Estimation of pKa* in the First Excited Singlet State

A Physicial Chemistry Experiment that Explores

Acid-Base Properties in the Excited State
B. Marciniak, H. Kozubek, and S. Paszyc
Faculty of Chemistry, Adam Mickiewicz University,SO-783 Poznan, Poland

The chemistry of an electronically excited species of a

molecule may differ markedly from that of its counterpart
ground-state state species. The lifetime of the former is
very short, for example, 10"-10"s for the first excited singlet state of typical organic wmpounds; further, the geometry and electronic charge distribution can be quite different than in the ground state. For a chemist, however, the
most interesting features of this state are the changes in
chemical properties and the reactivity of these excited species. They can take part in various chemical reactions

(photochemical reactions) different from those in the

ground state; however, they can also take part in the same
type of reactions as can molecules in the ground state. In
this latter case the difference in their reactivity can be observed in the differencein the values of rate constants and
eauilibrium constants when the reactions are studied.
Acid-base reactions are interesting example reactions
that can occur both in the mound
and excited states for the
same compound.
The acid-base reactions in excited states are some of the
most elementary processes both in photochemistry and
biochemistry and are, therefore, well-suited to form the
basis for an undergraduate physical chemistry experiment. To acquaint our students with this phenomenon, we
have chosen a simple experiment to illustrate the proton
transfer reaction in the excited state.
Acid-Base Reactions in the Ground and Excited States

Let us discuss the following equilibrium in aqueous solutions in the ground state:

Figure 1. Electronic energy levels of an acid AH and its conjugate

base A- in the ground and excited states (the Forster cycle).

where AH and A- symbolize acid and wnjugated base, respectively. The equilibrium constant for eq 1in dilute solntion is given by

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247

1.W3 l ( ~ r n ~ ' l

Figure 2. Absorption and fluorescence spectra of 2-naphthol in 0.1 M

HCI.

Figure 3. Absorption and fluorescence spectra of 2-naphthol in 0.1 M

NaOH.
pKa-pK.

and is expressed in terms of pK. (pK, = -logl&$.

The value of pK, depends on the electronic charge distribution. Since electronic excitation can modify charge densities, variations in acidity between the ground and excited
states can be observed. The acid-base equilibrium in the
electronically excited state is expressed as follows:

with the equilibrium constant K.* (pKa* = -logl&,*).

Since proton exchange can be a very fast proeess, an acidbase equilibrium between excited (AH)* and (A-)* molecules can be established, in spite of the short lifetime of the
excited species.
Several methods based on fluorescence intensity and
lifetime measurements have been employed to determine
the pK.* values of the lowest excited singlet state (13).We
suggest applying a simple and less time-consuming
method based on determination of the energy gap between
the ground and excited singlet states of the conjugated
acid and base. The thermodynamic cycle employed in this
case is known as the "Forster cycle" (4). This method has
been successfully used by various authors for many years
(see refs 1-31, Let us consider a diagram of the electronic
states for equilibria 1and 2 (see Fig. 1).
The difference in excited-state energies of the the HA
and A- forms can be expressed as the difference in enthalpy changes for reactions 1and 2:
(3)
Em-EA- = A H - r n
Using the relation AG = AH - TA5', one can obtain:
E,

- E ~ -= (AG + TAS)- ( AG*+ TAS*

( 4)

where AG and AG' are free energy changes of reaction in

the ground and excited states and AS and AS* are entropy
changes of reaction in the ground and excited states.
Assuming that the entropy of dissociation is the same in
both the ground and excited states (AS does not change
appreciably upon excitation, see ref. 51, approximating the
changes of AG, AH, and AS to the standard values, and
using the relation AG = -RT in K,, the following equation
can be obtained:
Em - EA- = AG - AG* = -RRln K. - ln K.')
And finally:
248

Journal of Chemical Education

(5)

