Beruflich Dokumente
Kultur Dokumente
H. STREHLOW
Max-Planck-Institut fiir biophysikalische Chemie (Karl-Friedrich-Bonhoeffer-Institut), CGttingen
(West Germany)
CONTENTS
I. INTRODUCTION
A+B %c (1)
kz
will be subjected to a step function in time (Fig. l(a)).
din K __g,-_AE
dp cpp RT
Advan. Mol. Relaxation Processes, 2 (1972) 235-249
RELAXATION TECHNIQUES IN FAST REACTION KINETICS 237
The deviations of the actual concentrations from their equilibrium values will be
designated as
Ac,+Ac, = 0 (9
and the stoichiometric equation
dAc
- kl(G+QAc+k2A c+k,(Ac)2+k, CACB-k2C, (7)
dt
k, (AC) is small compared with the other terms, as long as the shifts in concentra-
tion are much smaller than the concentrations. This term may, therefore, be
neglected. The last two terms vanish, since the 5 refer to equilibrium conditions.
Therefore, we are left with a linear differential equation, the solution of which is
1
- = k,(c,+c,)+k, (9
r
r is the relaxation time for the reaction, which may be determined experimentally
by measuring the change of the concentrations as a function of time.
If the outlined principle is to be realized for the measurement of fast chemical
reactions, three problems have to be solved.
(I) How to effect a very sudden jump in temperature, pressure or electric
field.
(2) How to measure the fast-changing, very small concentration differences.
(3) How is the measured relaxation time connected with the rate constants
and concentrations of the reactants? (Equation (9) is only a special case referring
to system (l).)
The first two experimental problems will be discussed with the description of
different chemical relaxation apparatus. The theoretical question of the dependence
of r on the reaction mechanism, the concentrations, and the equilibrium values
involved will then follow.
I. Temperature-jump technique
Fast temperature jumps have been realized by two different techniques, the
first of which has been used very extensively in the investigation of chemical relaxa-
tions. A high-voltage condenser is discharged through a solution containing the
chemical system to be investigated. The switching of the circuit is performed by a
spark gap. The temperature jump thus obtained is given by
with C the capacity of the capacitor, U the voltage, R the resistance, cP the specific
heat, p the density, and V the volume of the solution. Typical values are U = 50
kV, C = 0.1 yF, p = 1 g cmP3, V = 5 cm3, cP = 4.19 joule/grad, R = 40 R.
Under these conditions temperature jumps of 5 C can be achieved in about
RCj2 = 2 psec. With temperature jumps as high as this, relatively large shifts of
the equilibrium constants
AInK=- AH AT
RT2
result and optical detection methods with their inherent advantages may be used.
Absorption spectrometry is the technique most often used for the detection
of the concentration changes with time. If the reacting species involved in the
chemical reaction to be measured do not change the absorption of light sufficiently,
it is possible to couple another chemical reaction to the system which does absorb
light and is fast enough not to be rate-determining. pH indicators are often used as
coupled systems, since in many reactions proton transfer occurs.
Besides light absorption, optical rotation and fluorescence spectrometry
have been used, though less frequently, for the detection of concentration changes
in temperature-jump relaxation equipment.
Another way to perform fast temperature jumps is the absorption of light
either from a fast flash light6 or from a giant pulse laser7. Values of AT of roughly
1 C in 2 psec have thus been obtained. A similar technique is the absorption of
intense microwave pulses (AT - 0.7 C in 2 psec)*.
2. Pressure-jump technique
3. Field-jump technique
If, during a reaction, the electric moment changes, e.g. in the dissociation of
a weak electrolyte, the equilibrium constant is shifted by the application ofan electric
field jump, E, according to
d In K AEVE
dE =E
(11)
where AE is the change of the dielectric constant due to the chemical reaction.
Rather high electrical fields, of the order of 104-lo5 V cm-, are necessary to cause
a detectable shift in equilibrium. Therefore, only solutions with a low conductivity
may thus be investigated, because otherwise, in highly conducting media, the
electric field collapses too soon. The electric field is applied in pulse form either
from a large condenser with a switch-on and a switch-off spark gap14, or from the
discharge of a coaxial high voltage cable into the celli. Rather fast reactions can
thus be studied, either with conductivity or with absorption spectrometry as the
concentration monitor.
