Advances in Molecular Relaxation Processes 235

Elsevier Publishing Company, Amsterdam. Printed in the Netherlands

RELAXATION TECHNIQUES IN FAST REACTION KINETICS

H. STREHLOW
Max-Planck-Institut fiir biophysikalische Chemie (Karl-Friedrich-Bonhoeffer-Institut), CGttingen
(West Germany)

CONTENTS

I. Introduction ................................ 235

II. Chemical relaxation ............................. 236
A. Temperature-, pressure- and field-jump techniques .............. 236
1. Temperature-jump technique ...................... 238
2. Pressure-jump technique ........................ 239
3. Field-jump technique .......................... 239
III. Stationary methods ............................. 240
IV. The evaluation of relaxation times. ...................... 240
V. Mean life times as obtained from NMR line broadening and chemical relaxation times 241
A.NMR .................................. 243
1. Advantages .............................. 243
2. Disadvantages ............................. 246
B. Chemical relaxation ........................... 246
1. Advantages .............................. 246
2. Disadvantages ............................. 246
VI. A practical comparison of NMR line broadening and a relaxation technique applied to
the same chemical reaction .......................... 246
References ................................... 248

I. INTRODUCTION

In the early nineteen-fifties, two different kinds of relaxation techniques were

developed which both proved to be very useful in the investigation of rapid chemical
reactions. One of these techniques is nuclear magnetic relaxation in systems
with rapidly exchanging magnetic nuclei. It was first introduced by Gutowsky
et al. and has since been used in many laboratories. The other relaxation
method has been called chemical relaxation. It was mainly developed by Eigen
et al. and also has found widespread application. Chemical relaxation will mainly
be covered in this review. The advantages and drawbacks of both techniques will
be compared and a specific example will shortly be given of a chemical reaction
which has been investigated by NMR line broadening3 and by the pressure-jump
relaxation method4.

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236 H. STREHLOW

II. CHEMICAL RELAXATION

Chemical equilibrium constants depend on external parameters such as

temperature, pressure or electric field strength. If such parameters are rapidly
changed, momentarily the system will not be in equilibrium. Therefore, a chemical
reaction occurs which re-establishes equilibrium conditions. As long as the relative
change in the equilibrium constant is small - and in practice this is always the
case - the re-adjustment of the concentrations to their new equilibrium values
occurs at a rate which is proportional to the deviation of the momentary concen-
tration from its equilibrium value. By measuring the change of concentration as a
function of time, the rate constants of the chemical reaction may be obtained.
Aside from these transient methods, the stationary state of a reacting system under
the influence of a periodically changing external parameter is also changed by
chemical relaxation and may be used for the investigation of fast chemical reac-
tions (ultrasonic absorption, dielectric relaxation).

A. Temperature-, pressure- andfield-jump techniques

The most simple situation prevails if the external parameter is changed as

quickly as possible from one constant value to another. Ideally, the parameter,
e.g. the pressure on the reacting system

A+B %c (1)
kz
will be subjected to a step function in time (Fig. l(a)).

Fig. 1. Principle of pressure-jump relaxation.

The equilibrium constant is changed according to

din K __g,-_AE
dp cpp RT
Advan. Mol. Relaxation Processes, 2 (1972) 235-249
RELAXATION TECHNIQUES IN FAST REACTION KINETICS 237

(where K is the equilibrium constant, AV the volume of reaction, a the coefficient

of thermal expansion, c,, the specific heat, p the density, and AH the enthalpy of
the reaction) and the concentrations will approach their new equilibrium values
(Fig. l(b)). We shall now evaluate the rate law for this approach assuming a reac-
tion of type (1).
If cA, c, and cc are the instantaneous concentrations of A, B and C, re-
--
spectively, which change with time to their equilibrium values c,, , cB, and cc after
the pressure jump, we have the equation

The deviations of the actual concentrations from their equilibrium values will be
designated as

Aci E ci-c (4)

With the mass balance equation

Ac,+Ac, = 0 (9
and the stoichiometric equation

AC, = AC, = AC (6)

we obtain from eqn. (3)

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

AC = Ac(t = 0) exp (-t/z) (8)

with

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.

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238 H. STREHLOW

(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

AT=g [I-exp(-&)I (10)

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)*.

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RELAXATION TECHNIQUES IN FAST REACTION KINETICS 239

With these techniques, electrical conductance has been used as a monitor

of the concentration changes after the temperature jump. However, detection by
optical absorption has also been used in combination with the microwave pulse
technique.