. Em- EA=

2,3RT

where R is the gas constant (8.31 J mol-' K-'), T is temperature (K), and Em and EA- are the energies of the electronic transitions for the conjugated acid and base
determined as the 0-0 transition energies.
In the majority of absorption and fluorescence spectra in
solutions it is not so simple to determine the 0-0 transition precisely. An estimate may be made by taking the
value from the region where the absorption and fluorescence spectra of both acid and base overlap. These values
can be estimated, for example, by averaging the frequencies of absorption and fluorescence maxima of both acid
and base forms:

where Va and ?are wavenumbers (cm-'1 for the maxima of

absorption and fluorescence spectra, respectively; N is the
Avorradro constant (6.022 x lo2' mol',: h is the Planck constant (6.625 x
Js); and c is the speed of light in vacuum (3 x 10' ms").
This method is usually employed for the spectra with
well-resolved vibrational structure and, in this case,
Va and 3represent 0-0 transitions in absorption and fluorescence, respectively. When vibrational structure is not
observed in the absorption and fluorescence spectra, the
0-0 transition can be estimated as the wavenumber corresponding to the intersection point of mutually normalized absorption and emission spectra. Spectroscopic determination of 0-0 transitions in solutions for HA and Aforms has been recently discussed in reference 5.
In the following experiment, the value of pK.* for the
lowest excited singlet state of 2-naphthol is determined
using, a Forster cycle. This experiment illustrates, in a
simple way, the change of acid-base properties in the excited state as well as provides some basic knowledge about
absorption and luminescence spectroscopies. It has been
performed for more than five years in our laboratory (undergraduate course in physical chemistry) and has shown
a high degree of reliability in student hands.

Excited Singlet State pKa' Values for 2-Napthol in H20

Forster cycle

Fluorescence
titrationa

Kinetic analysisb

3.1 k0.3 (this workc)

3.0 f 0.1 (this workd)

2.5-3.1 (23)

2.83.0 (2,3)

2.6 f 0.1 (8)

2.7 i 0.2 (8)
2.8 f 0.1 (8)
'From the midpoim of fluorescencetitration curves.
b ~ the
n basis of dynamic analysis inwlving proton-induced fluorescence
) association
quenching processes, rate constants of proton dissociation ( k ~and
(h)were determined (K, = krih,.
'A typical value obtained by students using wavenumbeffi for maxima of abso tion and fluorescence (eq 7).to estimate a-, and &a.
a)A typical value obtained by students using the intersection p i n t of mutually
normalized absorption and fluorescencespectra to determine Ea- and EHA.
Experimental
I n this experiment, the absorption and fluorescence
spectra of 2-"aphtol solutions can'be measured using any
available absorption fipectrophotometer and spectrofluorimeter. I'he results presented here have been performed
using a Specord UV-VIS spectrophotomcter (Zeiss) and a
Pcrlun-Elmer MI'F 44A spertroflutnimcter.
Materials
2-Naphthol (Merck) was purified by repeated crystallization
from water and sublimation. HCI (38%.POCh) and NaOH (POCh)
were used as obtained. Double-distilled water was used to prepare
0.1 M HCI and 0.1 M NaOH solutions.
Solutions
Two solutions of 2-naphthol are prepared in the concentration
range of1 x lo4 M: one in 0.1M HCI and the other in 0.1 M NaOH.
They are used for the measurement ofahsomtion suedra in l-cm
cells. However. to avoid inner fdter and wn&ntra&n auenchine
e N x t s fil (seealso ref 7 the suluttons should bc di~urrrbfor flu":
re.icence mearuwments. Thus, 1 x 10' M 2-nnphthnl in 0.1 M
NnOli is rrrarnmcndd for fluore.iernce s t u d i e s .
Procedure
1. Record the absorption spectra in turn for the two 2-naphthol
M in 0.1 M HCI and 0.1 M NaOH, respecsolutions (e -1 x
tively), using a l-cm cell in the range of 2 4 M 0 n m (0.1 M HC1
or 0.1 M NaOH must he used in the reference cell, respectively).
2. Rewrd the fluorescence spectra of2-naphtholsolutions (c-1
x
M in 0.1 M NaOH) using a l-un eellin the rangeof32&560
nm (excitation wavelength 282 nm).
3. Record the fluorescence soectra of solvents in the same exuermental condltwns ss in pomr 2
I . Cnlmlntr rhr mamma of the lung wavelength absorptton
bands I wavcnumhrrs &,
.... and \.t.. m ,-'I and the maxmn ol fluorescence (wavenumbers .-.and .. in mi1).
5. Using eq 7, determine EHAand EA6. Using eq 6, calculate the value ofpK,* (for 2-naphthol pK. =
Results and Discussion
The absorption and fluorescence spectra of 2-naphthol
are measured in 0.1 M HCI and 0.1 M NaOH, where only