As demonstrated above (eqn. (9)) an expression for the relaxation rate may
be derived for a given reaction. In more complicated types of reaction systems,
more than one relaxation time will be observed. Without derivation, some expres-
sions for relaxation times for some practically important reactions are given below.
1
A$B - = k,+k, (12)
kz T
1
A+B SC - = k,(c,+c,)+k, (13)
kz r
ktz kz3
1
A+B +AB+C ~ =$[~k&(~k)-4rrk] (14)
kz1 ksz Tl,Z
where
c k = k,,(G+c,)+k,,+k23+k32
and
nk = kl2(CA+~)(k23+k32)+k21 k,,
km
1 kzs
A+B+ABSC -= _ G+G) +k
(15)
k32 r l+K(EJ4:+c,) 32
V. MEAN LIFE TIMES AS OBTAINED FROM NMR LINE BROADENING AND CHEMICAL RELAX-
ATION TIMES
For the sake of simplicity, we shall only compare the data for the most
simple reaction of type shown in eqn. (12) assuming that each of the species A and
B contains at least one nucleus with magnetic moment, e.g. a proton. Therefore,
we shall rewrite
AHSBH (12a)
kz
Advan. Mol. Relaxation Processes, 2 (1972) 235-249
242 H. STREHLOW
This most simple case is sufficient to demonstrate the differences in the two tech-
niques. If the proton experiences a chemical shift v,--v, in the state AH with respect
to the state BH, chemical exchange manifests itself in increasing the line widths in
the NMR spectrum. If the mean life times of the proton in the states AH and BH,
rA and zn respectively, are very long compared with (v~-v~)- and with T,, two
lines of line widths ~/XT, are observed (assuming a magnet of ideal homogeneity).
The only kinetic information provided in this case is an upper limit for the rate
of exchange. For T, > zA, zB > (v~-v~)-~, two broadened lines are observed
with the additional line widths
(16)
It is this slow case with two broadened, not yet overlapping, lines which supplies
especially useful kinetic information.
If r-l E (zi 1 +z, ) is of the order vA-vB, a single broad line with a line
width of the order vA-vB is observed. With decreasing r, this line sharpens again
and an exchange broadening of the coalesced single line is given by
where p, is the proton fraction in state AH andp, that in state BH. With extremely
fast reactions, the exchange broadening vanishes (rA, zB + 0 in eqn. (17)). In this
latter case, only a lower limit for the exchange rate is supplied provided that the
chemical shift is known or can be estimated.
The proton fractions and the life times are connected by
dCm_ k c CAH
dt
1 AH=-
: -_=
k1 (19
TA TA
and
_ d%H_
- k c
2BH=- CBH
: -_= k2
(20)
dt TB TB
In the slow case, eqn. (16) the single rate constants are thus obtained
directly. In the case of chemical relaxation, only the sum of the two rate constants
is determined
1
- = k,+k, = k,(l+K)
r
Only with additional information about the equilibrium constant, K = kJk2, can
the single rate constants be obtained. Correspondingly for the measurement of
A. NMR
1. Advantages
In the slow case, very direct and precise information is obtained on the
single rate constants, on equilibria and on activation parameters. In the fast
case with the application of the spin-echo technique the directness of information
is comparable to that of chemical relaxation. NMR technique is the only method
which allows the measurement of fast exchange reaction with no change in the
composition of the system, e.g. of the reaction
TABLE 1
Ionic reaction, proton Fast, small volume, Time per experiment high 12
transfer Fast, small volume Rates are measured at high pressures 13
2. Disadvantages
Only compounds with magnetic nuclei must be used. The sensitivity of NMR
is much inferior to that of chemical relaxation techniques. However, with modern
equipment this drawback of NMR will become much less serious. In the most
informative slow case, only a small range of average life times from about 1 set
to at most (depending on the chemical shift), 5 x lo- 3 set is accessible. In many
cases the time range is considerably smaller. The equipment is rather expensive
and the whole technique is more sophisticated than with chemical relaxation. This
is particularly true if spin coupling is involved or in cases where the chemical shifts
are small, or if the intermediate case (zAN (vA-va)- ) is investigated.
Another disadvantage is that the concentration ratio, pAlpa, should not
differ too much from unity. Similar arguments, however, apply also to chemical
relaxation.
