (Sept.

16, 1968)

Color and Its Measurements*

MICHAEL BORNSTEIN, Ph.D. t

Synopsis--An account is given for the fundamental principles of diffuse and tristimulus reflectancemeasurements. The experimental basisfor these measurements,including the CIE and Munsell systemsfor defining color space, is also discussed. These principles are supported with qualitative and quantitative examples for color matching, as well as interaction
studies with reflectance values and the Kubelka-Munk niques are also presented. equation. A review of several availa-

ble commercial color measuring devices, reference standards, and sample preparation tech-

INTRODUCTION

The stability and appearanceof colored cosmeticand pharmaceutical dosageforms are dependent on the dye or lake employed, as well as many other parameters. These may include adjuvant absorption coefficientsof microscopic and macroscopic structures as well as

otherphysicaland chemical properties (1). Althoughmostformulators still rely on empirical knowledgein the subject of color measurement, many articles have appeared with respect to color instrumentation. Swartz and Cooper (2) have reviewed a number of pharmaceutical colorantsand their properties. Lachman and associates have applied various parameters to color stability of tablet formulations (3-5). Goodhart, Lieberman, and associates 7) have alsostudiedthe stabil(6, ity of certified dyes in tablets. Raft (8, 9) has presentedreports of
color measurements obtained from FD&C colorants. measurements and their

The purposeof this communication to discuss is principlesand instruments used in diffuse and tristimulus reflectance

applicationto the development coloredpharmaceutical of dosage forms.

* Presented October 2, 1967, Sixth Annual A. Ph. A. Industrial Pharmaceutical Technology Meeting, Chicago p Pitman-Moore Division, Dow Chemical Co., Research Center, Zionsville, Ind. 46077. Present address, Eli Lilly & Co., Indianapolis, Ind. 46206.
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CONCEPTS OF COLOR

The sensationof coloris the result of radiant energy, between400 and

700mu, impingingthe eye (10). Sincethe phenomenon colorincludes of psychological well as physicalaspects, as color scalesand instruments are often designedto include both parameters. The psychological aspectsof colorare the resultof colorcodes storedin the brain, including association an individual hue suchas blue-greenwith a characteristic of sensation suchascoolness. Physicalaspects colorresult from the fact of
that visible radiant energyis necessary vision. for The basicprinciple on which tristimulus color measurementis based

depends the assumption mostcolors on that may be produced a comby

bination of red, blue, and green coloredlights. Red and green beams combine to form yellow, whereas blue and green combine to form a bluish-green color. A purple colorresultsfrom the combinationof red and blue; a white hue forms when the red, green, and blue primaries unite. By varying the amountsin the three primary beams,all intermediate colors can be produced. This phenomenonof uniting three
basic colors to form white is the basis for an additive color mixture.

Onemay alsoform a subtractivecolormixture by usingyellow,magenta, and cyan pigments. The resultant color darkenswith the subtractive mixture as more of thesefilters combine; when all three subtractiveprimaries unite, a black color is formed. Numerous systems have been developedto definecolor. This discussion will be primarily concerned with the CIE and Munsell systems.
CIE SYSTEM

There are two basicfoundations which colorimetrydepends. The on first is that color can be matched by a suitablemixture of three selected light radiationsand that if two colorsare matchedby three radiations, the mixture of these two colors is found additive by suitable optical means. The essential principles of this tristimulus color system were

first independently developed Ives (ll) andGuild (12). In 1931,the by Commission Internationale de l'Eclairge (CIE) standardizedthe color
mixture characteristicsof an "average observer" and developeda standard framework for a color specification. This standard observer represents a series of functions determined from data providedby observers matchingthe color at eachwavelength from 400 to 700 m, with mixturesfrom three primary light sources. The experimentalset-up for definingthe "average" human observer measures observer's the response the three primary colorsby focusing to

