1262 ANALYTICAL CHEMISTRY, VOL. 51, NO.
8, JULY 1979
(2) Very strong acid solutions digested the organic portion
of the silver mercaptide and result in an apparent increase
in solubility.
(3) An unsuccessful attempt to utilize dilute solutions of
nitric acid to remove adsorbed silver ion from the precipitate
resulted in no appreciable solubility losses, indicating a
negligible effect of hydrogen ion concentration on solubility.
(4) The general expression for the p H dependence of the
solubility ( S )of salts of weak acids of dissociation constants
(K,) is given by:
S2 = Ksp(1 + [H+]/K,)
Butler notes that when [H+]/K, is small compared to unity
(Le,,for solutions of little acidity or for insoluble salts of strong
acids), the solubility is independent of hydrogen ion con-
Alternative Graphical Methods for the Spectrophotometric
Analysis of Mixtures
Kenneth A. Connors' and Chukwuenweniwe J. Eboka
School of Pharmacy, University of Wisconsin, Madison, Wisconsin 53706
One method permits data to be taken at multiple wavelengths
to generate linear plots, from which the concentrations can
be determined; this method is applicable to mixtures of two
or three components. The second method is a graphical
technique for the solution of simultaneous equations. For
3component mixtures, the graphical solution Is carried out on
a triangular composition plot; for 4-component mixtures, a
3-dimensional construction is used. Results from these
methods on many mixtures are compared with the conven-
tional simultaneous equations method.
Consider this analogy between reaction kinetics and ab-
sorption spectroscopy: in kinetics the data display is es-
sentially a plot of concentration against time; in spectroscopy,
absorbance is plotted against wavelength. The formal sim-
ilarity between the time and wavelength axes suggested that
some recently described graphical techniques for the kinetic
analysis of mixtures ( I , 2) might be usefully applied to
spectrophotometric mixture analysis.
PRINCIPLES
Graphical Analysis Using Data at Many Wavelengths.
Throughout this paper we assume adherence to Beer's law and
additivity of absorbances; let the cell path length be 1.0 cm.
Then for the 2-component mixture of A and B, we can write
At = EACA + EBCB (1)
where A, is the absorbance of the mixture, and tl and ci are
the molar absorptivity and molar concentration of species i,
the absorbance and absorptivities referring to a common
wavelength. T o analyze the mixture spectrophotometrically,
tA and tB must be different functions of wavelength. Then,
from Equation 1,
At
-= CA +-
CB
CB
EA EA
0003-2700/79/0351-1262$01.OO/O
centration (as though no hydrolysis had occurred (9)).
LITERATURE CITED
(1) Borgstrum, P.; Reid, E. E. Ind. Eng. Chem., Anal. Ed. 1929, 1 , 186.
(2) Kunkei. R. K.; Buckley, J. E.; Gorin. G. Anal. Chem. 1959, 37, 1098.
(3) Wronski, M. Talanta, 1965, 72, 593.
(4) Cecil, 13.;McPhee, J. R. Biochem. J . 1955, 59, 234.
(5) Gruen, L. C.; Harrap. B. S. Anal. Biochem. 1971, 42, 377.
(6) Sluyterman, L. A. Biochem. Siophys. Acta 1957, 25, 402.
(7) Gupta, H. K. L.; Boltz, D. F. Microchem. J . 1971, 76, 571.
(8) Tseng, P. K. C.; Gutknecht, W. F. Anal. Chem. 1975, 4 7 , 2316.
(9) Butler, J. N. "Ionic Equilibrium, A Mathetmatical Approach"; Addison-
Wesley: Reading, Mass., 1964.
RECEIVED for review September 18, 1978. Accepted March
30, 1979. This work was supported by Grant No. CHE76-
07378 and Grant GP-37493X from the National Science
Foundation.
Thus a plot of A,/ t A vs. tg/ tA, all quantities evaluated at the
same wavelength, is made with data points taken a t as many
wavelengths as desired. The concentration cg is obtained from
the slope, and cA can be evaluated by extrapolation to CB/EA
= 0; alternatively, the sum cA +
cg is determined by inter-
polation a t the point where t B / t A = 1. Another way to treat
the data is to replot as At/tB vs. t * / t ~ ;then CA is found from
the slope. Yet another means is to extrapolate the line (for
Equation 2) to A , l t ~= 0; the intercept Q / C A = -cA/cB.
For a 3-component mixture Equation 3 can be written
At = ~AcA + EBCB + ECCC (3)
Define total concentration ct = cA + CB + CC, and fractional
compositions fA = CA/Ct, fg = cg/ct, fc = cC/c,; then Equation
3 becomes
(4)
Note that At/ct can be interpreted as an apparent molar
absorptivity for the mixture; Le., let A,/ct = tapp. Then upon
rearrangement,
(5)
+ +
where we have used the identity f A f B fc = 1. A plot of
the left-hand side against ( t B - t C ) / ( t A - tc), over a range of
wavelengths, yields the fractions.
For Equation 5 to be useful, the total concentration is
needed. This is usually accessible through the following
analysis. Suppose two of the components (say A and B)
exhibit a t least two iso-absorptive points, when the spectra
are compared on a molar basis. Thus, at wavelengths where
t A = E B , Equation 3 can be written as
and a plot of At/tA vs. tC/tA, using data only a t the iso-ab-
D 1979 American Chemical Society