2. Pressure-jump technique

Different kinds of pressure-jump apparatus have been described in the litera-

ture. In the most often used version, pressure (of the order of 100 atm) is applied
to the system to be investigated in an autoclave. The autoclave is closed by a
metal membrane which bursts spontaneously at this pressure. In about 50 psec
the pressure falls to 1 atm. Thus, relaxation times 2 100 psec can be measured.
The concentration changes are followed by conductivity measurements. A relative
change of resistance of 10e5 is about the limit of detectability. However, a general
drawback of conductivity measurements in relaxation techniques is the appreciable
loss in sensitivity if the solution contains non-relaxing electrolytes e.g. buffers.
Another version of the pressure-jump apparatus follows the course of
the reaction by measuring the temperature with a rapidly indicating thermistor
(NTC resistor), thus taking advantage of the heat of reaction. The range of relaxa-
tion times which can thus be measured is about 10-2-100 sec.
A third type of pressure-jump apparatus works with an increasing pressure
step12. As in gas shock wave technique, a shock wave may be produced in liquids
resulting in a very sudden pressure jump (N 1 psec) at the end of the shock tube.
This jump is much sharper than in the normal pressure-jump apparatus.
The time available for measurement is 21/v, where 1 is the length of the tube
and v the velocity of sound. 21/v is of the order of 14 msec. This version of the
pressure-jump technique is, therefore, a useful tool for measuring reactions which
are too fast for the more conventional pressure-jump apparatus. The concentration
changes are either followed by conductivity or - with a pressure jump of the order
lo3 atm - with absorption spectrophotometry13.

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

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240 H. STREHLOW

electric field collapses
from a large condenser
discharge of a coaxial
thus be studied, either
concentration monitor.
too soon. The electric field is applied in pulse form either
with a switch-on and a switch-off spark gap14, or from the
high voltage cable into the celli. Rather fast reactions can
with conductivity or with absorption spectrometry as the

III. STATIONARY METHODS

Instead of a stepwise perturbation of the chemical equilibrium, as discussed

in Section II, a periodical perturbation may also be applied as in an ultrasonic wave
or in an alternating electric field. If the reaction is very fast compared with the
frequency (l/z >> w) the system will respond in phase and no energy absorption
will occur. The energy absorbed in a half-wave by the system is dissipated in the
next half-wave of the oscillation. With very slow reaction (l/r << 0) there is a
phase shift of 90 but again no energy absorption, since the response of the slow
reaction cannot follow the excitation and its amplitude therefore vanishes. With
l/r = w a maximum of energy is absorbed with a phase shift of 45. Therefore,
chemical relaxation adds to the absorption of energy in ultrasonic16 and electric
high-frequency fields l4 the maximum effect occurring at a frequency o = l/z. In
the case of the chemical contribution to dielectric relaxation, eqn. (11) shows that
AlnK- A(,!?). Therefore, the equilibrium is shifted only sufficiently if the high
frequency field is superimposed with a high, constant electric field. With periodica
perturbation techniques, relaxation times as short as lo- lo set may be determined

IV. THE EVALUATION OF RELAXATION TIMES

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.

Type of reaction Relaxation time

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

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RELAXATION TECHNIQUES IN FAST REACTION KINETICS 241

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

(+ indicates that the equilibrium A + B 4 AB is very fast compared with AB+C;

eqn. (15) is obtained from eqn. (14) with k,,, k,, >> k,,, k32; K E cAB/cAcB.
The following characteristics of these equations are noteworthy. The relaxa-
tion times depend on both the forward and backward rate constants in an additive
manner. In general, they are functions of the concentrations which are different
for different types of reaction. Therefore, proposed mechanisms may be tested by
the determination of the concentration dependence of r. However, it should be
mentioned that only if the rate can be measured over a rather large range of con-
centration are the conclusions unambiguous, A considerable degree of experimen-
tal precision is required for that purpose. In many cases, modern equipment really
affords this precision provided that a careful evaluation of z is performed18. In
eqns. (12)-(15) for the sake of simplicity, the influence of the activity coefficients
has been neglected. With higher concentrations this is, of course, not permissible.
In principle, equilibrium constants may also be evaluated from the concentration
dependence of r. In most cases, however, more precise results are obtained by
combining relaxation measurements with conventionally determined equilibrium
constants.
Another way of obtaining equilibrium constants should be mentioned. The
amplitude of the relaxation effect, i.e. Ac(t = 0) in eqn. (8), provides information
on equilibrium constants which are sometimes not easily obtained with other tech-
niques. Though this method cannot be considered to be very precise, it may supply
important semi-quantitative data on equilibrium constants in complicated chemical
systemsi9.

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
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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

Av+ exchange = 4n(vA - vB)2it &A+ zB) (17)

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

PA~B = PB~A (18)

The rate constants and the average life times are given 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

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RELAXATION TECHNIQUES IN FAST REACTION KINETICS 243

activation parameters not only the temperature dependence of z must be evaluated

in chemical relaxation but also that of K, i.e. the enthalpy of the reaction must be
known from equilibrium measurements.
In the slow case, NMR measurements of the area under the line of AH and
BH, respectively, supplies the proton fractions pA and pB . Their ratio, pA/pB, is
independently obtained from the ratio of the life times, r&n, so that the consis-
tency of the measurement may be contrclled. From measurements of zA and zs
as a function of temperature, we obtain most directly the rate constants k, and
kz and the concentrations pA andp, at different temperatures as well as the two
energies of activation and the enthalpy of the reaction. The latter can be obtained
independently either from the temperature dependence of the areas under the two
absorption lines or from the difference between the two activation energies.
Thus, in the slow case, the NMR information is more direct and more
abundant than that obtained from chemical relaxation.
However, in the fast case, eqn. (17) NMR line broadening supplies less in-
formation than chemical relaxation. Equation (17) contains the sum of z, and ze
and, furthermore, the mole fractions pA and pB and the chemical shift (vA-vB)
which cannot be taken from a high resolution spectrum with coalesced absorption
lines. Therefore, as with chemical relaxation, additional information on the equilib-
rium constant must be available and an estimation of the chemical shift has to be
made. The latter difficulty is overcome with a suitable application of the spin-echo
technique.
We are now in a position to list the advantages and the drawbacks of the
two compared techniques.