COLOR AND ITS MEASUREMENT

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651

1.6

GREEN 'x

540

1.2

RED

I BLUE

[ 4o

.'c'

,oo

400

500

600

700

400

mu

Figure 1. Responseof the "standard CIE

observer" to an equal energy light source

Figure 2. Chromaticity diagram illustrating the visible spectrum locus measured with 10 spectrophotometric readings. The tristimulus chromaticity coordinates (x,y) for illuminant C are plotted near the center of the chart

the threelightson a screen the samelocationsothat they may be mixed in in properproportions. A monochromatic light source focused a spot is on just adjacentto the mixture of the three coloredlights. The observer views the screenthrough a cone angle of two degreesand is asked to adjust the three primary colorsuntil the mixture matchesthe monochromaticlight source,recordingthe relative amountsof the three lights necessaryfor the match. Figure 1 showstheserelative amounts of red, green,and blue lightsbetween400 and 700 mu neededby the observer for the match. The monochromaticlight is ideally a "white light," meaningthat it is an equal energysource containinglight from all visible wavelengths. Most standard light sourcesdo contain light of every color, but not in equal amounts. Illuminant A, found in standard incandescent tungstenlight sources, or has light at all wavelengths,with muchmore energyat longerwavelengths. Illuminant B is a light source equivalentto the noonsun. Illuminant C, representing daylight on the north side of a building, contains light of all wavelengths with much more energyin the blue part of the spectrum. Figure 2 showsthe three dimensions the CIE color solid in two dimensions of using x and y chromarlcity coordinates. These chromaticity coordinates calculatedby are expressingthe tristimulus values X, Y, Z, as fractions of their total These tristimulus values of a sample are either calculated from diffuse reflectance measurements to be discussed (9) later or they may be mea-

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DOMINAN

ILL0 'C'
F{gur 3. Chromaticity diagram (x,y) defining i]]um{nant C, dominant wavelength, and purity

sureddirectlyontristimulus eolorimeters. Only two coordinates needto be specified sincethe total of the x, y, and z chromaticitycoordinates equals unity. Here the coloraxisor chromaticity coordinates on the lie outsideof the triangle goingfrom blue to greento red, whereas white the to black axis or luminosity function is the center; this brightness axis wouldbe perpendicular the screen to with the white at the top andblack at the bottom. Nonspectrum colors representmixtures having the chromaticities represented any point alongthe straightline joiningthe at extremitiesof the spectrumlocusand are producedby mixing suitable

portions radiant of engery taken from extreme the short-wave than (less
440 m/) and long-wave(greaterthan 680 m/) regions the spectrum. of Colorsrepresented pointson straight lines betweenthe achromatic by pointC in Fig. 2 andthe spectrum locus called are spectral colors. The CIE system divides characteristics light from whichcolor the of is composed into severalcomponents includingluminance,dominant wavdength, and purity. Luminanceis the characteristic that differentiatesthe light reflectedfrom a standard white sample,illuminated with a 100-W lamp, from that of light reflectedfrom this samewhite samplewhen it is illuminatedby a 200-W lamp with all other things being equal. The dominant wavelength may be definedas the wavelength that appears bedominant the lightandisusually mostinto in the tensevariety of radiant energy the stimulus. Purity refers the dein to greeto whichthe dominant wavelength appears predominate the to in
light.

Figure3 shows the dominant that wavelength obtained plotting is by the chromaticitycoordinates the illuminant and sample. A line is of

COLOR

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White

8
9

IO
1 2 3
5

.10

Black

Neutral
colour

Chroma

Saturated
colour

Figure

Hue, value, and chroma coordinates of the Munsell system

drawn from the achromatic or illuminant point through the sample coordinates onto the locus of the diagram. This point on the locus is calledthe dominant wavelength. The per cent purity is determinedby the ratio of the distancefrom the illuminant point to the samplecoordinates, A, divided by the distancefrom the illuminant point to the spectrum locus,B, expressed per cent. Luminosity is expressed per in in cent Y, obtained directly from tristimulus colorimeters. This diagram in which each point representsthe chromaticity, independentof lumi-

nance,calledchromaticity ism, a diagram.

