Simplified Spectrophotometric Determination

of Acid Dissociation Constants

John 0. Frohligerl
Department of Occupational Health, Graduate School of Public Health, University of Pittsburgh, Pittsburgh, Pa. 15213
Joseph E. Dziedzicz and Omar W. Steward
Department of Chemistry, Duquesne University, Pittsburgh, Pa. 15219
A si mpl i f i ed met hod for t he spectrophotometric de-
t ermi nat i on of aci d dissociation constants has been
developed. Equations for calculating t he aci d dis-
sociation constants ar e present ed. The measure-
ment s ar e made on a system at equi l i bri um containing
a weak acid and t he sodium sal t of a second weak acid.
For each system, t he t ot al concent rat i on of t he two
aci ds and t he dissociation constant of one of t he acids
must be known, and t he concent rat i on of one of t he
anionic species must be det ermi ned spectrophoto-
met ri cal l y. Acid dissociation constants of t he t ype
RRR MCOOH where R, R, R may be H, CH,, or C6H,
and M may be C, Si, or Ge were det ermi ned i n 45 weight
per cent et hanol , 76 weight per cent ethanol, and di -
met hyl sulfoxide.
ACID DISSOCIATION CONSTANTS in nonaqueous systems have
been determined using potentiometric (1-9, conductimetric (8)
and spectrophotometric methods (9,lO). Although the poten-
tiometric method usually suffers from the lack of standard
buffer solutions, and unknown liquid junction potentials ( I I ) ,
it has been preferred over the more tedious spectrophoto-
metric procedure (12). The spectrophotometric procedure
requires that at least one species, either the anion or the un-
dissociated acid, have an absorption band region which ad-
heres to Beers law. After the spectra are obtained, the ab-
sorbances of several solutions buffered at different pH are
determined. When the activity of the anion equals the activity
of the undissociated acid, the pH equals pK,. Usually the
activity coefficients are taken to be unity, and concentrations
are used instead of activities.
I n order to measure the pK, of a substance that does not
have a pure absorption spectrum, indicators have been used.
A small known amount of an indicator with a known pK, is
To whomcorrespondence should beaddressed.
Present address, FMC Corp., Princeton, N. J .
( 1) C. D. Ritchie and P. D. Heffley, J. Amer. Chem. SOC., 87,5402
(2) E. Grunwald, ibid., 73, 4934 (1951).
(3) E. Grunwald and B. J . Berkowitz, ibid., p 4939.
(4) J . 0. Frohliger, R. A. Gartska, H. W. Irwin, and 0. W. Steward,
(1965).
ANAL. CHEM., 40, 1408 (1968).
(5) C. D. Ritchie and R. E. Uschold, J. Amer. Chem. Soc., 89,
1721 (1967).
(6) C. D. Ritchie and G. H. Megerle, ibid., p 1447.
(7) Ibid., p 1452.
(8) H. 0. Spivey and T. Shedlovsky, J. Phys. Chem., 71, 2171
(9) I. M. Kolthoff and T. B. Reddy, Inorg. Chem., 1, 189 (1962).
(10) B. W. Clare, D. Cook, E. C. F. KO, Y. C. Mac, and A. J .
Parker, J. Amer. Chem. SOC., 88, 1911 (1966).
(11) L. Meites and H. C. Thomas, Advanced Analytical Chem-
istry, McGraw-Hill Book Co., Inc., New York, N. Y. , 1958,
p 22.
(12) C. E. Meloan and R. W. Kiser, Problems and Experiments
in Instrumental Analysis, Charles E. Merrill Books, Inc.,
Columbus, Ohio, 1966, p 9.
(1967).
added to a solution containing known quantities of a weak
acid and its salt. The absorbance of the indicator at a known
wavelength is measured. The acid dissociation constant is
then calculated from the equation,
PKHA =pKmn +log [HA] - log [A-] - log 01
where ~K H I , is the dissociation constant of the indicator and
a! is the ratio of the absorbance of HI n to In-.