sorptive points of A and B, yields the concentration et as the
value of At/tA when cc/cA = 1. The condition for this de-
termination, namely the presence of at least two iso-absorptive
points for two of the three components, seems to be widely
met.
[We incidentally observe, reversing the analogy, that
three-component mixtures can be analyzed kinetically, if a
common product is generated, by casting the concentrations
in fractional form, as done above. Then a linear plot can be
obtained, obviating the need for the extrapolation used earlier
(])I.
Graphical Solutions of Simultaneous Equations. In
the conventional spectrophotometric analysis of an n-com-
ponent mixture, measurements are made a t n wavelengths,
and a set of n simultaneous equations is solved for the n
concentrations, after prior determination of n2 absorptivities
(coefficients) on samples of the individual components. This
technique is analogous t o the "method of proportional
equations" used in the kinetic analysis of mixtures ( 3 , 4 ) ,in
which measurements are made a t n times. For 3-component
mixtures a rapid graphical solution has been described (2);
this kinetic technique is now applied to spectrophotometric
analysis, and is extended to 4-component mixtures.
The 3-component problem is conventionally formulated as
in Equations 7-9, where e,, is the molar absorptivity of species
i a t wavelength j and A, is the absorbance of the mixture at
wavelength j
A2 = +
~ A ~ c A ~BZCB +~C~CC (8)
= tA$A + BBCB + tC3CC (9)
Dividing by total concentration ct gives the completely de-
termined set of equations.
= f A + f B -k f C
where by introducing the additional piece of information ct
it is possible to eliminate measurements a t the third wave-
length. I t is Equations 10-12 that can be solved graphically.
The total concentration is determined by means of Equation
6, as described earlier.
The fractional composition of any solution of A, B, C can
be represented by a point on a triangular composition diagram.
The apices of the equilateral triangle represent pure A, B, or
C; the edges represent all possible binary mixtures of AB, AC.
or BC; and ternary mixtures of ABC are specified by points
in the body of the diagram. The fractional composition of
any component is given by the linear fractional distance of
the point from the edge opposite the apex corresponding to
that component.
The six tl, values (Equations 10, 11) are evaluated on so-
lutions of pure A, B, C a t wavelengths l and 2, and these
numbers are entered on the triangular diagram at the ap-
propriate apices. The quantities Al/c, and A2/ct are evaluated
for the mixture.
Consider the data at wavelength 1. The quantity Al/ct (an
apparent absorptivity) must have a magnitude falling between
the members of two of the three pairs (CAI, tgJ, (CAI, tc1), (tgl,
tC1),for a 3-component mixture. By linear interpolation, points
on these two sides of the triangle are located corresponding
to Al/ct, and these points are joined by a straight line. Points
on this "tie-line'' represent all solutions having this value of
Al/ct a t wavelength 1.
In a similar way a second tie-line is constructed for data
a t wavelength 2. The point of intersection of the two tie-lines
is the only point that can satisfy Equations 10-12, and the
ANALYTICAL CHEMISTRY, VOL. 51, NO. 8, JULY 1979 1263
fractional composition of the mixture is read directly from
the graph.
The assumption of additivity of absorbances is equivalent
to the use of linear tie-lines and linear interpolation. In the
graphical solution as described (the "full-range" solution),
calibrating measurements are made on pure A, B, C, and the