MUNSELL SYSTEM

Another systemfor definingcolor space,called the Munsell system (13), is basedon a colorsolidillustrated in Fig. 4. The central vertical axisrepresents locusof neutral colorswith white at the top and black the at the bottom. In this system, lightnessof the sample, called value, is divided into a number of stepsfrom 0 to 10. The distanceof the sample from the central vertical axis is a function of the saturation or intensity

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of color and is called chrornaon the Munsell map. Chroma is also divided into a seriesof steps, with the neutral axis or gray being 0, whereasa fully saturatedsamplehasa chromaof 12. Color, or hueasit

is called in the Munsell system (14), is presentedby different planes around the vertical axis of the Munsell solid. In this system,the whole solid is divided into ten equal vertical segments with five principal hues (red, yellow, green, blue, and purple) occupyingthe central planesof alternate segments while intermediate hues (yellow-red, green-yellow, blue-green,purple-blue and red-purple) occupy the remaining planes.
Each hue segmentis further divided into ten sectionsnumbered 1 to 10, with the main hue segmentalways numbering5. The hue of a sampleis designated a number, indicating the section by of the segment, followedby symbols which showthe colorof the segment involved. For example, 10P indicatesthe hue section10 of the purple

segment. To completethe specification the sample,the value quanof tity followsthe hue which is then followedby a stroke and then the chroma. Here the colordefinedat 10 P / hasthe hue 10 P, the value5,
and the chroma of 8.
COLOR DIFFERENCE AND TOLERANCE

It is of interest to point out that color differences are not entirely linear throughout the entire CIE chromaticity diagram since,if one calculatestwo points on this diagram, another set of points twice as far apart do not necessarily have a totally linear difference color (9, 15). in In other words, equal distanceson the diagram do not always indicate the samedegreeof color change. Judd (16) devised Uniform ChromaticityScale(UCS) adopted the by the National Bureau of Standards(NBS). Adams (17) followedwith his chromatic-valuediagram which was acceptedby the American Society for Testing Materials (ASTM). MacAdam (18) investigatedcolordifferenceswhere the observermade a large number of matches on a series of test colors located at various points in the chromaticity diagram. The spreadin the colorsettingsnecessary make a match (Fig. 5) was to used by MacAdam as the criterion of sensitivity to color differences. The distances from points on the boundary of each ellipseto the central point within the ellipseapproximatelycorrespond the chromaticity to difference just perceptiblewith certainty under specified viewing conditions; this just perceptible color differenceis defined as one MacAdam unit. The orientation of the major axis of individual ellipsesis a function of the dominant wavelength and purity changes, but does not

COLOR

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Y 1.s 530 52.

0 'X 4

o.4-499

oo

Fgure5. MacAdam's perceptible chromaticitydifferences the CIE diagram. in The axis of each ellipse has been multiplied by 10 for illustrative purposes
MONOCHROMATOR

SOURCE

MPLE

PHOTO-SENSOR
Figure6. Schematicdiagramrepresenting major components a spectrophotometer the of or
colorimeter. Spectrophotometers use prismatic or grating monochrometers where colorimeters would contain filters

changewith lightness; i.e., the shape and orientation remain constant

at differentluminosities. The ellipses vary in size with a change do of lightness,becomingsmaller as lightnessincreases,since errors in makingcolordecisions decrease underimproved light-viewing conditions.
COLOR MEASURING INSTRUMENTS

Reflectance Spectrophotometers

This type of instrument,diagrammed Fig. 6, is basedon a beam of in monochromatic light penetrating into a sample. This light is scattered in many directions, partially absorbed, finally re-emerges the is and to

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400

700

400

700

SAMPLE REFLECTANCE (R)

SOURCEEMISSION(E)

RxE

SPECIFYING

THE

COLOR

OF A SAMPLE

Figure 7. Schematic diagram for interaction factors to produce color vision

surface. Measurements may be plotted as reflectancers. wavelength using a relatively nonabsorbing white referencestandard. This information is then usedfor quantitative Kubelka-Munk equationsor it may
be converted to tristimulus values which will be discussed.

