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J. Soc. CosmeticChemists,19, 649-667 (Sept. 16, 1968)

Color

and

Its Measurements*

MICHAEL

BORNSTEIN,

Ph.D. t

Synopsis--An accountis given for the fundamental principlesof diffuseand tristimulus re-

flectancemeasurements. The experimental basisfor thesemeasurements,including the

CIE

and Munsell systemsfor defining color space,is also discussed. These principles are

sup-

ported with

qualitative and quantitative examples for color matching, as well as interaction

studies with reflectance values and the Kubelka-Munk

equation.

A review of several availa-

ble commercial color measuring devices,referencestandards, and sample preparation tech-

niques are also presented.

INTRODUCTION

The stability and appearanceof colored cosmeticand pharma- ceutical dosageforms are dependent on the dye or lake employed, as

well as many other parameters. These may include adjuvant absorp-

tion coefficientsof microscopicand macroscopicstructures as well as

otherphysicalandchemicalproperties(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 associateshave applied various parameters to color stability of tablet formulations (3-5). Goodhart,Lieberman,and associates(6, 7) have alsostudiedthe stabil-

ity of certifieddyesin tablets. Raft (8, 9) has presentedreportsof

color measurements

obtained

from

FD&C

colorants.

The purposeof this communicationisto discussprinciplesandinstru-

ments

used in diffuse

and tristimulus

reflectance

measurements

and their

applicationto the developmentof coloredpharmaceuticaldosageforms.

* Presented October 2, 1967, Sixth Annual A. Ph. A. Industrial

logy Meeting, Chicago

Pharmaceutical

Techno-

p Pitman-Moore Division, Dow Chemical Co., Research Center, Zionsville, Ind. 46077.

Present address, Eli Lilly & Co., Indianapolis, Ind. 46206.

649

650 JOURNAL

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COSMETIC

CONCEPTS OF COLOR

CHEMISTS

The sensationof coloris the result of radiant energy,between400 and

700mu,impingingthe eye(10).

psychologicalas well as physicalaspects,colorscalesand instruments

are often designedto include both parameters. The psychologicalas-

pectsof colorare the resultof colorcodesstoredin the brain, including

associationof an individual hue suchas blue-greenwith a characteristic sensationsuchascoolness. Physicalaspectsof colorresultfrom the fact

Sincethe phenomenonof colorincludes

that visibleradiant energyisnecessaryfor vision.

The basicprinciple on which tristimulus colormeasurementis based

dependsonthe assumptionthat mostcolorsmay be producedby a com-

bination of red, blue, and green coloredlights.

combine to form yellow, whereas blue and green combine to form a

bluish-greencolor. A purplecolorresultsfrom the combinationof red

and blue; a white hue forms when the red, green, and blue primaries

Red and green beams

unite.

mediate colors can

By varying the amountsin the three primary beams,all inter-

be produced. This phenomenonof uniting three

basic colors to

form

white

is the

basis for

an additive

color mixture.

Onemay alsoform a subtractivecolormixtureby usingyellow,magenta, and cyan pigments. The resultant color darkenswith the subtractive

mixture asmore of thesefilterscombine; when all three subtractivepri-

maries unite, a black color is formed.

Numerous systemshave been

developedto definecolor.

This discussionwill be primarily concerned

with the CIE and Munsell systems.

CIE

SYSTEM

There are two basicfoundationson which colorimetrydepends. The first is that colorcan be matchedby a suitablemixture of three selected

light radiationsand that if two colorsare matchedby three radiations,

the mixture of these two colorsis found additive by suitable optical

means.

The essentialprinciples of this tristimulus color system were

first independentlydevelopedby Ives (ll)

CommissionInternationale de l'Eclairge (CIE) standardizedthe color

mixture characteristicsof an "average observer"and developeda stand- ard framework for a colorspecification.

andGuild (12).

In 1931,the

This standard observer represents a seriesof functions determined

from data providedby observersmatchingthe colorat eachwavelength

from 400 to 700m•, with mixturesfrom three primary light sources.

The experimentalset-upfor definingthe "average"human observer

measuresthe observer'sresponseto the three primary colorsby focusing

COLOR AND

ITS

MEASUREMENT

SPECTRUM

COLORS

651

 

1.6

 

GREEN• 'x

540

1.2

0

400

Figure 1.

500

m•u

600

700

Responseof the "standard CIE

observer" to an equal energy light source

søø

• •

I BLUE

•[ 4•o

400

Figure 2.

