Chemical Physics 7 (1975) 30-40

0 North-Holland Publishing Company

PMRSTUDlESONTHESTRUCTURESOFWATER-ETHYLALCOHOLMlXTURES

A. COCCIA, P.L.INDOVINA,F. PODO* and V. VITI

Labomrori di Fisica. Isriruro Supertire di Sanira 1 Roma. Italy

Received 7 August 1974

Revised manuscript received 17 October 1974

The PMR signals of each individual proton species present in water-elhanol mixtures were analyzed throughout
the entire range of composition. Chemical shifts and line shapes were studied as a function of ethanol mole fraction
UJ. temperature, and working frequency, from -50 to +8OC. at 60.100 and 220 MHz.
The experimental results arc discussed in terms of possible mechanisms of molecular aggregation in the various
regions of ethanol concentration. There is evidence that addition of small quantities of ethanol to water promotes
H-bonding association among water molecules (at I = 20C,f <, 0.08). At intermediate ethanol concentrations (at
r = 2OC.O.25 5f 5 0.75). the linear dependence offexhibited the chemical shift of the water signal evidences
thafwtthe water structures are progressively disrupted by increasing alcohol concentration. At the higher ethanol con-
centration (at 2OC./z 0.8) the substantial independence of both ethanol and water O_Hchemical shifts from the
concentration suggests that water molecules either coordinate or/and are incorporated into the linear aggregates
peculiar to pure ethanol.
The width of the/range in which the hydroxyl signals coalesce is progressively reduced with decreasing temper-
ature.
We qualitatively tested the applicability of an adiabatic two-site exchange model 10 the hydroxyl protonsof these
tixtutes. This model is corrccl!y applicable to solutions at both extremes of the concentration range, but it cannot
describe the linewidth behaviour of the mixturesat intermediate concentrations.