B. Chemical relaxation
1. Advantages
These techniques are applicable over a larger time range (although only with
an arsenal of different relaxation apparatus; see Table 1). With many techniques,
solutions with small concentration may also be investigated. The apparatus is less
complicated and expensive than NMR equipment. For most reactions at least one
relaxation technique may be found which is especially suited for the problem
and supplies precise data.
2. Disadvantages
As with NMR, irreversible reactions cannot be investigated. Most equipment
is not available commercially. The exponential decay curves may often be disturbed
by heat exchange processes or other artefacts. Therefore, it is difficult to get a
relaxation time with a precision better than about f 5 %.
A definite advantage of both NMR line broadening and chemical relaxation
techniques is the simplicity of the mathematical treatment. All kinetic differential
equations are linearized. Therefore, advantage should be taken of chemical relaxa-
tion techniques also in the case of slow reactions, where conventional techniques
are applicable.The increased simplicity in evaluation of the rate laws oftenwill com-
pensate for the change in experimental technique.
By using eqn. (15) the rate constants could be evaluated from the measured
relaxation times. The reaction was found to be acid-catalyzed
kz3 = k&+k&cn (22)
and
k 32 = k;2+k;2cH (23)
The two k were much higher than the corresponding values for the hydration of
acetaldehyde, This fact was explained by assuming an inner-molecular acid
catalysis.
In aqueous solutions of pyruvic acid, the methyl groups in the hydrated and
the unhydrated form of the acid show two lines in the proton NMR spectrum. From
the intensity of the lines the equilibrium constant and from the line widths the
kinetics may be evaluated. With small concentrations of H30f ions the reaction
is rather slow and the absorption lines are broadened to only a small extent. Pre-
liminary measurements of the equilibrium and the rate constants for reaction (21)
with NMR led to rate constants about 3 times as large as the corresponding values
obtained by the pressure-jump technique. These NMR investigations22 have been
performed with high concentrations of pyruvic acid (344) and with the addition
of a high concentration of HCl in order to obtain (easily measurable) large and
broad signals. In order to explain this discrepancy, further NMR measurements
were performed with varied concentrations of pyruvic acid (0.14-10 M) and of
HCl (0.1-5 M) at different temperatures3. The results of these investigations may
thus be summarized: from the measurement of the equilibrium constant KH = kz3/
k,, at different concentrations, it became clear that the reaction (21) had to be
rewritten as
CH,COCOO- + H30+ + 2H20 + CH,COCOOH+ 3H,O +
CH,C(OH),COOH .2H,O (21a)
A trihydrate is formed, the structure of which was proposed to be as shown in
Fig. 2.
1 ..
P 0
\
F-0
_-b
H ....O/~-o\H
"'H 'C-H
H'
Fig. 2. Proposed structure of pyruvic acid trihydrate3.
The above-mentioned difference in the rate constants was due to activity coeffi-
cients very different from unity in the concentrated solutions. Both NMR and chemi-
cal relaxation measurements lead to consistent results when a small correction is
applied for the fact that a trihydrate was formed. The measurements of Kn at low
concentrations with uv absorption photometry, which were used in the evaluation
of the pressure-jump experiments, did not show the existence of a trihydrate. An
interesting effect was observed in the line width measurements. With only small
concentration of HCl, it was found that the concentration ratio, as obtained from
the area under the absorption line and from the ratio of the line widths, did not
agree. The reason is that the line width of the hydrate is not only due to the kinetic
broadening according to eqn. (19) but is also enlarged by hindered rotation of the
methyl group. The two water molecules forming a hydrogen-bonded ring between
the carboxylic proton to one of the geminal OH oxygen atoms make the molecule
rigid with the consequence that hindered rotation of the methyl group occurs.
Thus, from a pure kinetic argument, the proposed structure of the trihydrate has
been strengthened. Besides, the relatively large negative entropy of hydration sug-
gests more than one molecule of water in the hydrate.
In Table 2, the data as obtained by the two techniques are collected. The
table clearly shows the usefulness of applying different techniques to the same
system. Whereas the measurements at low concentrations of H+ ions are very
imprecise with NMR and rather reliable with chemical relaxation, the activation
parameters and the thermodynamic data are better evaluated by NMR techniques.
TABLE 2
THERMODYNAMIC
AND KINETIC DATA FORTHE HYDRATION REACTIONOF PYRUVICACID
REFERENCES