Commercial instruments include the Hardy General Electric Spectrophotometer,Bausch& Lomb Spectronic505 with reflectance attachment, as well as the Beckman DU Spectrophotometer with the reflectanceaccessory. The G. E. instrument has a recorderand automatically
converts reflectance data to tristimulus values. The Bausch & Lomb

instrument has a recorder whereas the Beckman DU is a manual spectrophotometer.

Tristimulus Instruments

It should be pointed out that the CIE system was developedto eliminateeye variationsby usingthe "standardobserver." The principle behind tristimulus colorimeters,illustrated in Fig. 7, is as follows: A light source, strikesa samplehavinga reflectance E, curve,R. This interaction resultsin a reflectanceenergy,RE, which is specificfor each wavelength; this is alsothe energy striking the eye. This resultingRE passes filtersand is multiplied by eachof the hypotheticalcolormixthe ture curves,9, and , representing colorvisionof the standardobserver in the CIE system. This produces three new curves,each having an area representedby the tristimulus values X, Y, and Z. The above manipulationsagain indicate that the CIE systemspecifies color by a three quantities,X, Y, and Z, calledtristimulusvalues. These values

COLOR

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representthe amounts of primary red, green, and blue color that the standard observer would need to get a match. Ii each of these tristimulusvaluesis divided by the sum of three, the resulting values x, y, and z, called chromaticity coordinates,give the proportion of the total stimulus attributed to each primary color. Furthermore, since the sum of the three chromaticity coordinates unity, the valuesof x and 3' is plotted on the chromaticity diagram may be used alone to specify the color. The third achromatic dimension of lightness or darkness is specifiedby the tristimulus value. The manipulations included in tristimuluscolorimetryare mathematically presentedbelow: Weighted Ordinate Method Calculation of Chromaticity Coordinates

X = ExC'Rx .X
oo

700

x=

X
X + Y + Z

Y = oo 'Ex c'RX':?x
Z = Ex c'RX.zX
oo

700

y=X
z=

y
+ Y + Z

700

a
X + Y + Z

z = I--

(x-t-y)

The Hardy General Electric Spectrophotometer, previously discussed,provides spectral reflectancecurves in addition to tristimulus
values. This combination results in nonmetameric matches in color

formulations which are colorssimilar in appearance under all light sources. Tristimulus instruments alone often produce metameric matches whichlookthe same onlyif similarviewingconditions used. are Instrument Development Laboratories(IDL) market the Color-Eye whichis an abridged spectrophotometer giving10 or 16 visiblewavelength points as well as tristimulus values. The instrument is also de-

signed measure to fluorescence a sample of since tristimulus the filtersare placed between sample detector illustrated Fig. 8. A comthe and as in puter may alsobe purchased with the instrumentto directly measure
color difference in MacAdam units.

A competitive tristimulus colorimeter called the Hunterlab D-25

Color Difference Meter (19),* schematically presented Fig. 9, inin

cludesvacuum phototubes, calibratedtristimulusfilters, and a transis* HunterAssociates Laboratory, Inc., 9529LeeHighway, Fairfax,Va. 22080.

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REFLECTANCE -----,,,f

SPECULAR--lt INSERT ''-----.._GHT SOURCE

REFLECTANCE STANDARD

SAMPLE /< ....