•.'c'

RED

••

,oo

Chromaticity diagram illustrating

the visible spectrum locus measured with 10

spectrophotometric readings. The tristimu-

lus chromaticity coordinates (x,y) for illumi-

nant C are plotted near the center of the chart

the threelightsona screenin the samelocationsothat they may bemixed in properproportions. A monochromaticlight sourceisfocusedona spot

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 mono-

chromaticlight source,recordingthe relative amountsof the threelights

necessaryfor the match.

Figure 1 showstheserelative amountsof 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 equalenergysourcecontaininglight from all visible

wavelengths. Most standard light sourcesdo contain light of every color, but not in equal amounts. Illuminant A, found in standard in-

candescentor tungstenlight sources,has light at all wavelengths,with muchmoreenergyat longerwavelengths. Illuminant B isa light source

equivalentto the noonsun.

north side of a building, containslight of all wavelengthswith much

more energyin the blue part of the spectrum. Figure 2 showsthe three

Illuminant C, representingdaylighton the

dimensionsof the CIE

marlcity coordinates.

expressingthe tristimulus values X, Y, Z, as fractions of their total

These tristimulus values of a sample are either calculated from diffuse

reflectancemeasurements(9) to be discussedlater or they may be mea-

color solid in two dimensionsusingx and y chro-

Thesechromaticity coordinatesare calculatedby

652 JOURNAL

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•DOMINA

ILL0'C'½•

F{gur½3.

X

Chromaticity diagram (x,y) defining

i]]um{nant C, dominant wavelength, and purity

sureddirectlyontristimuluseolorimeters. Onlytwocoordinatesneedto be specifiedsincethe total of the x, y, and z chromaticitycoordinates

equalsunity.

Herethecoloraxisor chromaticitycoordinateslie onthe

outsideof the trianglegoingfrom blueto greento red, whereasthe white

to black axis or luminosityfunctionis the center; this brightnessaxis

wouldbeperpendicularto the screenwith the whiteat the top andblack

at the bottom.

Nonspectrumcolorsrepresentmixtures having the

chromaticitiesrepresentedat any point alongthe straightlinejoiningthe extremitiesof the spectrumlocusand are producedby mixing suitable

portionsofradiantengerytakenfromtheextremeshort-wave(lessthan

440 m/•) and long-wave(greaterthan 680 m/•) regionsof the spectrum. Colorsrepresentedby pointson straightlinesbetweenthe achromatic

pointCin Fig.2 andthespectrumlocusarecalledspectralcolors.

The CIE systemdividesthe characteristicsof light fromwhichcolor

is composedinto severalcomponentsincludingluminance,dominant

wavdength,and purity. Luminanceis the characteristicthat differ-

entiatesthe light reflectedfrom a standardwhite sample,illuminated

with a 100-W lamp, from that of light reflectedfrom this samewhite

samplewhenit is illuminatedby a 200-Wlamp with all other things beingequal. The dominantwavelengthmay be definedas the wave-

lengththat appearsto bedominantin thelightandisusuallythemostin-

tensevarietyof radiantenergyin the stimulus. Purity refersto the de-

greeto whichthe dominantwavelengthappearsto predominatein the

light.

Figure3 showsthat thedominantwavelengthisobtainedbyplotting

the chromaticitycoordinatesof the illuminantand sample. A line is

COLOR AND ITS MEASUREMENT 653 White 8 9 IO 1 2 3 5 .10 Black
COLOR
AND
ITS
MEASUREMENT
653
White
8
9
IO
1
2
3
5
.10
Black
Neutral
Saturated
colour
Chroma
colour

Figure

Hue, value, and chroma coordinates of the Munsell system

drawn from the achromaticor illuminant point through the sampleco-

ordinates onto the locus of the diagram.

This point on the locus is

calledthe dominantwavelength. The per cent purity is determinedby

the ratio of the distancefrom the illuminant point to the samplecoordi-

nates,A, divided by the distancefrom the illuminant point to the spec-

trum locus,B, expressedin per cent. Luminosity is expressedin per

cent Y, obtained directly from tristimulus colorimeters. This diagram

in which each point representsthe chromaticity, independentof lumi-

nance,ism,calledachromaticitydiagram.