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

NH; + NH3 5 NH, + NH;

k

or the kinetic measurement of hindered molecular rotation. Of course, chemical

relaxation cannot be applied to such cases, since the equilibrium constant is unity
under all conditions.
Another advantage of NMR is the need for only a fraction of a cm3 of solution,
the concentration of which, however, should be as high as possible.

Advan. Mol. Relaxation Processes, 2 (1972) 235-249

244

TABLE 1

SURVEY OF CHEMICAL RELAXATION TFSHNIQUES

Technique AT, Ap, AE Detection of Ac by Time range Volume of

produced by Zower limit Upper limit solution
(see) (set) needed (cm3)

Temperature-jump Discharge of Optical absorption 5 x 10-6 0.2 3-10

capacitor (rotation, fluores-
cence)

Flash light Conductivity 2x10-5 2x10-2 0.3

Laser Conductivity 2x10-6 2 x10-2 0.01

Microwave Conductivity, 2x10-6 2 x 10-Z 0.1

optical absorption

Pressure-jump Autoclave Conductivity, 1o-4 10 0.3

with rupture thermometry, lo-2 100 50
disc optical absorption 10-b 1 5

Shock wave Conductivity, 2 x 10-e 2x10-3 0.1

in liquids optical absorption 2 x 10-G 4x10-3 5

Field-jump Capacitor Conductivity 10-7 10-a 10

switch-on
switch-off

Cable Optical absorption 5 x 10-a 5 x 10-S 2

discharge

Stationary, Ultrasonic Dissipation of lo-0 10-S 2%1000

ultrasonic wave acoustical energy

Phase angle in 10-7 10-a 0.1

conductivity bridge

Stationary, High electric Dielectric loss 5 x10-9 10-e 1

dielectric field with
superimposed
high-frequency
field

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 RELAXATION TECHNIQUES IN FAST REACTION KINETICS 245

Type of reactions Advantages Disadvantages ReJ

Biochemical reactions, Very widely applicable High electrolyte concentration 5

complex formation, necessary
proton transfer

Ionic reactions Fast, simple, small Possibility of flash photolysis 6

volumes

Ionic reactions Very fast, extremely Not simple in application 7

small volumes

Ionic reactions Conductivity and optical Expensive equipment 8, 9

absorption possible,
gentle disturbance of
equilibrium

Ionic reactions, bio- Simple, small volume, Not very fast 10

chemical reactions sensitive Rather slow 11
Not very fast

Ionic reaction, proton Fast, small volume, Time per experiment high 12
transfer Fast, small volume Rates are measured at high pressures 13

Dissociation of weak High dilution possible, High dilution necessary. 14

electrolytes, proton very fast Sophisticated equipment
transfer

Dissociation of ueak High dilution possible, High dilution necessary. 15

electrolytes, proton very fast. Measurements Sophisticated equipment
transfer in non-aqueous media

Ionic reactions, Very fast Not sensitive large volumes. 16

association of un- A series of apparatus for a time
charged molecules, range 1O-9-1O-5 set
biochemical reactions

Ionic reactions Fast, small volume Cumbersome to use. 21

Biochemical reactions, Very fast Experimentally difficult 17

hydrogen bonding
reactions

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246 H. STREHLOW

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.

VI. A PRACTICAL COMPARISON OF NMR LINE BROADENING AND A RELAXATION TECH-

NIQUE APPLIED TO THE SAME CHEMICAL REACTION

The kinetics of hydration of pyruvic acid were investigated by the pressure-

Aduan. Mol. Relaxation Processes, 2 (1972) 235-249

RELAXATION TECHNIQUES IN FAST REACTION KINETICS 247

jump technique 4. It was concluded that the reaction proceeds as

kz3
CH,COCOO - + H,O + + CH,COCOOH+ H,O + CH,C(OH)$ZOOH (21)

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.

Advan. Mol. Relaxation Processes, 2 (1972) 235-249

 248 H. STREHLOW

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

k kH &I AH: ASf: AH AS Method

(set- ) (M-see- ) (kcallmole) kcaljmole callgrdmole kcal/mole callgrd mole

Hydration 0.55kO.05 6.310.7 9.0*0.6 Relaxation

(0.5&0.4) 5.0*1.5 10.0&0.5 9.4 -24 -7.1 -23 NMR

Dehydra- 0.22&0.02 2.5*0.3 Relaxation

tion (l*l) 2.010.8 17.3*0.5 16.7 +1 +7.1 +23 NMR
-._____

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RELAXATION TECHNIQUES IN FAST REACTION KINETICS 249

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