I n this investigation a simplified approach to the indicator
method is presented that permits the determination of dis-
sociation constants of compounds which have either an un-
stable acid form or an unstable base form. The procedure
used in this method does not require that both the acid form
and the base form of the compound be available, that a buffer
solution be prepared, or that the pH of the solution be deter-
mined by an independent method. This method has the
added advantage that a spectrophotometric measurement is
made at one wavelength on one species and thus does not re-
quire an elaborate experimental procedure. As many as 12
separate measurements can be made in 1 hour.
The simplified spectrophotometric method utilizes the
equilibrium conditions of weak acids and bases.
HA +Na+Z- + HZ +Na+A-
(1)
The concentration relationships involved in an ionic equilib-
rium of a weak acid with the base form of a second weak acid
are,
(3)
[H+l +[Na+l =[A-I +[Z-I (6)
when [A]T and [ZIT are the analytical concentrations of the
species present in the system. These equations hold as long
as the autodissociation of the solvent is negligible. I n the
equilibrium system described by Equations 2 through 6, [A]T
and [ZIT can be obtained by dissolving a weighed amount of
either the acid or base form into a known volume of solvent.
Then, if [Z-] can be measured spectrophotometrically and one
of the ionization constants is known, the equations can be
solved and the other dissociation constant calculated. Since
one of the two acids is in the base form and one of the two
ionization constants is known, there are four possible combi-
nations of the variables which can be used to solve Equations
2 through 6. The four combinations or cases are given in
Table I. I n all cases [Z-] is determined spectrophotomet-
rically.
ANALYTICAL CHEMISTRY, VOL. 42, NO. 11, SEPTEMBER 1970 1189
Table I. Cases for the Determination
of Acid Dissociation Constants
Known
dissociation
Case No. constant Acid form Baseform
I KHZ HA Z-
I1 KEA HA Z-
I11 KHZ HZ A-
I V KEA HZ A-
Table 11. Dissociation Constants
Determined by Direct Spectrophotometry
2,6-Dinitrophenol 45wt Ethanol-water 3.97 f 0.04
2,4-Dinitrophenol 76wt Ethanol-water 4.76 i Z0.02
2,4-Dinitrophenol Dimethyl sulfoxide 5.05 i Z0.02
Compound Solvent PK=
Case I. The acid dissociation constant of the base form is
known and the anion of the base form is measured spectro-
photometrically.
[H+] =KHZ (2 - 1)
(7)
[HA] =[A], - [A-I (9)
Case 11. The acid dissociation constant of the acid form is
known and the anion concentration of the base form is
measured spectrophotometrically. The expression for the
[H+] is a quadratic.
[H+12 +(KHA +[HZI) [H+l -
KHA ([A], - "1) =0 (10)
[HZI =[ZIT - [z-1 (11)
Case 111. The acid dissociation constant of the acid form
is known and the anion concentration of the acid form is
measured spectrophotometrically.
[HA] =[Z-] - KHZ (Q - 1)
[Z-I
Case IV. The acid dissociation constant of the base form
is known and the anion concentration of the acid form is
measured spectrophotometrically. The expression for the
[H+] is again a quadratic equation.
[H+I2 +(KEA +[A]T - [Z-I)[H+l - KHA[Z-] =0 (15)
[HA] =[ZIT - [z-] (1 6)
EXPERIMENTAL
Apparatus. All spectrophotometric measurements were
made on a Cary Model 14 Spectrophotometer using 10-cm
cells at 25.0 i 0.1 "C. Calculations were carried out on a
Control Data G-20 Computer.