DIRECT LICHT STOPS

STRAY LIGHT STOPS

TNSSSION
TPNSMISSION STANDARD

ZEROING SLIT

MICROMETRIC

SLIT

(VERTICAL

ApERATURE)

SPLIT LENS

'
,
. TRISTIMULUS ABRIDGED SPE CTROPHOTOME FILTERS and

ROTATING ,,,, "FLICKER" MmmO , ,

STOP
t

TER

PHOTOMULTIPLIER
I

Figure 8.

Block diagram of the I.D.L. Color-Eye

torized color measurement circuit. The readoutis presented X, ,Z in tristimulus values as well as L, a, b scales(20) which closelycorrelate with the Munsell system. The L measures lightnessor value, whereas the a and b readingsrepresentchromaticity coordinates. A computer may be purchasedwith the instrument to give direct color difference
measurements in NBS units. The Hunterlab Color Difference Meter

doesnot offer the 10 or 16 wavelengthspectrophotometric points offered in the Color-Eye, which are useful wherenonmetamericmatchesare required. The Hunter colorimeter may, however, be used in combination with a Beckman DU or other diffusereflectance spectrophotometer if nonmetameric matches are required and may be applied to routine control of pharmaceuticalcolor formulations.
Another commercial instrument, called the Davidson and Hemmend-

inger Colorant Mixture Computer (COMIC), enablesthe coloristto measure reflectedlight from a sampleof variouswavelengths, usingK/S

COLOR

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(359

COLOR-MEASUREMENT CIRCUIT

..

L
a -b

L _ TRISTIMU LUS
FILTEIS CLEAR

METHACRYLATE
LITE PIPE

Figure 9.

Block diagram of the Hunterlab

D-25 Color Difference Meter

valuesto make a nonmetameric match (21). The techniques involvedto perform thesecalculations will be discussed.
REFERENCE STANDARDS

Sincemost tristimulusdata are a comparison luminosity and chroof maticity, referencestandardsmust be used as a means of comparison. An ideal reflectancereferencestandard would diffuselyreflect 100% of the visible light impinged on its surfaceat all wavelengths. Magnesium oxide,magnesium carbonate,barium sulfate,and white vitrolite have application as reflectance standards. A disadvantage with MgO, MgCOa, and BaSO4 is that they are brittle and yellow with age. The yellowing process slowestwith BaSO4. Their advantage, however, is is that these standardshave a diffusereflectanceof about 97-99% in the visible wavelengths,makinx reflectancereading almost absolute.

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White Vitrolite, usedas an NBS referencestandard,is an opal glass material with a fire-polishedsurface. The absolutereflectanceis 90% over most of the visible spectrum, requiring CIE correction factors at each wavelength. Vitrolite is a permanent standard, is easily cleaned
and excellent for routine colorimetric work.

SAMPLEPREPARATION TECHNIQUES
Powders

Sample powdersare presentedto most tristimulus colorimetersin a

manner similar to reference standards. A dish with a 4 in. diameter and

/-in. depthis sufficient a sample as holder. The powder oftenpacked is and smoothed with a spatula; a glasscoverslip may be placedover the sample,provided the referencestandardhas a similar cover.
Tablets

Since the 2- to 4-in. sample viewing area found in most tristimulus colorimetersis greater than most tablets, it is suggestedthat sample holdersof in. or smaller be made, and the tablets measuredindividually wherehigh precision required. The light beam of the instrument is would have to be adjusted here in order to decreasethe beam diameter hitting the individual tablet.
Suspensions

The reflectanceof opaquesuspensions may be measuredfrom a plastic cylinder with a glassbottom. Caution shouldbe exercised be sure to that the precipitate is well suspended, resultingin uniform colorreadings.
Clear Solutions

The color of clear solutions is best measured

with transmittance

tri-

stimuluscolorimetrysincereflectance measurements often lead to excessive light scattering. If reflectancemeasurementis required, one may place a standardizedwhite ceramicbackgroundin the samplecell; the clear solution transmits the light onto the background which in turn reflectsthis light to the photodetector. The thicknessof the solutionmust be controlled by adjusting the volume of sample used; a 5-ml glass sampleholder is feasiblefor darker or highly coloredsolutionswhereasa volume of 10 ml may be usedfor nearly clear and colorless solutions. It should be noted that the light beams travel twice the distance with this technique,making the reading approximatelytwice the stimulusvalues obtained with normal reflectancetechniques.

