The Photophysical Properties of 2-Naphthol

A Physical Chemistry Experiment

Richard Boyer, George Deckey, Charles Marzzacco, Maureen Mulvaney, and Catherine Schwab
Department of Physical Sciences, Rhode Island College, Providence, Rl 02908
Arthur M. Halpern
Department of Chemistry, Northeastern University, Boston, MA 02115

Phenolic compounds such as 2-naphthol are known to be

much stronger acids in their lowest excited singlet states than
in their ground states (1-5). These molecules exhibit two
fluorescence emission bands, a short-wavelength one origi-
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nating from the free acid and a long one originating from the
conjugate base. According to a method developed by Forster,
the ionization constant for the excited molecule, A’*, is related
to the ground state Ka and the spectral frequency shift ob-
served when the free acid deprotonates (1, 2). The excited
state ionization constant can also be determined by a fluoro-
metric titration method (3, 6), as well as a dynamic method
which involves determining the rate constants for the excited
state deprotonation-protonation reaction from an analysis of
the fluorescence decay curves of the free acid and the conju-
gate base (7-9). In the case of 2-naphthol, the ground state
pKa has been determined to be 9.5, while the values obtained
for the excited state range from 2,5 to 3.5 depending on the
method used to determine it (10).
The photophysica! properties of 2-naphthol have been the
subject of several undergraduate research studies at Rhode
Island College. We have also adapted this study to an under-
graduate physical chemistry experiment which is now used
at RIC. The students determine the ground state ionization
constant by analyzing the absorption spectra of 2-naphthol
in acidic, basic, as well as buffered solutions in the pH range
of 9.1 to 9.7. The excited state ionization constant is deter-
mined by the Forster cycle method from the ground state
ionization constant and the spectral frequency shift upon
going from the free 2-naphthol to its conjugate base. This first 4
experiment, performed in the first semester of Physical Figure 1. The absorption spectra of various 2.0 X 10 M aqueous solutions
of 2-naphthol: (A) 0.10 M NaOH; (8) pH = 9.73 buffered solution; (C) pH = 9.44
Chemistry, entails the topics of thermodynamics and equi- buffered solution; (D) pH = 9.13 buffered solution; (E) 0.01 ATH2S04 solution,
librium, which are covered in our first semester. During the The buffer was NH4CI-NH3.
second semester, when the topic of chemical kinetics is cov-
ered, an experiment involving the determination of the rate
constants for the excited state deprotonation-protonation has been obtained for the ground state pKa. Clearly 2-naph-
reaction is performed. thol is a very weak acid in its ground electronic state.
The excited state dissociation constant is determined by
use of the Forster cycle method. In order to apply this method,
The Ground and Excited State Ionization Constants the 0,0 electronic transition frequencies for each of the two
The absorption spectra of 2-naphthol in acidic, basic, and species must be measured. One way to obtain this, is to de-
buffered solutions are shown in Figure 1. The spectrum of the termine the average frequency at the absorption and emission
acid solution (E) is due to the 2-naphthol free acid absorption maxima for each species. The relationship between pAa, pA”
while that of the basic solution (A) is due to the 2-naphthoxide and the transition frequencies of the free acid, fnoh, and the
ion, the conjugate base of 2-naphthol. Buffered solutions in conjugate base, fno-. is given below:
pH range of 9.1 to 9.7 (spectra B D) exhibit spectra which are pAj =
pA„ —

intermediate between that of the free acid 2-naphthol and that
of the conjugate base. By analyzing these spectra at 350 nm,
it is possible to determine the concentrations of each of the
two species. Since the free acid does not absorb at 350 nm, the
concentration of the 2-naphthoxide ion can be determined
from the absorbance. The concentration of the free acid is then
obtained by subtracting the 2-naphthoxide ion concentration
from the total concentration. When these concentrations are
combined with the hydrogen ion concentration as measured
in terms of the pH, the ground state dissociation constant can
be calculated. From an analysis of the spectra, a value of 9.47
(JV/!/2.303AT)(i'noh —
fno-)
The result of 3.5 which we obtain for pKa, is on the high side
of the published values (1-5, 10). The high value probably
results from the estimation of the 0,0 transition frequency
from the average of the frequencies at the absorption and
emission maxima for each species. This method provides a
good estimate of the 0,0 frequency only if there is a good
mirror image relationship between the absorption and the
emission spectra (10, 11). The absorption and emission
spectra of the 2-naphthoxide ion do show a good mirror image
relationship, however, the spectra of the 2-naphthol do not