MUNSELL

SYSTEM

Another systemfor definingcolor space,calledthe Munsell system (13), is basedon a colorsolidillustratedin Fig. 4. The central vertical

axisrepresentsthe locusof neutral colorswith white at the top and black

at the bottom. In this system,lightnessof the sample, called value,is

dividedinto a numberof stepsfrom 0 to 10. The distanceof the sample

from the central vertical axis is a function of the saturation or intensity

654 JOURNAL

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of color and is called chrornaon the Munsell map.

Chroma is also

divided into a

whereasa fully saturatedsamplehasa chromaof 12.

is called in the Munsell system (14), is presentedby different planes

seriesof steps,with the neutral axis or gray being 0,

Color,or hueasit

aroundthe vertical axisof the Munsell solid.

solidis divided into ten equal vertical segmentswith five principal hues

(red, yellow, green,blue, and purple) occupyingthe central planesof alternate segmentswhile intermediatehues (yellow-red,green-yellow, blue-green,purple-blueand red-purple) occupythe remainingplanes.

Each hue segmentis further divided into ten sectionsnumbered 1 to 10, with the main hue segmentalwaysnumbering5.

In this system,the whole

The hue of a sampleis designatedby a number,indicatingthe section

of the segment,followedby symbolswhichshowthe colorof the segment

involved. For example,10P indicatesthe hue section10 of the purple

segment. To completethe specificationof the sample,the value quan-

tity followsthe hue which is then followedby a stroke and then the

chroma. Herethe colordefinedat 10P •/• hasthe hue10P, thevalue5,

and the chroma

of 8.

COLOR DIFFERENCE

AND TOLERANCE

It is of interest to point out that color differencesare not

linear throughout the entire CIE chromaticity diagram since,if

entirely

one cal-

culatestwo points on this diagram, another set of points twice as far

apart do not necessarilyhave a totally linear differencein color(9, 15).

In other words, equal distanceson the diagram do not always indicate

the samedegreeof colorchange.

Judd (16) devisedthe UniformChromaticityScale(UCS) adoptedby

the National Bureauof Standards(NBS).

chromatic-valuediagram which was acceptedby the American Society

Adams (17) followedwith his

for Testing Materials (ASTM).

MacAdam (18)

investigatedcolordif-

ferenceswhere the observermade a large number of matcheson a series

of test colorslocated at various points in the chromaticity diagram.

The spreadin the colorsettingsnecessaryto make a match (Fig. 5) was

used by MacAdam as the criterion of sensitivity to color differences.

The distancesfrom points on the boundaryof eachellipseto the central

point within the ellipseapproximatelycorrespondto the chromaticity

differencejust perceptiblewith certainty under specifiedviewingcondi-

tions; this just perceptible color differenceis defined as one MacAdam

unit.

tion of the dominant wavelength and purity changes, but does not

The orientation of the major axisof individual ellipsesis a func-

COLOR

AND

ITS

Y 1.s52.•530

•0

•'X

o.4-499

•4•

MEASUREMENT

•oo

655

F•gure5.

The axis of each ellipse has been multiplied by 10 for illustrative

MacAdam'sperceptiblechromaticitydifferencesin the CIE diagram.

purposes

MONOCHROMATOR

SOURCE

MPLE

PHOTO-SENSO

Figure6.

Schematicdiagramrepresentingthe major componentsof a spectrophotometeror

colorimeter.

Spectrophotometers use prismatic or grating monochrometers where colori-

meters

would

contain

filters

changewith lightness; i.e., the

shapeand orientation remain constant

at differentluminosities.The ellipsesdo vary in sizewith a change

of

makingcolordecisionsdecreaseunderimprovedlight-viewingconditions.

lightness,becomingsmaller as lightnessincreases,since errors in

COLOR MEASURING INSTRUMENTS

ReflectanceSpectrophotometers

This type of instrument,diagrammedin Fig. 6, isbasedon a beamof

monochromaticlight penetratinginto a sample. This light is scattered

in many directions,is partially absorbed,andfinallyre-emergesto the

656 JOURNAL

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400

SOCIETY

700

SAMPLEREFLECTANCE (R)

RxE

OF

COSMETIC

400

700

SOURCEEMISSION(E)

CHEMISTS

SPECIFYING

Figure 7.

THE

COLOR

OF A SAMPLE

Schematic diagram for interaction

factors to produce color vision

surface. Measurementsmay be plotted as reflectancers. wavelength usinga relatively nonabsorbingwhite referencestandard. This infor-

mation is then usedfor quantitative Kubelka-Munk equationsor it may

be converted

to tristimulus

values

which

will

be discussed.