I. introduction tures were reviewed in 1966 by Franks and Ives [4] ,

who critically examined the abnormalities shown
Several studies suggested that the peculiar solvent by these systems in many classical physico-chemical
behaviour of water is related to its unusual structural and thermodynamic properties. However, due to the
properties, i.e., the ability of the molecules to form averaged character of the information provided by
extensive three-dimensional networks, by means of such properties, only indirect insight into the struc-
almost tetrahedrallyarranged hydrogen bonds [ 1,2]. tures can be attained at a local molecular level. A
The possibility of extending this concept to other more powerful approach is provided by high resolu-
liquids or mixed solvents composed of molecules con- tion NMR spectroscopy, since hydrogen bonding life-
taining hydroxyl groups was discussed recently 131. times can be derived from chemical shift measure-
In order to obtain more exhaustive information ments [S] and proton exchange rates through line-
on the role of such three-dimensional hydrogen bond- shape [5,6] and relaxation studies [7].
ng association in water and its binary mixtures, fur- The ethanol concentration at which the two OIj
ther insight is needed of the modifications induced signals merge together, c*, was located around 50
in water structure by the presence of monohydric mole per cent at 20C (40.7 MHz) by Weinberg and
alcohols which can form linear (or cyclic) aggregates Zimmerman [8]. Ageno and Indovina [9] reported
only, by means of cooperative hydrogen bonding [4]. that the (extrapolated) concentrations where the
Several structural properties of alcohol-water mix- EtOH signal begins to appear are 19 and 24 mole per
cent respectively at 0 and 32C (60 MHz). The con-
* To whom inquiries should be directed. centration where the two signals merge is strongly
 A. Gxcia et aL/PMR studies on water-ethyl
dependent on the addition of traces of bases or acids
(1O-6-1O-5 molell-I) [lO,ll].
The temperature dependence of c* in a 2: 1 etha-
nol:water mixture was studied by Schneider and
Reeves 161.
Chemical shifts and relaxation times were recent-
ly studied by Oakes [!2] in water-rich ethanol-water
mixtures in an attempt to ascertain the relative im-
portance of water-alcohol interaction terms due
respectively to the hydroxyl and the hydrocarbon
function of the latter.
Exchange broadening of spin-spin triplets was
studied in ethanol-rich mixtures by Paterson [13] by
using an extension of the McConnel method for ki-
netic analysis of molecular processes [ 141 .
A first conclusion drawn from these studies is the
need for a detailed parallel study of chemical shifts
and lineshapes over the entire composition range of
the two cosolvents. No systematic studies have been
reported so far, which elucidate (a) the dependence
of c* on the working frequency;(b) the dependence
on temperature of the chemical shifts of the ethanol
and water hydroxyl groups in the various intervals of
the mixture composition.
Such studies were undertaken in the present work*.
The results are treated in terms of the possrble differ-
ent mechanisms of molecular aggregation dominating
in the various alcohol concentration regions.
2. Experimental
Ethanol (EtOH) 99.8% pure, analytical grade, was
purchased from Merck AC Darmstadt and used with-
out any further purification. Bidistilled water was
purchased from Carlo Erba and successively filtered
and deionized by means of a three-cartridge Super-Q
System purchased from the Millipore Corporation.
The ethanol-water solutior?s were prepared volume-
trically and determined by means of burettes with a
0.05 ml precision. Combined errors on the composi-
tions were estimated to be less than 0.5%.
The same samples were used for the measurements
at different PMR working frequencies. The spectra
were recorded under slow passage conditions and well
below the r.f. saturation levels, by means of a HA-100
* This work has been partially reported elsewhere [ 151.
alcohol mixtures 3L
and an A-60 Vsrian standard spectrometerl, both
equipped with a Varian model-4340 variable temper-
ature accessory. The HA-100 spectrometer was used
in the field-locked mode, while the A-60 spectro-
meter is stabilized by an internal field-frequency lock
system. The measurements at 220 MHz were per-
formed on a HR-220 Varian spectrometer8.
The chemical shifts were measured by using cldoro-
form as external reference in coaxial tubes as well as
the methyl and methylcne proton signals of ethyl al-
cohol, as internal refcrcnces. The chemical shifts were
evaluated within the limits of +-0.005 ppm, by ap-
plying the side-band method [ 16.171 in repeated
measurements. When evaluated with respect to the
external reference, the chemical shifts were corrected
for the different diamagnetic volume susceptibilities
of the sample and refcrencc, by using a method de-
scribed elsewhere [ 181.
A standard densimeter DhlfL-02 (Anton Paac KC,
Graz) was used to determine the density of the solu-
tions, as required when evaluating tile volume suscep-
tibilities of the mixtures. Density measurement er-
rors, combined with those due to oscillations of the
temperature control system, were estimated to be
It 5 X low4 g/cm3. Our density measurements on
water-ethanol solutions, at 2OC, are in agreement
with those reported by I.C.T. [ 191.
The temperature of each NMR measurement was
tested by using methanol or ethylene glycol standard
samples, previously call&rated against a Cu-constantan
thermocouple, placed into an open sample tube in-
serted in the probe. The combined errors of tempera-
ture measurements were estimated at + lC.
An IBM 7040 Computer* was used for best-fitting
procedures. for numerical calculations of line shapes
in the studies of proton exchange phenomena, etc.
3. Results
The chemical shifts of the hydroxyl groups in
water-ethanol systems, measured at 100 MHz and
t NMR facilities of the Biological Chemistry and Physics Lab-
oratories of the lstituto Superiore di SYwid.
* By kind permission of the Technisch Chemisches Laborato-
rium - Eidgenoessische Technis&e Hochschule - Ziirich
* In use at the Physics Laboratories of the Istituto Superiore
di Sani&
32 A. Gxcin et d/PMR studieson water-ethyl ak&~l mixtu~

I I I I I i I

240 -

230 -

220 -

210-

200 -
I

190
:1 I
I : I
, I
0.00 0.25 0.50 0.75 f 1.00

Fii. 1. Chemical shifts of the hydroxyl signals in water-ethanol mixtures. relative to exterml ehl&oform at 100 MHz and 20C.
The line shapes of the OH signaIs are sketched in at the top cf is the ethanol mole fraction).