nature of the entire plane is defined by its properties at the
apices. If the mixtures should behave nonideally (nonad-
ditively), empirical compensation can be made by using for
calibrating measurements three solutions whose compositions
define a triangle smaller than the entire compositional plane,
this smaller area including the sample mixture. Such
"mid-range'' and "local" solutions have been used for kinetic
analyses ( 2 ) . A virtue of this graphical technique is that it
reveals a t a glance appropriate compositions of calibration
standards (after a trial analysis with a full-range solution to
give an approximate sample composition).
The 3-component problem requires for its graphical solution
measurements a t two wavelengths, knowledge of the total
concentration, and representation on a triangular 2-dimen-
sional plot. Extension to the 4-component problem requires
three wavelengths and graphical solution in three dimensions.
The appropriate figure is a regular tetrahedron, each apex
representing a pure component, the edges the six possible
binary mixtures, the faces the four ternary mixtures, and
points inside the tetrahedron the 4-component mixtures.
Linear interpolation is used as before to define all points on
edges corresponding to the value for A l / c t for wavelength 1.
These points, connected, define a plane. Similar treatment
a t wavelength 2 defines another plane. The intersection of
these planes determines a line. The plane defined by the
measurements at the third wavelength will intersect this line
a t a point representing the sample composition.
The technique is a simple, rapid means for solving a set of
four simultaneous equations. It requires the total concen-
tration ct, which does not appear to be generally accessible:
hence an independent measure of ct must be available. For
the kinetic application ( 2 ) ,when a common product is gen-
erated, ct can be easily obtained.
These graphical solutions are generalizations of routinely
used methods for analyses of one or two components based
on calibration curves, the sample concentration being located
as a point on a line (or rather, taking experimental uncertainty
into account, as a line segment). In the 3-component case,
the sample composition corresponds to an area element,
whereas for the 4-component system, it is a volume element.
EXPERIMENTAL
Materials. Acetylsalicylic acid (Merck)was recrystallized from
acetone; mp 135-136 "C, lit. 135 "C ( 5 ) . Salicylic acid (Portz)
was recrystallized from water; mp 159-160 "C, lit. 159.5-160.5
"C (6). Tetracaine hydrochloride (Pfaltz and Bauer) was re-
crystallized from water; mp 147-148 "C, lit. 147 "C (7). Benzocaine
(Aldrich) was recrystallized from aqueous ethanol; mp 89-90 O C ,
lit. 89-90 "C (8). Sulfathiazole and sulfanilamide (Merck) were
recrystallized from alcohol; mp 202-203 "C and 164-165 "C,
respectively, lit. 202-202.5 "C (9) and 163-164 O C (10). p -
Hydroxybenzoic acid (Eastman) was recrystallized from water;
mp 213-214 "C, lit. 214-215 "C (11). 2,4-Dihydroxypyridineand
2,3-pyridinedicarboxylicacid (Aldrich) were recrystallized from
aqueous ethanol; mp 263-264 "C and 190 "C, respectively, lit.
26&265 "C (12)and 190 "C (13). trans-Cinnamic acid (Eastman)
was recrystallized from aqueous ethanol; mp 133-134 "C, lit.
134.5-135 "C (24).
Other chemicals were used without further purification.
Standard buffers were prepared according to Bower and Bates
( 1 5 , 16).
Apparatus. Spectrophotometric measurements were made
with a Cary 14 recording spectrophotometer fitted with a
thermostated cell compartment. pH was measured with an Orion
Model 801 pH meter.
1264 ANALYTICAL CHEMISTRY, VOL. 51, NO. 8 , JULY 1979