Commercial instrumentsinclude the Hardy General Electric Spec-

trophotometer,Bausch& Lomb Spectronic505 with reflectanceattach- ment, as well as the BeckmanDU Spectrophotometerwith the reflect-

anceaccessory. The G. E. instrument hasa recorderand automatically

converts

reflectance

data

to tristimulus

values.

The

Bausch

&

Lomb

instrument has a recorder whereas the Beckman DU is a

trophotometer.

manual spec-

It

Tristimulus

Instruments

shouldbe pointed out that the CIE

system was developedto

eliminateeye variationsby usingthe "standardobserver." The princi- ple behind tristimulus colorimeters,illustrated in Fig. 7, is as follows:

A light source,E, strikesa samplehavinga reflectancecurve,R.

This

interaction resultsin a reflectanceenergy,RE, which is specificfor each

wavelength; this is alsothe energystriking the eye.

This resultingRE

passesthe filtersand ismultipliedby eachof the hypotheticalcolormix-

ture curvesœ,9, and•, representingcolorvisionof the standardobserver

in the CIE system. This producesthree new curves,eachhaving an

area representedby the tristimulus values X,

Y, and Z.

The above

manipulationsagain indicatethat the CIE systemspecifiesa colorby

three quantities,X,

Y, and Z, calledtristimulusvalues. Thesevalues

COLOR

AND

ITS

MEASUREMENT

657

representthe amounts of primary red, green, and blue color that the

standard observerwould need to get a match. Ii each of these tri-

stimulusvaluesis divided by the sum of three, the resultingvaluesx, y,

and z, called chromaticity coordinates,give the proportion of the total stimulus attributed to each primary color. Furthermore, since the

sumof the three chromaticitycoordinatesis unity, the valuesof x and 3'

plotted on the chromaticity diagram may be used alone to specifythe

color. The third achromatic dimension of lightness or darkness is specifiedby the ¾ tristimulus value. The manipulationsincluded in

tristimuluscolorimetryaremathematically presentedbelow:

Weighted Ordinate

Method

X

=

700

•oo

ExC'Rx.•X

700

Y = •

•oo

'Exc'RX':?x

Z

700

= •

Exc'RX.zX

•oo

Calculation of

Chromaticity Coordinates

x =

y =

z =

z =

X

X

X

I--

+

+

+

X

Y

y

Y

a

Y

+

+

+

Z

Z

Z

(x-t-y)

The Hardy General Electric Spectrophotometer,previouslydis-

cussed,provides spectralreflectancecurvesin addition to tristimulus

values.

This

combination

results in nonmetameric

matches in color

formulationswhich are colorssimilarin appearanceunder all light

sources.Tristimulus instrumentsalone often produce metameric

matcheswhichlookthe sameonlyif similarviewingconditionsareused.

Instrument DevelopmentLaboratories(IDL)

whichis an abridgedspectrophotometergiving10 or 16 visiblewave-

market the Color-Eye

length points as well as tristimulus values.

The instrument is also de-

signedto measurefluorescenceof a samplesincethetristimulusfiltersare

placedbetweenthesampleanddetectorasillustratedin Fig. 8.

puter may alsobe purchasedwith the instrumentto directlymeasure

A com-

color difference in MacAdam

units.

A competitive tristimulus colorimeter called the Hunterlab D-25

ColorDifferenceMeter (19),* schematicallypresentedin Fig. 9, in-

cludesvacuumphototubes,calibratedtristimulusfilters,and a transis-

* HunterAssociatesLaboratory,Inc.,9529LeeHighway,Fairfax,Va. 22080.

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SPECULARINSERT'•'-•----

REFLECTANCE-----,,,•f

--lt

SAMPLE /•<

T•NS•SSION

ZEROING SLIT

SPLITLENS

•'•

••GHTSOURCE

REFLECTANCE

STANDARD

-

DIRECT

LICHT

STOPS

STRAY

LIGHT

STOPS

TP•NSMISSION

STANDARD

MICROMETRIC

SLIT

(VERTICAL

ApERATURE)

ROTATING"FLICKER"

MmmO•

STOP

, •,,,,,••

,

 

.

TRISTIMULUS

and

 

ABRIDGED

SPE CTROPHOTOME

TER

t

FILTERS

PHOTOMULTIPLIER

Figure 8.

I

I

Block diagram of the I.D.L.