20C with respect to external chloroform, are plotted
versus the ethanol mole fractionfin fig. I. The typical
features of the hydroxyf signaIs in the various f regions
are sketched an top of the figure, indicating line shapes
and conditions of coalescence of the O_Hsignals. As
ethanol is added to water, the single sharp symmetri-
cai hydroxyl signal (see fig. 2a) is fust shifted towards
lower Gelds, reaching a ~imum 5.5 Hz deep, at f=
0.08; it broadens but the chemical shift remains quite
constant up to f zO.20. Above f ~0.20, the signal
becomes more and more asymmetric and finally two
maxima appear around f z 0.30 to 0.35 (see fig. Zb).
The upper-field Ofisignal is shifted linearly with/
towards higher fields up tof- 0.80. The down-field
signal is shifted towards the position of the pure etha-
nol resonance. Area measurements indicate that the
former signal is due to the waker protons and the
latter to the ethanol hydroxyl. Me~~emen~ carried
out at 60 and 220 MHz display features analogous to
those shown in fg. 1_
Fig. 3 shows the linewidths (Av1.12) of the hy-
droxyl signals, measured at 60 and 100 MHz. The
linewidth values of the single O_Hsignal observed at
concentrationsfQ 0.30 are reported in fig. 3a, while
fig 3b shows the linewidth of the water signal in the
region f> 0.40. It is important to note that the iine-
widths of the hydroxyl signals are larger at 100 than
at 60 MHz, in the range of 0.00 <I< 0.75. The half-
heist-veldts are equal for f> 0.80. The behavi-
our observed at 220 MHz is similar to that at the
other frequencies for both above and below f= 0.8.
The chemical shifts of hydroxyl signals measured
with respect to the methylene group are plotted ver-
sus temperature in fig. 4. At every concentration
 A. Coccia el al./PhfR studies on warer-erhyl alcohol mirrurcs 33

1 1

I
.I
I
23
I __
I_
01
.4

s

s

3

.a

Fig. 3. Linewidths of the O~signals in water-ethanol

Sf

mix-
tures at 2OOC.as a function of ethanol mole fraction: (a) etk3-
nol and water hydroxyl signals in coalescence. &I) water hy-
droxyl sign&; (0) 100 MHz. (0) 60 MHz.

t < -20C and at f = 0.235 when I < -30C. The trip-

Fig 2. PMRspectra recorded at 100 MHzand 20C, for
ethanol-water solutions at different ethanol mole fractions_
The signals correspond, in order of the increasing resonance
field, to the ethanol hydroxyl. water and meahylene protons
Atf = 0.149. the ethanol hydroxyl and water protons appear
as a single signal.
examined, water and ethanol hydroxyl protons gave
rise to two separate resonances when the temperature
wag lowered sufficiently. Complete coalescence of
these signals is observed atf= 0.424. when t > +20DC,
atf= 0.235 when t > OC and at f= 0.073 when t >
-20C. The ethanol hydroxyl triplet structure is re-
solved at f = 0.632 when z < +30C, at f = 0.424 when
let structure of ethanol hydroxyl is always undetect-
able at f= 0.073 in the temperature range explored
and is poorly resolved at f = 0.235, probably because
of the high viscosity of these solutions at tempera-
tures lower than -3OY.
Above f= 0.6 the chemical shift of the ethanol
hydroxyl group (relative to CE12 chemical shift) in
solution equals that of pure ethanol at all tempera-
tures; in the interval 0.4 <f < 0.6. this is true only
at low temperatures. In water-rich mixtures, the etha-
nol hydroxyl appears at lower fields than in pure
ethanol. On the other hand, in mixtures withf> 0.9,
the chemical shift behaviour of the water protons
in unlike that of pure water [20]. Its temperature
dependence parallels that of the ethanol hydroxyl
within roughly 5%.
The chemical shifts of methyl and methylene
groups, with respect to external chloroform, obtained
at 60 MHz and 20C. are reported in fg- 5. These
resonances are gradually shifted towards higher fields,
as the ethanoI concentration increases, undergoing
overall shifts of about 0.09 and 0.13 ppm. respective-
ly. On the other hand, measurements performed at
various concentrations, with varying temperature
between about -20 and +70C, show that the chern-
ical shirts of the all@ groups are practically temper-
ature-independent.
34 A. Coccia er al. fPMR studies on ware?-ethyl alcohol mixtures