acid or only base forms were obsewed. The measured absorption and wrrected (for apparatus response) fluorescence spectra are presented in Figures 2 and 3. The solvents used do not show a n y emission u n d e r t h e
experimental conditions used.
Following the procedure described in the experimental
section, the value of pK,* for the excited singlet state of
2-naphthol was estimated a s pK,* = 3.1 0.3. This value
shows that for 2-naphthol the increase in acidity with excitationis very large, 6 pK, units (in the ground state pK.
= 9.5).
If the student's time is not limited, he or she can estimate 0-0 transitions for acid and base forms a t the intersection point of mutually normalized absorption and emission spectra (Figs. 2 and 3). I n this case, however, the
fluorescence spectra must he wrrected for apparatus response, which can be done automatically (MPF 44A) or by
the "point by point" method (see 6).As is described in reference 5. this is a better aonroximation to the 0-0 transition for 2-naphthol than &e average of the corresponding
absorption and luminescence maxima. The pK.* values obtained by students in our laboratory as well a s those taken
from the literature are summarized in the table. The pK.*
values obtained for 2-naphthol in the f r s t excited singlet
state using the Forster cvcle are in good agreement with
those measured by different more t&e-co&uming methods.
Even the results obtained by the approximation of 0-0
transition as the average
.. value of wavenumhers for the
maxima of absorption and fluorescence spectra teq 7, arc
com~arablcwtth the data taken from the literature (see
table).
This exueriment can be extended bv the determination of
fluorescence gpectra of 2-naphthol as a function of pH to
see ifthe resultant -titration curves" eivc the samc cxctted
state pK.* value as fmm the Forster cycle method. The detailed description of pKS* determination b s the fluorescence titrati'n and kinetic analysis method;including the
casc of 2-naphthol, can be found in references 2 . 3 , and 8.
Finally, a student can also measure the fluorescence
spectra for different excitation wavelengths (ex.. 282 nm
Gves excitation to the S2 state; 315 nkand 3 G n m give
excitation to the St state for the HAand A- forms, respectively) and prove that the fluorescence handshape of 2naphthol and &naptholate in solution and its position do
not depend on the excitation wavelength.

Acknowledgment
Financial support from the Ministry of National Education, is gratefully acknowledged.
Literature Cited
1. Barltmp, J A ; Coyle, J. D. P~incipkaofPhotochernisfry; Wiley: Nev York, 1978: pp
d.
.C 7

2. Idand, J. F;Wyatt,PA.H.Adu. Phys. Org Chem. 1976, 12. 131.

Ed; Pe'gam'gamn:Odord,
3. Vander Donekt, E.P*ogmm in Reaction Kimtics; Porter, 0..
197O:Vol. 5. D 273.
4. ~ o r s t e r , ' ~ h . ~ ' ~ k c f r n clSM,51,42.
h~rn.
5. Grabowski,Z. R.:Grabowska,A.Z. Phys. Chem, NeueFolgp 1916, 101,197.
6. Parker, C.A. Phololurni~sc~nce
of Solutions; Elsevier: New York, 1968, p 220 and p
252.

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