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QUANTITATIVE COMPUTATION COLOR OF ANDCOLOR FORMULATION

Kubelka-Munk Method

Sincea number of different dye combinationsare often possible when matching a given standard and the useof many FD&C dyesis becoming limited, formulators must often resort to color combinationsfor matching purposes. However, many matchesare metameric and therefore require spectrophotometric well as tristimulus analysis. Spectrophotometric as
matches, used in combination with tristimulus values of a mixture, tend

to retain the characteristicfeatures of each colorant. An existingproblem with spectrophotometric reflectancecurvesis that these curves do not directly follow Beer's law since concentrationis not directly linear with reflectance. Kubelka (22) developednumerousformulasfor correlating reflectancewith concentrationby making scatteringand surface difference corrections. It was found that the ratio of light absorptionto light scattering at a given wavelength is proportional to the concentration of the dye in the sample. The relationshipshownhere is derived from the Kubelka-Munk equation.

( - )
Where R = 1.0 at 100% reflectance.

()

Relationship K/S to concentration of

K/$
Where

= kc

(2)

K = light absorbed S = light scattered

k = constantof proportionality
C = concentration of colorant

SinceK/S factorsfor eachdye at a particular wavelengthare additive when mixed together,this principlemay be usedas a basisfor computing the amountsof variousdyesnecessary match a given standard. to A sample equationfor findingK/S of a colorantmixture is:
(K/$),x. = a(K/S)A + b(K/$) + c(r/$)c +
Where

...w(K/X)whe se (3)

a = concentration

of colorant of colorant

A C

b = concentration
c = concentration w = concentration

of colorant B
of white base

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This equationwould be usedas follows: The K/S for each dye and excipient are first obtained by measuringthe diffusereflectancefor a known concentration of the dye and excipient or white base at a given wavelength. This R value may be substituted in the Kubelka-Munk equation (eq. 1), in order to calculatethe K/S values, or these may be obtained directly from tableswhich giveK/S valuesfor reflectance reading between0 and 100%. The K/S value of the diluent shouldbe subtracted from each K/S of the dye to obtain the correctedK/S values. For example,one can calculatethe K/S valuesof three dyes, blue, red, and yellow,separately onewavelength. The total K/S valuesat that one at wavelengthwill equal the K/S value of a brown, which resultsfrom the proper concentrations the above three dyes. Therefore, if the of value of the sampleis knownat three wavelengths and the K/S valuesof the blue, red, and yellow (at any concentration) are also known at the samewavelength,one may set up three simultaneous equationsto calculate the actual concentrationsof blue, red, and yellow used to make the match. The Davidson and Hemmendinger COMIC Computer performs these calculationsat 16 wavelengthsbetween 400 and 700 m/ and alsocalculates tristimulusvaluesfor the purpose colormatching (21). of
WeightedOrdinate Method

This method, mathematically illustrated earlier in this presentation, is a meansof calculatingtristimulus valuesand chromaticity coordinates
from reflectance data. It should also be stressed that x, y, and are

tristimulus values resultingfrom the averagevisual observerand are used as imaginary primaries under specificillumination for tristimulus calculations. The values X, Y, and Z, at any wavelength, correspond to the magnitude of these primaries needed by the standard observerto match a color. In addition, chromaticity coordinates,x, y, and z, are the tristimulus valuesX, Y, and Z expressed fractionsof their total, as which equal one. These chromaticity coordinatesof the tristimulus values are then plotted on an x, y chromaticity diagram and the spectrum locus is located. The weighted ordinate method is a means of determining tristimulus valuesand samplelightnesseither from spectrophotometric reflectancecurvesor directly using tristimulus colorimetry. Using this method, the relative energy of the light sourceE c (for illuminant C) at a particular wavelength, which is found in published color tables (23), is multiplied by the tristimulusvalue c and reflectance value for the samewavelengthbetween400 and 700 m/, usually 10 m/ apart. The values are then summedover the total range to yield the X, Y, and