Table I. Spectral Data for Analysis of a Mixture of

Sulfathiazole and Sulfanilamide"
h,nm EST/cSN i o 5A t I c s N
240 1.22 4.18
245 1.10 4.15
250 0.99 3.90
255 0.94 3.77 IO~A,
260 0.87 3.75
26 5 0.77 3.61
270 0.84 3.71
275 1.40 4.41
280 2.60 5.97
285 4.12 7.93 t
290 5.59 9.19
29 5 6.98 11.73 ' 0 2 4 6 8 1
300 8.34 13.51 "T'%N
305 9.31 14.47
Figure 1. Plot of Equation 13 for a sulfathiazole (ST)-sulfanilamide (SN)
@ 1.30 X l O - ' M sulfathiazole and 2.62 X h'I sulfa- mixture. Data from Table I
nilamide.

Procedures. Sample mixtures were prepared from stock

solutions of the individual components. For mixtures of ben-
zocaine and tetracaine hydrochloride, and of sulfathiazole and 4-
sulfanilamide, 95% ethanol was the solvent. For mixtures of
benzoic, salicylic, and p-hydroxybenzoic acids; and of benzoic,
salicylic, p-hydroxybenzoic, and m-hydroxybenzoic acids, the
solvent was 0.02 M NaOH. For mixtures of salicylic and ace-
tylsalicylic acids, chloroform was the solvent. For mixtures of 3-
2,3-dihydroxypyridine, 2,3-pyridinedicarboxylic acid, and 2,6-
pyridinedicarboxylic acid; of 2,4-dichlorophenol, 2,5-dichloro-
phenol, and 2,6-dichlorophenol; and of 2,4-dihydroxypyridine,
2,3-dihydroxypyridine, 2,3-pyridinedicarboxylicacid, and 2,6-
pyridinedicarboxylic acid, water-alcohol (1:l) was the solvent.
In determining acid dissociation constants, buffer solutions were
prepared with HC1, NaOH, and sodium acetate. The total solute r
04
0 08 12
concentration was held constant within a study; for benzoic acid
this concentration was 7.5 X M, for trans-cinnamic acid it %'EST
was 4.5 X M. Acid dissociation constants were determined Flgure 2. Plot of Equation 14 for a sulfathiazole-sulfanilamide mixture.
at 25 "C. Data from Table I

RESULTS AND DISCUSSION
Graphical Analysis Using Data at Many Wavelengths.
Analyses based on Equation 2 can be exemplified by mea-
surements on mixtures of sulfathiazole (ST) and sulfanilamide
(SN). Table I lists data required to make the plot. Figure
1 is graphed according to Equation 13.
T h e plot of the same data in terms of Equation 14 is shown
in Figure 2.
The plots are linear; an interesting feature is that successive
points on the line need not refer to successive wavelength
readings.
Mixtures of benzocaine and tetracaine and of aspirin and
salicylic acid also were analyzed in this way. Table I1
summarizes these results. Plots were made according to both
forms of the equation for all mixtures, and each component
was determined from both a slope and an intercept reading.
The mean absolute errors (difference between "taken" and
"found" concentrations) were essentially the same for the two
procedures. The mean error for a particular component
appeared to be independent of concentration. Of course the
relative error is thus highly concentration dependent, and the
percent recovery and confidence limit data in Table I1 are
based on the specified concentration ranges, though the
absolute errors given include some lower concentrations. The
results in Table 11 are not based on replicate determinations
of a mixture, but rather on determinations of many mixtures.
The spectrophotometric data for all of these mixtures were
also treated by the conventional technique, namely using
simultaneous equations set up at two wavelengths. The mean
percent recoveries were comparable with those in Table 11;
in 5 of the 6 cases, however, the confidence limits were wider
with the conventional technique than with the new graphical