Reagents. The acids and salts, obtained from commercial
sources, were purified as indicated below: benzoic acid,
salicylic acid, 4-nitrophenol, 2,4-dinitrophenol (Fisher Certi-
fied Reagent Grade), 2,6-dinitrophenol (Eastman Grade)
dimethylphenylacetic acid (City Chemical Co.), diphenyl-
methylacetic acid, and triphenylacetic acid (Aldrich Chemical
Co.) were crystallized several times from ethanol-water;
bromcresol purple (Fisher Scientific Co.) from acetic acid;
sodium benzoate (Allied Chemical Corp.) from acetone-
water; sodium salicylate (Allied Chemical Corp.) from
ethanol. Dimethylphenylsilane-, diphenylmethylsilane-, tri-
phenylsilane-, and triphenylgermanecarboxylic acid were
prepared and described previously (13) by a modification of
the method of Gilman and coworkers (14,15) and were crystal-
lized several times from benzene-petroleum ether or petro-
leum ether. Sodium 4-nitrophenoxide, sodium 2,4-diNtro-
phenoxide, and sodium 2,6-dinitrophenoxide were prepared
from the corresponding acid forms and were crystallized
several times from distilled water.
Solvents. Dimethyl sulfoxide (Fisher Certified Reagent
Grade) was distilled under reduced pressure from calcium
hydride, bp 55 "C (4.1 mm). The solvents, dimethyl sulf-
oxide, 95% ethanol (USP Reagent), and distilled water,
employed in the determination of the pK, values of the acids,
were distilled prior to use. Purified dimethyl sulfoxide was
stored in the dark under a nitrogen atmosphere. The 45 wt
z ethanol-water solvent was prepared by adding 495 ml
of water at 25 "C to a 1-liter volumetric flask. This was then
diluted to the mark with 95 % ethanol at 25 "C. I n a similar
manner, the 76 wt ethanol-water solvent was prepared.
I n this case, 150 ml of water was used.
Spectrophotometric Procedures. A known volume of sol-
vent containing a known concentration of the species which
shows no absorbance at the wavelength employed was placed
in a 10-cm cuvette. The cell was allowed to equilibrate in
the temperature controlled cell compartment of the spectro-
photometer. An aliquot of the indicator solution was added
from a microburet (0.001-ml subdivision), the cell was shaken
to mix the solution, and the absorbance was recorded. Ad-
ditional aliquots were added, and the absorbance was
recorded after each addition. I n this manner, as many as
eight measurements could be obtained. A second analysis
was made in every case using different concentrations of the
solutions.
RESULTS AND DISCUSSION
The determination of the acid dissociation constant by this
method requires that one of the two compounds used have a
known acid dissociation constant. Three compounds were
chosen as the standards, sodium 2,6-dinitrophenoxide for the
45 wt z ethanol-water solvent, sodium 2,4-dinitrophenoxide
for the 76 wt Z ethanol-water solvent, and 2,4-dinitrophenol
for the dimethyl sulfoxide solvent. The values obtained are
shown in Table 11.
The application of the spectrophotometric method depends
upon the equilibrium conditions of the equation.
HA +NaZ =NaA +HZ
(19)
If the equilibrium is shifted too far to the right or left, the
results will not be valid. The equilibrium conditions are
controlled by the acid dissociation constants and the analytical
concentration of two species used in the determination. Al-
though it is not possible to accurately determine the necessary
equilibrium conditions prior to the measurement, the pro-
cedure of adding small increments of the absorbing species
from a microburet offsets this disadvantage. This procedure
(13) 0. W. Steward, H. W. Irwin, R. A. Gartska, and J. 0. Froh-
(14) A. G. Brook and H. Gilman, J. Amer. Chem. SOC., 77, 2322
(15) H. Gilman and W. J. Trepka, J. Org. Chem., 25, 2201 (1960).
liger, J. Chem. SOC. ( A) , 3119(1968).
(1955).
1190 ANALYTICAL CHEMISTRY, VOL. 42, NO. 11, SEPTEMBER 1970
Table III. pK, Values for Acids in Dimethyl Sulfoxide at 25 "C Using All Four Casesa
PK.
Acid Base Detns Case No. Found Lit.