630 Journal of Chemical Education

 B

Figure 3. The fluorescence spectrum of 2-naphthol in 0.10 M sulfuric acid

Figure 2. The fluorescence spectra of 2-naphthol in 0.10 M sulfuric acid (A) and
in 0.10 M sodium hydroxide (B). Spectrum A is that of the free acid, and spectrum
(Spectrum A). The remaining spectra are of 2-naphthol in solutions with am-
monium acetate concentrations of 0.004 /W(B), 0.008 M(C), 0.016 M(D), 0.024
B is that of the conjugate base.
M(E), 0.040 M(F), and 0.072 M(G).

In dilute sulfuric acid solution, excited 2-naphthol mole-

as can be seen from Figures and 2. Some of the assumptions
1 culeswill decay by fluoresence or nonradiative processes only.
involved in the Forster cycle have been discussed by Jaffe and Therefore, the quantum yield of fluorescence, T°, will be given
Lloyd Jones (11). by the expression below:
A comparison of the ground and excited state pKa’s of 2-
Rate Fluorescence
naphthol shows that the molecule is a stronger acid in its ex- _

cited state by about six orders of magnitude. Rate Fluorescence + Rate Nonradiative Decay

Kinetics of the Excited State Deprotonation-Protonation t. ftf[NOH*] kt _

Reaction ftf[NOH*J fenr[NOH*[ kr+knr

+

The rate constant for the deprotonation of 2-naphthol in In the presence of ammonium acetate (pH = 7), in addition
its lowest excited singlet state can be determined from an to fluorescence and nonradiative decay, the two deprotonation
analysis of the fluorescence spectra of this system in ammo- reactions can occur. Therefore, the quantum yield of fluo-
nium acetate solutions. These spectra as well as the spectrum rescence will be equal to the rate of fluorescence divided by
of 2-naphthol in a 0.10 M sulfuric acid solution are shown in the sum of the rates of fluorescence, nonradiative decay, sol-
Figure 3. The spectrum of the sulfuric acid solution (A) shows vent assisted deprotonation and acetate assisted deprotona-
emission from the free acid, NOH, only. This is as expected tion.
since the pH is much lower than the ground and excited p/fa’s.
The spectra in ammonium acetate solutions of increasing
_ftf[NOH*]_
+
fef[NOH*] *nr[NOH*] + kd[NOH*] + A>Ac[NOH*][AC-[
strength (B-F), show emission from both the free acid (Amax
=
360 nm) and from the conjugate base (Amax = 420 nm). The
k{+ km + kd + AaJAc ]
pH of these solutions is 7.0 and, therefore, the free acid form
of 2-naphthol is the dominant species in the ground state. The The ratio of the quantum yield of fluorescence in the ab-
sence of deprotonation (sulfuric acid solution) to that in the
long wavelength emission occurs because the 2-naphthol
molecule, after absorbing a photon, deprotonates to form the presence of deprotonation (ammonium acetate solution), 0°/0,
excited 2-naphthoxide ion. Since the intensity of the longer is shown below:
wavelength 2-naphthoxide emission band increases with the -kAc [Ac-] I°/I
concentration of the buffer, NH4AC must be active in effecting $°/4> =
1 + —+ =

kf “F hnf k{ + knr
the deprotonation, presumably through the acetate ion acting
as a base. Spectrum A shows no conjugate base emission be- This is a Stern-Volmer-like relationship, and the two rate
cause in an acidic solution such as this, with a pH below 1.0, constants for deprotonation can easily be obtained from it.
the equilibrium lies far to the left even in the excited state. The ratio of the fluorescence intensity of the free acid in sul-
Therefore, those molecules that do deprotonate, are imme- furic acid solution to that in ammonium acetate solution has
diately reprotonated. been substituted for since it is more easily measured.
The diagram shown below illustrates the mechanism that A plot of I°/I versus the acetate ion concentration should
was used to analyze the data: yield a straight line with a slope of k^J(kf + knr) and an in-
tercept of 1 + kj(kf + k„T). Our experimental plot, shown in
NOH noh* —-*-NO“* + H+ + Ac- ^>NO-* + HAc Figure 4, shows good linearity with an intercept greater than
unity.
In order to determine k ac and from the slope and inter-
| hv cept, it is necessary to obtain a value for the sum of the radi-
NOH
ative and nonradiative rate constants, and km. These are
The following mechanism has been used to analyze the determined from fluorescence decay data which are provided
data: to the students. These data are presented in the table and were