Color-Eye

torizedcolormeasurementcircuit.

tristimulus values as well as L, a, b scales(20) which closelycorrelate

with the Munsell system. The L measureslightnessor value, whereas

the a and b readingsrepresentchromaticity coordinates. A computer may be purchasedwith the instrument to give direct color difference

The readoutispresentedin X, ¾,Z

measurements

in

NBS

units.

The

Hunterlab

Color

Difference

Meter

doesnot offerthe 10 or 16 wavelengthspectrophotometricpoints offered

in the Color-Eye, which are usefulwherenonmetamericmatchesare re- quired. The Hunter colorimetermay, however, be used in combina- tion with a Beckman DU or other diffusereflectancespectrophotometer if nonmetamericmatchesare required and may be applied to routine control of pharmaceuticalcolorformulations.

Another commercial instrument, called the Davidson and Hemmend-

inger Colorant Mixture Computer (COMIC),

measurereflectedlight from a sampleof variouswavelengths,usingK/S

enablesthe coloristto

COLOR

AND

ITS

MEASUREMENT

COLOR-MEASUREMENT

CIRCUIT

.¸.

¸

¸

a

L•

-b

CLEAR

METHACRYLATE

LITE

PIPE

L _TRISTIMULUS

FILTEI•S

(359

Figure 9.

Block

diagram

of the Hunterlab

D-25 Color Difference Meter

valuesto makea nonmetamericmatch (21).

performthesecalculationswill be discussed.

The techniquesinvolvedto

REFERENCE

STANDARDS

Sincemosttristimulusdata are a comparisonof luminosityand chro-

maticity, referencestandardsmust be used as a means of comparison.

An ideal reflectancereferencestandardwould diffuselyreflect 100% of

the visible light impinged on its surfaceat all wavelengths.

Magnesium

oxide,magnesiumcarbonate,barium sulfate,andwhite vitrolite have ap-

plication as reflectance standards. A disadvantage with MgO,

MgCOa, and BaSO4is that they are brittle and yellow with age. The

yellowingprocessis slowestwith BaSO4. Their advantage,however, is that these standardshave a diffusereflectanceof about 97-99% in the

visiblewavelengths,makinx reflectancereadingalmostabsolute.

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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 correctionfactors at

each wavelength. Vitrolite is a permanent standard,is easily cleaned

and excellent

for routine

colorimetric

work.

SAMPLEPREPARATIONTECHNIQUES

Powders

Samplepowdersare presentedto most tristimulus colorimetersin a

manner

similar

to reference

standards.

A dish with

a 4 in. diameter

and

•/•-in.depthissufficientasa sampleholder. Thepowderisoftenpacked

and smoothedwith a spatula; a glasscoverslipmay be placedover the

sample,providedthe referencestandardhasa similarcover.

Tablets

Sincethe 2- to 4-in. sampleviewing area found in most tristimulus colorimetersis greater than most tablets, it is suggestedthat sample holdersof • in. or smallerbe made, and the tablets measuredindividu-

ally wherehigh precisionis required. The light beamof the instrument

would have to be adjusted here in order to decreasethe beam diameter

hitting the individual tablet.

Suspensions

The reflectanceof opaquesuspensionsmay be measuredfrom a plas-

Caution shouldbe exercisedto be sure

tic cylinderwith a glassbottom.

that the precipitateis well suspended,resultingin uniform colorreadings.

The

color of clear

Clear Solutions

solutions

is best measured

with

transmittance

tri-

stimuluscolorimetrysincereflectancemeasurementsoften lead to exces- sive light scattering. If reflectancemeasurementis required, one may place a standardizedwhite ceramicbackgroundin the samplecell; the

clear solutiontransmits the light onto the backgroundwhich in turn re-

flectsthis light to the photodetector.

The thicknessof the solutionmust

be controlled by adjusting the volume of sampleused; a 5-ml glass

sampleholder is feasiblefor darker or highly coloredsolutionswhereasa

volumeof 10 ml may be usedfor nearly clearand colorlesssolutions. It

shouldbe noted that the light beamstravel twice the distancewith this

technique,making the readingapproximatelytwice the stimulusvalues

obtainedwith normal reflectancetechniques.

