EXPERIMENT 34

Excited-State Properties of 2-Naphthol

Part II: Deprotonation and Protonation Rate Constants
Objective
To determine the deprotonation and protonation rate constants of 2-naphthol in
its lowest excited singlet state in aqueous solution.

Introduction
In the previous experiment, we determined acidity constants for aqueous
2-naphthol (ArOH) for both the ground and lowest excited (singlet) states. These
constants pertain to the equilibrium

k
ArOH  H2O 0ˆ ArO
 H3O,
d
ˆ9 (1)
kp

where the rate constants for the forward (deprotonation) and reverse (protona-
tion) reactions are indicated as kp and kd, respectively. A similar equilibrium can
be written for the electronically excited-state species, which is produced via pho-
ton absorption:

kd
ˆ9 ArO
*  H3O,
ArOH*  H2O 0ˆ (2)
kp

in which the values of the forward- and reverse-rate constants may be different
from those in the ground state because of differences in the properties of the
2-naphthol in these two states (for example, different Ka values).
We can express the ratio of the concentrations of free acid and the conjugate
base as a function of the pH:

 
[ArOH]
log   pKa
pH, (3a)
[ArO
]

where we use molar concentrations to approximate activities. An analogous

equation,

 
[ArOH*]
log   pK*
a
pH (3b)
[ArO
*]

applies to excited state species. Equations (3a) and (3b) show that if the pH of
the solution is less than pKa of 2-naphthol (in either electronic state), the free acid
form will predominate over that of conjugate base: [ArOH]  [ArO
]. Likewise,
if pH  pKa, then [ArO
]  [ArOH].
Suppose that by using a suitable buffer, the pH of the medium is established
to be less than pKa but greater than pK*. a The ground state of the system will
then consist primarily of ArOH. Electronic excitation via light absorption will in-
stantaneously (
10
13 s) transform ArOH into ArOH*. We may assume that in
this experiment, the buffer holds the pH of the medium constant during and af-
ter electronic excitation. This is a valid assumption because the number of pho-
tons absorbed per unit volume is much less than the ground-state concentration
 Experiment 34 11-9

of ArOH. Thus [ArOH*]

[ArOH]; moreover, ArOH* will spontaneously dis-

sociate to form ArO
* in order to establish new equilibrium conditions. Under
these circumstances, [ArO
*] must be greater than [ArOH*] because pH  pK* a
[see equation (3a)]. In fact, most of the fluorescence observed from ArO
* takes
place from species that were formed via ArOH* deprotonation after elecronic ex-
citation. As excited-state equilibrium is approached, the ArOH* concentration
decreases while that of ArO
* increases. The strategy of this experiment in de-
termining kd and kp is to measure the dependence of [ArOH*] on the pH of the
solution. [ArOH*] is monitored through its fluorescence intensity If, assuming
that it is proportional to [ArOH*] (see the next section). The pH is established
(and varied) using an ammonium acetate buffer.

Kinetic Analysis
Because in this experiment pH
pKa, we consider only light absorption by the
protonated form ArOH:

ArOH  habs
ArOH*. (absorption)

The ArOH* thus produced is, like any excited state, metastable, and when it re-
laxes (dissipates the excitation energy) it can undergo a number of different de-
cay processes, such as

kr
1. ArOH* ¶l ArOH  hfluor (fluorescence) rate  kr [ArOH*].

knr
2. ArOH* ¶l ArOH  heat (nonradiative decay) rate  knr [ArOH*]

kd
3. ArOH* ¶l ArO
*  H(aq) (deprotonation) rate  kd [ArOH*]

kAc

4. ArOH*  Ac
¶l ArO
*  HAc (deprotonation via Ac
) rate  kAc
[ArOH*][Ac
]

In addition to radiative (fluorescence) decay (1) and nonradiative relaxation

(2), ArOH* can undergo “unassisted” (3) and “acetate-assisted” (4) deprotona-
tion. This distinction is significant because the rate of deprotonation will be en-
hanced in the presence of the acetate ion in the bimolecular step indicated in
process 4. Undoubtedly, solvent plays a role in the unassisted deprotonation (3),
but this step can be considered pseudo first order in ArOH* because the con-
centration of “solvent” is so much larger than [ArOH*]. The reverse steps of the
deprotonation processes, which are bimolecular and proportional to [H3O] and
[HAc] (see steps 3 and 4, respectively), are ignored because under these experi-
mental conditions, [H3O] and [HAc] are very small.
If the pH of the solution is much lower than pK* a (for example, in the pres-
ence of sulfuric acid), deprotonation by either process is suppressed and fluores-
cence from ArOH* predominates. In this case, the fluorescence intensity If0, which
is proportional to the ratio of the rate of radiative decay to the total ArOH* de-
cay rate, can be expressed

Ckr[ArOH*]
If0   , (4)
kr[ArOH*]  knr[ArOH*]
11-10 PART 11 Photophysics and Molecular Spectroscopy

or, canceling [ArOH*],

Ckr
If0,   , (5)
kr  knr

where C is an instrumental constant.