Table 11. Analytical Results on Two-Component Mixtures by Equation 2

wavelength 10' conc/M recovery 95% confidence
component range, nm range taken mean error %a limits, % b
sulfathiazole 240 to 305 0.5-2.6 0.02 99.3 i0.8
sulfanilamide 0.6-2.6 0.05 100.9 1.7
tetracaine 265 t o 325 1.0-1.7 0.02 99.3 0.9
benzocaine 1.6-2.6 0.06 100.8 3.3
salicylic acid 260 t o 295 1.7-6.4 0.11 100.7 1.3
aspirin 3.7-3.8 0.06 97.8 1.2
Based on 7 t o 1 3 separate mixtures. Based on Student's t distribution.
 ANALYTICAL CHEMISTRY, VOL. 51, NO. 8, JULY 1979 1265

Table 111. Data for Triangular Graphical Analysis of a

Three-Component Mixturea
A, nm 2b 25 26 E app
ro4r, 294 2313 1285 378 1203
281 2046 2830 2340 249 5
a Concentrations: 24, 3.38 X 10. M;25, 7.07 X 10.
M ; 26, 5.40 X 10. M .
I 1
0 04 08 12
c23P/E26P ~.

Figure 3. Plot of Equation 15 to obtain total concentration of a 3- Table IV. Analytical Results for
component mixture of 26P, 23P, and 23D (see text),total concentration Three-Component Mixtures
9.63 x 10-5 M Percent Recovery i95% Confidence Limits
by b y linear bY
triangular plottingsimultaneous
plottingb (Eq. 5 ) b equations
:ompo-
C ( 2 wave- ( multiple ( 3 wave-
nenta lengths) wavelengths) lengths)
26Pc 100.3 2 4.6 102.0 i 3.6 98.6 z 5.8
231 23Pc 100.8 i 2.2 98.2 i 2.8 97.4 i 4.2
23DC 100.3 i 2.5 100.9 r 2.3 102.5 i 3.4
24d 98.9 i 2.7 96.7 2 4.0 99.8 ? 2.7
I / I 25d 98.7 c 3.2 98.0 c 2.4 97.0 i 5.3
Y o 2 4 6 8 lb 26d 100.6 t 3.1 102.0 r 4.0 102.6 i 5.2
26P- 23D a See text for abbreviations. Requires also a determi-
23P- 23D nation of total concentration. Based on 10 mixtures.
d Based o n 8 mixtures.
Figure 4. Plot of Equation 16 for a mixture of 26P (3.24 X M),
23P (4.21 X M), and 23D (2.17 X M)

method. This is a reasonable result, because the graphical

approach uses more data. Whether the improvement is
deemed an advantage is a function of the particular analysis,
that is, the nature of the spectra and the use to be made of
the results.
Some 3-component mixtures were analyzed with Equations
5 and 6. For mixtures of 2,6-pyridinedicarboxylicacid (26P),
2,3-pyridinedicarboxylicacid (23P),and 2,3-dihydroxypyridine
(23D), Equation 6 was written in the form