COLOR

AND

ITS

MEASUREMENT

661

QUANTITATIVECOMPUTATIONOFCOLORANDCOLORFORMULATION

Kubelka-Munk

Method

Sincea number of different dye combinationsare often possiblewhen matchinga givenstandardand the useof many FD&C dyesis becoming

limited, formulators must often resort to colorcombinationsfor matching

purposes. However, many matchesare metameric and thereforerequire

spectrophotometricaswell astristimulus analysis. Spectrophotometric

matches, used in combination with tristimulus values of a mixture, tend

to retain the characteristicfeaturesof eachcolorant. An existingprob-

lem with spectrophotometricreflectancecurvesis that thesecurvesdo

not directly follow Beer's law sinceconcentrationis not directly linear

with reflectance. Kubelka (22) developednumerousformulasfor cor-

relating reflectancewith concentrationby making scatteringand surface differencecorrections. It wasfound that the ratio of light absorptionto light scatteringat a given wavelengthis proportional to the concentra-

tion of the dye in the sample. The relationshipshownhere is derived

from the Kubelka-Munk equation.

(• - •)•

Where R = 1.0 at 100% reflectance.

RelationshipofK/S to concentration

Where

K/$

=

kc

K

= light absorbed

 

S

= light scattered

k

= constantof proportionality

C

=

concentration

of colorant

(•)

(2)

SinceK/S factorsfor eachdye at a particular wavelengthare addi-

tive whenmixed together,this principlemay be usedasa basisfor com-

puting the amountsof variousdyesnecessaryto match a givenstandard.

A sampleequationfor findingK/S of a colorantmixtureis:

(K/$),•x.

Where

= a(K/S)A + b(K/$)•

+ c(r/$)c

+

a

=

concentration

of colorant

A

b

=

concentration

of colorant

B

c

=

concentration

of colorant

C

w

=

concentration

of white

base

w(K/X)wh•e

•se

(3)

662 JOURNAL

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This equationwouldbeusedas follows: The K/S

CHEMISTS

for eachdye and ex-

cipient are first obtainedby measuringthe diffusereflectancefor a known concentrationof the dye and excipient or white base at a given wave- length. This R value may be substituted in the Kubelka-Munk equa-

tion (eq. 1), in order to calculatethe K/S values,or thesemay be ob-

taineddirectlyfrom tableswhichgiveK/S

between0 and 100%. The K/S valueof the diluentshouldbe 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,separatelyat onewavelength. The total K/S valuesat that one

wavelengthwill equal the K/S value of a brown, whichresultsfrom the

properconcentrationsof the abovethree dyes. Therefore,if the valueof the sampleisknownat threewavelengthsand the K/S valuesof

the blue, red, and yellow (at any concentration)are alsoknown at the samewavelength,onemay set up three simultaneousequationsto calcu-

late the actual concentrationsof blue, red, and yellow usedto make the

valuesfor reflectancereading

match.

The Davidson and Hemmendinger COMIC

Computer per-

forms thesecalculationsat 16 wavelengthsbetween400 and 700 m/• and

alsocalculatestristimulusvaluesfor the purposeof colormatching(21).

WeightedOrdinateMethod

This method, mathematically illustrated earlier in this presentation,

is a meansof calculatingtristimulusvaluesand chromaticity coordinates

from reflectance data.

It

should also be stressed that x, y, and • are

tristimulus valuesresultingfrom the averagevisual observerand areused

as imaginary primaries under specificillumination for tristimulus cal- culations. The valuesX, Y, and Z, at any wavelength, correspondto

the magnitude of these primaries neededby the standard observerto

match a color. In addition, chromaticity coordinates,x, y, and z, are

the tristimulusvaluesX, Y, and Z expressedas fractionsof their total,

which equal one. These chromaticity coordinatesof the tristimulus

values are then plotted on an x, y chromaticity diagram and the spec- trum locus is located. The weighted ordinate method is a means of

determiningtristimulusvaluesand samplelightnesseither from spectro- photometricreflectancecurvesor directly usingtristimulus colorimetry. Using this method, the relative energyof the light sourceE c(for illumi- nant C) at a particular wavelength, which is found in publishedcolor

tables(23), ismultiplied by the tristimulusvalue •candreflectancevalue

for the samewavelengthbetween400 and 700 m/•, usually10 m/• apart.

The valuesare then summedover the total range to yield the X, Y, and

100

80-

60-

'

COLOR

AND

I

400 500

ITS

540

MEASUREMENT

•mu

I

600

I

700

66;3

Figure 10. Diffuse reflectancespectra of FD&C Red #3 Dye (100 mg)

carbonate, USP (2.00 g). Key: A, standard dye spectrum: B, new sample lot spectrum

and light magnesium

Z tristimulusvalues.

expressingthe tristimulusvaluesasfractionsof their total values.