In contrast, when pH  pK* a (but less than pKa) under NH4Ac buffer condi-
tions, the deprotonation steps become kinetically important, and thus the de-
nominator of equation (4) will contain the aditional terms kd[ArOH*] and
kAc
[ArOH*][Ac
]. Therefore, the ArOH* fluorescence intensity, now denoted
as If, become [see equation (5)]

Ckr
If   . (6)
kr  knr  kd  k


Ac[Ac ]

The deprotonation of ArOH* causes a diminution in its fluorescence intensity;

thus If
If0. Assuming that [ArOH*] is identical in all the solutions studied, the
ratio of ArOH* fluorescence intensity in a solution containing sulfuric acid (low
pH) to that containing ammonium acetate buffer (higher pH) is obtained by di-
viding equation (5) by (6):

If0 kr  knr  kd  kAc
[Ac
]

   . (7)
If kr  knr

We can rearrange equation (7) to a more convenient form,

If0 kAc
[Ac
]
 
kd

1     (8)
If kr  knr kr  knr

or

If0
 

1  0kd  0kAc
[Ac
],
If

where 0  1/(kr  knr) and is the “lifetime” of ArOH* in the absence of signif-
icant deprotonation. A plot of ( If0/If
1) versus [Ac
] should be linear with slope
0kAc
and intercept 0kd. To determine kd, one must obtain 0 from a separate
experiment.
The information provided by this type of study, which involves time-
independent, or steady-state, measurements could also be obtained directly using
a transient, or kinetic, approach by monitoring the fluorescence decay of ArOH*.
After photoexcitation by a very short pulse of light (

10
9 s), the ArOH* flu-
orescence intensity follows the first-order decay law

If (t)  [ArOH*]0exp{
(kr  knr  kd  kAc
[Ac
])t}, (9)

where [ArOH*]0 is the concentration of photoexcited ArOH produced immedi-

ately after excitation (at t  0) and t is the time after excitation. Note again that
equation (9) represents the proportionality between fluorescence intensity and ex-
cited-state concentration. The coefficient of t in equation (9) is the reciprocal of
the fluorescence lifetime of ArOH*, (1/ Ac
), in the presence of the NH4Ac buffer.
 Experiment 34 11-11

The information provided by the steady-state Stern-Volmer-like plot—equation

(8)—could be directly obtained from a plot of 1/ Ac
versus [Ac
]. These exper-
iments can be carried out using a nanosecond (10
9 s) fluorescence decay
spectrometer.
In this experiment, you will obtain kd using steady-state approach previously
described. You can obtain the value of 0 from the provided data for the time de-
pendence of ArOH* fluorescence intensity. This information comes from a fluo-
rescence decay experiment (see the Appendix to this experiment). We emphasize
again that in deriving equations (4) to (8), it is assumed that throughout the se-
ries of fluorescence intensity measurements, first in sulfuric acid and then in dif-
ferent NH4Ac buffer solutions, the concentration of ArOH* is invariant. This
condition requires that the amount of light absorbed by ArOH per unit time be
constant; thus, not only must the formal concentration of 2-naphthol be identi-
cal in each of the samples but also the intensity of the excitation source must not
fluctuate. Satisfying these conditions is crucial for the success of the experiment.
Once you obtain a value of kd from the analysis of the data as discussed, you
can determine the value of kp (the protonation rate constant for the excited state
naphthoxy ion) from K* a because

kd
a  
K* (10)
kp

for this set of elementary reactions.

Safety Precautions
◆ Always wear safety goggles; these glasses should block ultraviolet light.
Ordinary plastic safety goggles or glasses may not be effective in absorbing
all the ultraviolet radiation. Check with your instructor.
◆ 2-Naphthol is an irritant. If you are to prepare the solutions from solid
material, you must wear gloves; if possible, work in a fume hood.
◆ Be sure you have been instructed to use proper pipetting techniques when
handling 2-naphthol. Never pipet by mouth.
◆ When using the fluorimeter, be sure that any ozone produced by the
ultraviolet source is vented. Ozone is an irritating, dangerous gas that has a
sharp, pungent odor. If you notice this kind of odor during the experiment,
inform your instructor at once. The laboratory must be immediately
ventilated and, if necessary, evacuated.