and applied a t the 26P, 23D, iso-absorptive points a t 234,

247.8, and 278.3 nm. This plot is shown in Figure 3. From
such plots the total concentration was determined with a
recovery of 100.1 f 0.8% (10 mixtures).
Equation 5 was then written as Equation 16.
<app - t23D t26P - t23D
= f23P + ~-
23P - t23D 23P - t23D
A plot according to this equation is shown in Figure 4. For
9 mixtures (minimum individual concentration 1.1x lo- M),
these results were obtained: for 26P, 102.0 f 3.6%; for 23P,
98.2 f 2.8% ; for 23D, 100.9 f 2.3%. The wavelength range
used in the plots was 260 to 285 nm.
Mixtures of 2,4-dichlorophenol, 2,5-dichlorophenol, and
2,6-dichlorophenol were treated in the same way. Total
concentrations were found using the iso-absorptive points at
286.3, 289.0, and 291.5 nm for the 2,4 and 2,5 compounds; for
8 mixtures the results were 99.7 0.5%. The individual *
concentrations were found from plots of Equation 5, the results
being, for 2,4-dichlorophenol, 96.7 f 4.0%: for 2,5-di-
*
chlorophenol, 98.0 2.4%; for 2,6-dichlorophenol, 102.0 i
4.0%. The wavelength range used in the plots was 270 to 294
nm.
The construction of these plots can be time-consuming, but
if many mixtures of the same components must be analyzed,
the time per analysis becomes very reasonable, because the
molar absorptivity functions (e.g., the abscissa function in
378 1 A/ 1203
1285
2830
Figure 5. Graphical analysis of a 3-component mixture. Data from
Table 111. The underlined data refer to 281 nm
Equation 16) are common to all the samples. Only the values
of A , and tappchange with the sample.
Graphical Solution of Simultaneous Equations. The
f26P (16) triangular composition diagram was applied to the analysis
of mixtures of 2,4-dichlorophenol (24), 2,5-dichlorophenol (25),
and 2,6-dichlorophenol (26). Table I11 gives the data for one
of these mixtures. Figure 5 shows how the data are plotted.
In this figure, compound 24 is designated A, 25 is B, and 26
is C. The construction of the sample tie-lines by linear in-
terpolation between the apex values will be obvious from the
figure. In practice commerically available triangular graph
paper is used; the grid markings are not shown in Figure 5.
The technique was also applied to mixtures of 26P, 26D,
and 23D (see abbreviations given in preceding section). The
analytical results by the triangular plotting method, by the
linear plotting method, and by conventional simultaneous
equations are gathered in Table IV. These results suggest
that there is no clearcut choice among the three approaches.
I t seems possible that if the spectra of the three compounds
are very similar, the linear plotting method, which makes use
of all the available data, may yield the most reliable analyses,
whereas if the spectra are markedly different either the
triangular plot or conventional simultaneous equations may
be preferable. Much experience with many kinds of sample
1266 ANALYTICAL CHEMISTRY, VOL. 51, NO. 8, JULY 1979
D
C measurements a t a single wavelength, since only the ratio of
D
c (4 determinations) was 4.17 i 0.04 (literature (17)4.19). The
(C
Figure 6. Construction of solution for a 4-component mixture; data
from Table V (drawings of 3dimensional regular tetrahedron). (a) Plane
constructed for 285 nm by linear interpolation between apices; the edges
of the plane are drawn in heavy lines, representing a string stretched
between these points. (b) The 285-nm plane is drawn in light lines;
the 260-nm plane is shown in heavy lines. The intersection of the two
planes is marked by laying a wire (arrow) across the intersections of
the strings. (c) Here the 285 and 260 nm planes are drawn lightly, as
is the wire marking their intersection. The 230-nm plane is shown in
heavy lines, and a second wire (arrow) defines the line of intersection
between the 230- and 285-nm planes. The point where the two wires
intersect (circle) gives the fractional composition of the sample mixture,