Chromaticity coordinatesare then calculatedby

The

luminosity or lightness is determined directly from the Y tristimulus

value expressedin per cent.

Although there are other available methodsfor calculatingtristimu-

lus values(23), the weightedordinatetechniqueservesasa goodmeans

for deriving colorvalues from diffusereflectancemeasurements.

I•HARMACEUTICAL

APPLICATION

Quality Controlof FDiC

Dyes

The purity and quality of pharmaceuticaldyesmay be controlled, as

illustrated with the following example: A manufacturer purchasesa

newlot ofFD&C Red#3dye. Thepredeterminedstandardspectrumof

this dye compared to a MgCO3 referencestandard is shown in Fig. 10

The spectrumfor the standard dye is also diluted in a 1:20 ratio with

MgCO3, sinceit is important that the colorcomponentbe highly diluted

with a relatively nonabsorbingdiluent. This ensuresa similar grain size

for the dye and referencestandard, causingthe referenceand sample scatteringcoefficientsto canceleachother in comparisonmeasurements.

This facilitatesscatteringto beindependentof wavelength(24).

664 JOURNAL

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The specificationsfor 100 mg of standard dye diluted with 2.00 g of

MgCO3, (Fig. 10,A) are asfollows'

= 0.1102); Tolerance = •- 10%. A new lot of FD&C dye (Fig. 10,B)

givesthe followingspectrophotometricvalues after 100mg of the dyehas

beendiluted with 2.00 g of MgCO3 USP' (K/S = 0.0909).

Xm•x= 540mu; R = 62.8% (K/S

X

= 540 m•;

R

=

65.5%

SinceK/S values are proportional to concentration,the purity of the

new lot may be found from the calculationsshownbelow, assigninga

purity of 100% to the standarddye.

K/Ssta.

Csta.

K/Xsamrle

_

Csample

Where

K

= absorptioncoefficient

S

= scatteringcoefficient

C

= dyeconcentrationin %

0.02

0.0909

=

oo%

--;

Csamp•e= 81.6%

Csample

(4)

The new samplelot shouldbe rejected,sinceit contains18.4•c im-

purities.

It

should be emphasized that the colorist must check the

linearity of K/S valueswith concentration,and the experimentsshould

preferablybeperformedwithin a closeconcentrationrangein orderto en- surebetter accuracy(24).

Tristimulus colorimetersmay also be usedto control the color and

lightnessof pharmaceutical dyes.

chromaticity values for a known standard dye and establishingpermis-

sible color differencesfor new lots.

trolled by comparing the sample's Y tristimulus value to that set for

the standarddye.

new samplelots of FD&C dyes.

This is done by plotting x and y

The sample lightnessmay be con-

This is a rapid and easyquality controltechniquefor

Dye-AdjuvantChemisorptionStudies

Severalarticleshave appearedin the literature with respectto color stability and other changesresulting from the interaction of dyeswith

pharmaceuticaladjuvants (25-27).

sorptionstudy (25) usingdiffusereflectancetechniquesare presentedin

Resultsof a dye-adjuvantchemi-

Figs. 11 and 12.

The former representsthe results of equilibrating

FD&C Red #3 dyewith starchUSP in an aqueousdispersionmedium,

followedby lyophylization(25).

lOO

Figure11.

g).

Key:

lOO

A

COLOR

2•50

AND

ITS

300

MEASUREMENT

350I

4.00

A

5JO 600

005

Diffusereflectancespectraof FD&C Red •3 Dye (30 mg) and starch,USP (10.00

A, control; B, sample;

C,sampleexposedto 184-hourartificiallight at 2000 f.c.

2hO

2[0

300

3150

4•)0

5•0

6•0

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, sampleexposedto 184-hourartificial light at

2000

f.c.

In Fig. 11, ,4 is the spectrophotometricreflectancecurveof the con- trol, consistingof a triturated dry physicalmixture of the dye and adju-

rant.

CurveB showsthis spectrumof the samedye-starchcombination

placedin a suitable container,with 20 ml of distilledwater added.

sampleis then equilibratedfor 24 hoursat 30øCand the material is dried

by lyophilization.

sampleis exposedto 184 hours of artificial light at 2000 f.c. using an

Curve C resultedwhen the equilibrated and dried

This

Envira-Lite

Cabinet.*

Figure 12, ,4, B, and C representa FD&C Red #3-lactosecontrol,

sample,and light-exposedsample,respectively. A comparisonof Figs.