COLOR

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66;3

100

'

80-

60-

400

500

540

600

700

mu

Figure 10. Diffuse reflectancespectra of FD&C Red #3 Dye (100 mg) and light magnesium carbonate, USP (2.00 g). Key: A, standard dye spectrum: B, new sample lot spectrum

Z tristimulusvalues. Chromaticity coordinates then calculatedby are expressing tristimulus values as fractions of their total values. The the luminosity or lightness is determined directly from the Y tristimulus value expressed per cent. in Although there are other available methodsfor calculating tristimulus values(23), the weightedordinatetechniqueserves a goodmeans as
for deriving color values from diffuse reflectancemeasurements.
IHARMACEUTICAL APPLICATION

Quality Controlof FDiC Dyes The purity and quality of pharmaceutical dyes may be controlled, as illustrated with the following example: A manufacturer purchasesa

newlot of FD&C Red#3 dye. The predetermined standard spectrum of

this dye compared to a MgCO3 reference standard is shown in Fig. 10 The spectrum for the standard dye is also diluted in a 1:20 ratio with MgCO3, sinceit is important that the color componentbe highly diluted with a relatively nonabsorbingdiluent. This ensures similar grain size a for the dye and reference standard, causing the reference and sample scatteringcoefficients canceleach other in comparison to measurements. This facilitatesscatteringto be independentof wavelength(24).

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The specifications 100 mg of standard dye diluted with 2.00 g of for MgCO3, (Fig. 10,A) are asfollows' Xmx 540 mu; R = 62.8% (K/S = = 0.1102); Tolerance = - 10%. A new lot of FD&C dye (Fig. 10,B) givesthe followingspectrophotometric values after 100 mg of the dye has been diluted with 2.00 g of MgCO3 USP' X..... = 540 m; R = 65.5% (K/S = 0.0909).
Since K/S values are proportional to concentration,the purity of the new lot may be found from the calculationsshown below, assigninga purity of 100% to the standarddye.
K/Ssta. Csta. _ K/Xsamrle Csample
Where

(4)

K = absorptioncoefficient S = scatteringcoefficient C = dye concentration % in

0.02
0.0909

oo% = --;

Csample

Csampe 81.6% =

The new samplelot shouldbe rejected,sinceit contains18.4c impurities. It should be emphasized that the colorist must check the linearity of K/S valueswith concentration,and the experiments should preferablybe performedwithin a closeconcentration rangein order to ensurebetter accuracy(24). Tristimulus colorimetersmay also be used to control the color and lightness of pharmaceutical dyes. This is done by plotting x and y chromaticity values for a known standard dye and establishingpermissible color differencesfor new lots. The sample lightnessmay be controlled by comparing the sample's Y tristimulus value to that set for the standard dye. This is a rapid and easyquality control techniquefor new samplelots of FD&C dyes.

Dye-A djuvantChemisorption Studies Several articles have appearedin the literature with respectto color stability and other changesresulting from the interaction of dyes with pharmaceuticaladjuvants (25-27). Results of a dye-adjuvant chemisorptionstudy (25) usingdiffusereflectance techniques presented are in Figs. 11 and 12. The former representsthe results of equilibrating

FD&C Red #3 dye with starchUSP in an aqueous dispersion medium,

followed lyophylization(25). by

COLOR
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005

250

300

I 350

4.00

5JO 600

Figure11. Diffusereflectance spectraof FD&C Red 3 Dye (30 mg) and starch, USP (10.00 g). Key: A, control; B, sample; C, sampleexposed 184-hourartificiallight at 2000 f.c. to
lOO

2hO

2[0

300

3150

4)0

50 60

9Jo

Figure 12. Diffuse reflectance spectra of FD&C Red #3 Dye (30 mg) and lactose, USP (10.00 g). Key: A, control; B, sample; C, sample exposedto 184-hour artificial light at
2000 f.c.