which is calculated by measuring the fractional distance of this point
from each of the sides
mixtures will be required to establish these points.
Turning to 4-component mixtures, we require a 3-di-
mensional representation. A regular tetrahedron framework
was constructed of wood strips, each side being about 50 cm
long and marked off in 100 units to aid in interpolation. The
sample points, located by interpolation, were marked with
pins, and these were connected with string to define the planes.
Details of the construction are given by Figure 6, which shows
the solution of a 4-component mixture of 26P, 23P, 23D, and
Table V . D a t a for T e t r a h e d r a l S o l u t i o n o f
F o u r - C o m p o n e n t Mixture (Figure 6 ) a
*, nm 23P f26P cz3D END capp
285 1133 2292 5877 4029 3873
260 2303 3753 1203 2762 2540
230 6178 5614 3751 2222 3948
a In F i g u r e 6, A = 23P, B = 26P, C = 23D, D = 24D.
T h e c o n c e n t r a t i o n s are: A, 0.80 x 10.' M ; 8,3.76 X
10-5M ; c, 3.54 x 10-5M ; D, 3.83 x 10-5 M.
2,4-dihydroxypyridine (24D). The data for this analysis are
given in Table V. For the purpose of demonstrating the utility
of this graphical solution technique, the total concentration
of the mixture was taken as a known quantity.
Nine mixtures of 26P, 23P, 23D, and 24D were analyzed,
the minimum fractional composition of any single component
being 0.07. The mean error, over 36 components and without
regard to sign, was 0.02 in the fractional composition. Nine
mixtures of benzoic, salicylic, rn-hydroxybenzoic, and p -
hydroxybenzoic acids were analyzed, using measurements at
225,235, and 245 nm. The mean fractional error was 0.02 over
the 36 individual results.
Determination of Acid Dissociation Constants. The
dissociation constant K, of a weak acid HA can be determined
spectrophotometrically if the spectra of the conjugate acid and
base forms are different. This is usually accomplished by
concentrations need be known, as shown in Equation 17,
where K,' is the apparent dissociation constant. K,' can be
corrected to the thermodynamic constant K,by applying the
Debye-Huckel equat,ion to estimate the ionic activity coef-
ficient.
If the spectra of HA and A- are not greatly different, it may
prove advantageous to use Equation 2 to determine cHAand
cA- on the basis of measurements a t many wavelengths. T o
demonstrate the applicability of this technique some acid
dissociation constants have been measured.
Benzoic acid was studied a t pH 3.58 and pH 4.46, at 25 "C.
The wavelength range was 220 to 246 nm. The resulting pK,
pK, of trans-cinnamic acid (4 determinations, 215 to 305 nm)
was found to be 4.49 f 0.03 (literature (17) 4.44).
LITERATURE CITED
(1) K. A. Connors, Anal. Chem., 48, 87 (1978).
(2) K. A. Connors, Anal. Chem., 49, 1650 (1977).
(3) R. G. Garmon and C. N. Reilley, Anal. Chem., 34, 600 (1982).
(4) H. B. Mark, Jr., and G. A. Rechnitz, Kinetics in Analytical Chemistry",
Wiley-Interscience, New York, 1968.
(5) T. Higuchi and J. L. Lach, J . A m . Pharm. Assoc., Sci. Ed., 43, 527
(1954).
(6) T. Higuchi and R. Kuramoto, J . Am. Pharm. Assoc., Sci. Ed., 42, 398
(1954).
(7) H. Doser. Arch. Pharm., 281, 251 (1943).
(8) R. Adams and F. L. Cohen, Org. Syn., 8, 66 (1928).
(9) W. A. Lott and F. H. Bergeim. J . Am. Chem. Soc., 61, 359 (1939).
(10) L. F. Fieser, "Experiments in Organic Chemistry", 3rd ed.,Heath and Co..
Boston, Mass., 1955, p 147.
(11) I. A. Pearl. J . Ora. Chem., 12. 85 (1947).
G. Errera, Ber., 51, 1687 (1898).
E. Sucharda. Ber.. 58, 1727 (1925).
M. L. Bender, G. R. Schonbaum, and B. Zerner, J . Am. Chem. SoC.,
84. 2540 (1962).
V. E. Bower and R. G. Bates, J. Res. Natl. Bur. Stand., 55, 197 (1955).
V. E. Bower and R . G. Bates, Anal. Chem.. 28, 1322 (1956).
G. Kwtijm, W. Vogel. and K. Andussow, "DissociationConstants of Organic
Acids in Aqueous Solution", Butterworths, London, 1961.
RECEIVEDfor review March 9,1979. Accepted April 30,1979.