11 and 12 indicatesthat both systemsundergointensespectrophoto-

metricchangesduringequilibration,especiallyat the Xm•xof 540 m•.

It

is of interest to note that the dye-starchinteraction is far weakerthan the

dye-lactosecomplexsincethere is about 78% fading observedat the

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

666 JOURNAL

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X in the starchsampleascomparedto about4% fadingin the lactose

sample(25).

These studies and others previously conducted on drug-adjuvant

interactions(28) point out the needfor dyeincompatibilitytestsin con-

junction with other considerationsin the formulation of pharmaceuti-

cals.

CONCLUSION

The fundamental measurementprindples indicate that the use of instrumentsfor the control of colorwill continueto be of great benefitin

the cosmeticand pharmaceuticalindustry.

will not be totally solvedwith the aid of instrumentation,the amount of

information gainedfrom thesetechniquesmore than justifiesthe useof

Although future problems

these

methods

for the

control

of color.

(Received December 18, 1967)

REFERENCES

<1)

Lach, J. L., and Bornstein, M.,

Diffuse reflectance studies of solid-solid interactions I,

J.

Pharm. Sci., 54, 1730 (1965).

<2)

Swartz, C. J., and Cooper, J., Colorants for pharmaceuticals,Ibid., 51, 89 (1962).

<3)

Lachman, L., Swartz, C. J., Urbanyi, T., and Cooper, J., Color stability of tablet formu-

lations II, Ibid., 49, 165 (1960).

<4)

Lachman, L., Weinstein, S., Swartz, C. J., Urbanyi, T., and Cooper, J., Color stability

of tablet formulations III, Ibid., 50, 141 (1961).

<5)

Lachman, L., Urbanyi, T., Weinstein, S., Cooper, J., and Swartz, C. J., Color stability of tablet formulations V, Ibid., 51,321 (1962).

(6)

Goodhart, F. W., Kelly, M. A., and Lieberman, H. A., Characterization of tablet colors

obtainable from some certified dyes, Ibid., 54, 1799 (1965).

(7)

Everhard, M. E., Dickcius, D. A., and Goodhart, F. W., Spectrophotometric reflectance

method for matching the color of solid dosageforms, Ibid., 53, 173 (1964).

(8)

Raft, A.M.,

Measurement of a color gamut obtained from FD & C colorants,Ibid., 5/i,

380 (1964).

(9)

Raft, A. M., Tristimulus color measurementsin fading studies and other color changes

of pharmaceuticaldosageforms, J. Soc. CosmeticChemists,18,367 (1967).

(10)

Harris, C., Jr., ColorInstrumentationSeminar, Instrument Development Laboratories,

Attleboro,

Mass., 1966.

(11)

Ives, H. E., The transformation of color mixture equationsfrom one systemto another iI,

J.

Franklin Inst., 195, 23 (1923).

(12)

Guild, J., The colorimetricpropertiesof the spectrum,Phil. Trans. Royal Soc.,London,

A230, 149 (1931).

 

(13)

Nickcrson,D., History of the Munscll colorsystemand its scientificapplication,J. Opt.

(14)

Soc.Am., 30, 575 (1940). Wright, W. D., The Measurementof Colour,3rd Ed., D. Van Nostrand Co., Inc., Prince-

ton, N.J.,

1964.

(15)

Committee on Colorimctry, The Scienceof Color,Optical Society of America, Washing-

COLOR

AND

ITS

MEASUREMENT

667

(16)

Judd, D. B., A maxwell triangle yielding uniform ehromatieity scales,J. Opt. Soc.Am., 25, 24 (1935).

(17)

Adams, E. Q., X-Z planeson the 1931 I.C.I. systemof 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., Colorin 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 (Sep-

tember 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., Selectionof the optimum concentrationrange for

reflectance spectrophotometric analysis, Talanta, 13, 1319 (1966).

 

(25)

Bornstein, M., Walsh, J. P. Munden, B. J. and Laeh, J. L., Diffuse reflectancestudies

of dye-adjuvant ehemisorption, J. Pharm. Sci., 56, 1410 (1967).

 

(26)

Laehman, L., Kuramoto, R., and Cooper, J., A study of the interaction

between qua-

(27)

ternary ammonium compoundsand several certified dyes, Ibid., 47, 871 (1958). 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-solidinteractions II,

Ibid., 55, 1033 (1966).