Procedure Using Scanning Fluorimeter

1. Prepare a series of aqueous solutions in 25-mL volumetric flasks, each
having the same ArOH concentration (about 4.0  10
4 M). One of them
will be 0.1 M in H2SO4 (for If0), another
0.1 M in NaOH (in order
to observe predominantly ArO
* fluorescence). The remainder of the
solutions will have varying NH4Ac concentrations between
0.01 M and

0.10 M. Study at least five NH4Ac-containing ArOH solutions in this
range. Stock solutions of H2SO4, NaOH, ArOH, and NH4Ac will be
provided. Label each solution and record the ambient temperature.
2. You will be shown how to operate the fluorimeter. Using an excitation
wavelength of 320 nm, obtain the fluorescence spectra of the ArOH
11-12 PART 11 Photophysics and Molecular Spectroscopy

solutions starting with the solution containing H2SO4. Next, obtain the
fluorescence spectrum of the NaOH-containing solution. Then proceed with
the NH4Ac-containing solutions in order of increasing NH4Ac
concentraion. It is recommended that you display these spectra on a
common wavelength scale. If the excitation source remains steady and the
solutions have the same bulk ArOH concentrations, a distinct isostilbic
(equal brightness) point should be produced. This is the common
wavelength point of all the ArOH fluorescence spectra. See Experiment 34
for a further discussion of the isostilbic point.
3. If a fixed-wavelength fluorimeter is used or if time permits, perform a
second determination of data at the emission wavelength of the fluorimeter
corresponding to the maximum for the protonated ArOH* (
360 nm).
First, place the H2SO4-containing sample in the cavity and establish the
“maximum” intensity setting on the chart paper by moving the pen close to
its full displacement (or just read and record the signal strength). Carefully
and systematically obtain values of the fluorescence intensity of the
buffered solutions in order of increasing NH4Ac concentrations. If there is
any doubt about the constancy of the instrument, remeasure If0 and
compare it with the original value. If the agreement is unsatisfactory, you
will have to repeat the series of measurements.
Data Analysis
1. Using the time-dependent fluorescence intensity data provided in the
Appendix for ArOH in 0.10 M H2SO4, determine 0. The fluorescence
quantum efficiency of ArOH under these conditions has been determined
to be 0.18; this quantity is equal to kr 0. Report values of both kr and knr
for ArOH.
2. Tabulate If0 and the If and corresponding [Ac
] values for the samples, and
construct a Stern-Volmer-like plot indicated by equation (8). Determine
values of kd and kAc
and their standard deviations using linear regression.
Consider the error in 0 [obtained in step (1)] in your error analysis of the
rate constants.
3. Determine kp from your previously obtained value of K*
a [see equation (10)].

4. Tabulate all the rate constants determined and include estimates of their
respective uncertainties.
5. Using the Stokes-Einstein-Smolouchowski (SES) equation for a diffusion-
controlled rate constant (see Experiment 22), calculate kdiff:

8000RT
kdiff   (dm3 mol
1 s
1),
3

where  is the solvent viscosity. The indicated units for kdiff are obtained if
R and  are in SI units, that is, 8.314 J K
1, and in N m
2 s, respectively
(1 cP  10
3 N m
2 s). Compare your values of the second-order rate
constants kd and kAc
with kdiff. You can use the viscosity of water at the
appropriate temperature for this comparison. The SES equation applies to
the reaction between two neutral species (or a neutral and a charged
reaction pair). For anion–cation pairs (each of single charge), the rate
constant is about an order of magnitude larger than kdiff.
 Experiment 34 11-13

Questions and Further Thoughts

1. The pH of the aqueous medium is assumed to be unchanged as a result of electronic
excitation of 2-naphthol. Why is this justified?
2. Can you predict how the value of the deprotonation rate constant of ArOD* (ArOD)
would differ from that of ArOH* (ArOH)? What would you need to know to answer
this question?
3. Can you suggest an experiment in which the deprotonation rate constant of ArOH
(ground state) could be determined?
4. Ozone is sometimes produced by ultraviolet light sources. What is the mechanism by
which ozone is produced? Can you suggest a way in which the ozone production by a
given ultraviolet source can be eliminated?
5. As the source of acetate ion you used ammonium acetate. Why is this compound cho-
sen? What would be the advantage or disadvantage of using sodium acetate?

Further Readings
2-Naphthol Protolysis
R. Boyer, G. Deckey, C. Marzzacco, M. Mulvaney, C. Schwab, and A. M. Halpern, J.
Chem. Educ., 62:630, 1985.
J. Van Stam and J. E. Loefroth, J. Chem. Educ., 63:181 (1986).

Fluorescence and Photophysics

J. R. Lakowicz, Principles of Fluorescence Spectroscopy, Plenum Press (New York), 1983.
N. J. Turro, Modern Molecular Photochemistry, Benjamin/Cummings (Menlo Park, CA),
1978.

Appendix

Fluorescence Decay Data for 2-Naphthol

in 0.10 M H2SO4 at 25°C
Time (ns) Intensity*

0.00 21753
1.00 18907
2.00 16380
3.00 14171
4.00 12432
5.00 10757
6.00 9288
7.00 8138
8.00 7083
9.00 6014
10.00 5350

*Photons emitted per unit time.