In Fig. 11, ,4 is the spectrophotometric reflectancecurve of the control, consisting a triturated dry physicalmixture of the dye and adjuof rant. Curve B shows this spectrumof the samedye-starchcombination placedin a suitable container, with 20 ml of distilled water added. This sampleis then equilibratedfor 24 hours at 30 C and the material is dried by lyophilization. Curve C resulted when the equilibrated and dried sampleis exposedto 184 hours of artificial light at 2000 f.c. using an
Envira-Lite Cabinet.*

Figure 12, ,4, B, and C representa FD&C Red #3-lactosecontrol, sample,and light-exposed sample,respectively. A comparison Figs. of 11 and 12 indicatesthat both systems undergointensespectrophotometric changes duringequilibration,especially the Xmx 540 m. It at of
is of interest to note that the dye-starchinteraction is far weaker than the

dye-lactosecomplexsincethere is about 78% fading observedat the

* Thermal Research, Inc., Thermal Road, Iselin, N.J.

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X.... in the starchsampleas compared about4% fadingin the lactose to sample(25). These studies and others previously conducted on drug-adjuvant interactions (28) point out the needfor dye incompatibilitytestsin conjunction with other considerations the formulation of pharmaceutiin
cals.

CONCLUSION

The fundamental measurement prindples indicate that the use of instruments for the control of color will continue to be of great benefit in the cosmeticand pharmaceuticalindustry. Although future problems will not be totally solvedwith the aid of instrumentation,the amount of information gainedfrom thesetechniques more than justifiesthe useof
these methods for the control of color.

(Received December 18, 1967)

REFERENCES
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(16) Judd, D. B., A maxwell triangle yielding uniform ehromatieity scales,J. Opt. Soc. Am., 25, 24 (1935). (17) Adams, E. Q., X-Z planes on the 1931 I.C.I. system of colorimetry, Ibid., 32,168 (1942). (18) MacAdam, D. L., Visual sensitivities to color differences in daylight, Ibid., 32, 247 (1942). (19) Hunter, R. S., Photoelectric color difference meter, Ibid., 48, 985 (1958). (20) Judd, D. B., and Wyszeeki, G., Color in BusinessScienceand Industry, 2nd Ed., John Wiley and Sons, Inc., New York, N.Y., 1963. (21) Stanziola, R., Practical colour instrumentation for the dyer, Can. Textile J., 1-5 (September 17, 1965). (22) Kubdka, P., New contributions to the optics of intensely light scattering materials, J. Opt. Soc. Am., 38, 448, 1067 (1948). (23) Hardy, A. C., Handbookof Colorimetry,The M.I.T. Press, Cambridge, Mass., 1936. (24) Lieu, V. T., and Frodyma, M. M., Selection of the optimum concentration range for reflectance spectrophotometric analysis, Talanta, 13, 1319 (1966). (25) Bornstein, M., Walsh, J. P. Munden, B. J. and Laeh, J. L., Diffuse reflectance studies of dye-adjuvant ehemisorption, J. Pharm. Sci., 56, 1410 (1967). (26) Laehman, L., Kuramoto, R., and Cooper, J., A study of the interaction between quaternary ammonium compounds and several certified dyes, Ibid., 47, 871 (1958). (27) Scott, M. W., Goudie, A. J., and Huetteman, A. J., Accelerated color loss of certified dyes in the presenceof nonionic surfaetants, Ibid., 49, 467 (1960). (28) Bornstein, M., and Lach, J. L., Diffuse reflectance studies of solid-solid interactions II, Ibid., 55, 1033 (1966).