2,4-Dinitrophenol 9 5.05 f 0.02bpc 5.2d
Salicylic ~- acid Sodium 2,4-dinitrophenoxide 8 I 6.79 f 0.10 6. 9~
Bromcresol purple Sodiumsalicylate 13 IV 10.08 f 0.10
Bromocresol purple , 9 111 10.06 f 0.17 10.0dge11.0, Sodiumbenzoate
--
Benzoic acid
Acetic acid
--
Sodium4-nitrophenoxide
SodiumCnitrophenoxide
14
10
I1 9.87 f 0.01
I 11.41 f 0.02
a Underlined compounds are compounds for which dissociation constants were determined.
I , pK, value determined by direct spectrophotometry.
c Standard deviation.
d Ref. (10).
e Ref. (9).
Ref. (16).
0 Ref. (5).
9.9d 10.40
11.4~ 11.60
Table IV. pK, Values Determined in Various Solvents at 25 "C
-
45 Wt Ethanol-Water0
No. PKL3
M.p., "C detns Found Lit.d
11 5.61 f 0.016 5.64 f 0.06
34 -35 23 6.41 f 0.08
79.5-80 11 6.05 f 0.01 6.00 f 0.03
177.5-180 11 5.81 f 0.01 5.77 f 0.04
274 -275
56.5-58 16 6.06 f 0.05' 5.96 f 0.10
139 -140 11 5.97 f 0.030 5.66 f 0.05
183 -185
dec
dec
dec
187 -190
a Case I: base sodium 2,6-dinitrophenoxide.
b Case I: base sodium 2,4-dinitr ophenoxide.
c Case I: base sodium 4-nitrophenoxide.
d Ref. (13).
* Standard deviation.
1 Small amount of base-catalyzed decomposition of the acid.
0 Significant base-catalyzed decomposition of the acid.
~
No.
detns
12
19
6
12
10
12
10
9
11
76Wt Ethanol-Water6 Dimethyl sulfoxidec
PKG No.
Found Lit.d detns
6.57 f 0.028
7.96 f 0.05 13
7.45 f 0.04 7.45 f 0.02 16
7.15 f 0.09 7.20 f 0.03 24
6.78 f 0.02 6.70 f 0.03 21
7.28 f 0.05
7.04 f 0.05
6.10 f 0.10
6.27 f 0.03 6.32 f 0.02 6
6.78 f 0.02
7.03 f 0.09
6.23 f 0.04
P K ~
12.39 f 0.128
11.10 f 0.05
10.00 f 0.04
9.29 f 0.07
8.43 f 0.06
gives a wide concentration variation in the system and the
subsequent additions can be adjusted to give absorbance
values that yield valid results. The concentration ranges used
in the method are usually dilute enough to allow activity
effects to be neglected. No corrections for activity were made
in these measurements.
To avoid large differences in the ionization constants of
HA and HZ, it is sometimes necessary to utilize compounds
with intermediate ionization constants. Table I11shows how
the pK, of 4-nitrophenol was obtained from the known pK,
of 2,4-dinitrophenol by the use of several intermediate com-
pounds. All four equilibrium cases were employed since
some of the compounds used do not have absorption spectra
in the visible region.
Table IV shows the results of the determinations of acid
dissociation constants in 45 wt x ethanol-water solvent on a
(16) C. D. Ritchie and R. E. Uschold, J. Amer. Chem. SOC., 90,
2821 (1968).
series of carboxylic acids. The values obtained by this
method agree well with the values obtained by a potentio-
metric method (23). Similar results are found in 76 wt x
ethanol-water solvent, except that the pK, for acetic acid
appears to be lower than the values reported in the literature.
These results are shown in Table IV.
The method also was applied to the solvent dimethyl
sulfoxide. These results are given in Table IV. The silicon-
substituted carboxylic acids were very unstable in this solvent
and their dissociation constants could not be determined.
RECEIVED for review February 25, 1970. Accepted J une 18,
1970. Presented in part at the 154th National Meeting,
American Chemical Society, Chicago, Ill,, Sept. 1957. The
authors gratefully acknowledge the financial support of the
Dow Corning Corporation, Midland, Mich., and a grant
from the National Science Foundation for the Cary Model
14 Spectrophotometer.
ANALYTICAL CHEMI STRY, VOL. 42, NO. 11, SEPTEMBER 1970 1191