NOH + hv — NOH* Absorption

NOH* NOH + hv Fluorescence; Rate =
fef[NOH*[
NOH* —
NOH + heat Nonradiative Decay; Rate =
/enr[NOH*[
NOH* —
NO-* + H+ Deprotonation; Rate =
&d[NOH*[
NOH* + Ac- -* NO-* + HAc Acetate Assisted Deprotonation; Rate =
&ac[NOH*][Ac_]

Volume 62 Number 7 July 1985 631

 Fluorescence Lifetime Data for 2-Naphthol in 0.10 M H2S04 obtained by the single photon counting method applied to
2-naphthol in a 0.1 M sulfuric acid aqueous solution. Since the
Intensity
Time (ns)
excited 2-naphthol decays by first-order kinetics, a plot of the
(photons emitted/time)
natural log of the intensity versus time will be linear with a
0.0 21753 slope of (k( + knr). A value of 7.01 ns has been determined
—

1.0 18907 for the fluorescence lifetime, corresponding to a value of 1.43

2.0 16380 X 108 s-1 for the sum of kf and knl. When this value is com-
3.0 14171
bined with the values obtained for the slope and intercept of
4.0 12432
5.0 10757
the Stern-Volmer plot, values of 6.0 X 107 s-1 and 2.3 X 109
6.0 9288 1 mol-1 s-1 are obtained for kd and kt,c, respectively. These
7.0 8138 values agree well with published values (9,11).
8.0 7083 The rate constant for the reverse reaction, kp, the reaction
9.0 6014 of the hydronium ion with the 2-naphthoxide ion can also be
10.0 5350 calculated from the excited state ionization constant that was
determined from the Forster cycle method and kd from the
relationship K'a = kjkp. The value obtained by using this
relationship is 1.9 X 10111 mol-1 s-1. This value is rather large
but not out of the ordinary considering that it is the rate
constant for a diffusion-controlled reaction between the highly
mobile hydronium ion and another ion of opposite charge.
Conclusion
Students seem to enjoy doing this experiment and working
up the data. The experiment involves so many of the concepts
that they are exposed to in physical chemistry. If some stu-
dents are interested, the experiment can be extended by re-
peating the experiment in various alcohol-water mixtures
instead of using water as the solvent. It has been found that
the addition of alcohol to the solvent severely reduces the
deprotonation rate constants (12). Various substituted
naphthols and other phenolic compounds could also be
studied.

Acknowledgment
The authors acknowledge the generous support of the
Rhode Island College Faculty Research Fund.
Literature Cited
(1) Forster, T., Naturwiss., 36,186 (1949).
(2) Forster, T., Z. Electrochem., 54,531 (1950).
(3) Weller, A., Z. Electrochem., 56,662 (1952).
(4) Weller, A., Z. Phys. Chem. (Frankfurt), 3, 238 (1955).
(5) Weller, A., Z. Phys. Chem. (Frankfurt), 17, 224 (1958).
(6) Rosenberg, J. L., and Brinn, I., J. Phys. Chem., 76,3558 (1972).
(7) Laws, W. R., and Brand, L., J. Phys. Chem S3,795 (1979).
,

(8) Harris, C. M„ and Selinger, B. K., J. Phys. Chem., 84, 891 (1980).
[NH4Ac] (9) Tsutsumi, K., and Shizuka, H., Z. Phys. Chem., 122, 129 (1980).
(10) Vander Doncktr, E., Prog. Reaction Kinetics, 5,273 (1970).
Figure 4. Stern-Volmer plot for the quenching of the free acid 2-naphthol (11) Jaffe, H. H., and Lloyd Jones, H., J. Org. Chem., 30, 964 (1965).
emission by ammonium acetate. 1° represents the fluorescence intensity of (12) Huppert, D., Kolodney, E., Gutman, M., and Nachliel, E.,J. Amer. Chem. Soc., 104,
2-naphfhol in a 0.10 MH2S04 solution. 6949(1982).

632 Journal of Chemical Education