perature - in the range 20 to 75OC - for water-

ethanol mixtures [22], this interpretation agrees
with the substantial independence on the tempera-
ture of this chemical shift. The low number of the
experimental points, and their scattering, prevents
us from distinguishing between different concentra-
tion ranges.
The chemical shifts of the hydroxyl protons in-
dicate that the behaviour of water-alcohol mixtures
cannot be discussed in terms of a single molecular
mechanism throughout the entire concentration range.
Franks and Ives [4] reached similar conclusions in
the interpretation of various physical-chemical tech-
niques. The tntal concentration range was divided
therefore into four partial ranges, distinguished above
6C- alI by different line shapes of the hydroxyl signals:
(a) 0.00 <f-s 0.08; (b) 0.08 512 0.20; (c) 0.20 sj-
5 0.80; (d) 0.80 5 f 5 1.oO.
The chemical shift difference between pure water
4Q- . tcO.976
a 0 at 20C and water in ethanol-rich mixtures is about
X rio.925 ;
(I
o tzO.632 : o 0.33 ppm (fig. 1). This number can be compared with
6. the chemical shift of about 2.5 ppm between water
20-
o tzO.424
l.!20 at room temperature and water vapour at 18OC [23].
A fm0.073 (In EIOH)
L I 1 1 I I 1 1 1 t Assuming that in very dilute solutions of water in
-60 -40 -20 0 20 40 60 60 t (C) ethanol. water molecules are bonded only to alcohol
molecules, one can conclude that the chemical shift
Fig. 4. Chemical shifts of the hydroxyl signalsof ethanol, corresponding to the ethanol-water bond is about
water and water-ethanol mixtures, measured as a function equal or slightly smaller than that corresponding to
of temperature at 60 MHz. All are plotted relative to the
a water-water bond.
ethanol methylene group as internal reference. (The water
mezurements ae taken from ref. [20 I.) The fact that in range (a) the water and ethanol
hydroxyl protons give rise to a practically symmetri-
cal single signal is attriiuted to proton exchange 1241.
4. Discussion However, the appearance of the minimum in the plot
of the OH chemical shift versusf(fig. 1) cannot be
4.1. Chemical shifts at 20C completely attributed to such exchange phenomena.
This conclusion (also in agreement with independent
The chemical shift measurements of the ethanol studies recently reported on aqueous mixtures of
alkyl protons were performed primarily with the aim ethanol and other monohydric alcohols [ 12.24-261)
of recognizing whether their resonance position is is based on the following considerations. The low-
concentration dependent or not, so as to choose be- field shift of the collapsed Olj signal is necessarily
tareen the use of external and internal references. due, at least to some extent, to an increase in H-bond-
However, the uptield shifts undergone by the methyl ing association. The increase can be in principle due
and methylene resonances can result mainly from a either to the formation of new water-ethanol H-bonds,
reaction field effect [21] indicating that the alkyl or/and to incremented water-water association, fa-
group sees surroundings that become less and less voured by the presence of small amounts of ethanol
polar with increase in alcohol concentration. Since molecules. The formation of fairly strong H-bonds
the contribution of the dielectric constant to the re- between water and ethanol is actually suggested by
action field [21] is almost independent of the tem- the rather high value of the heat of hydration of
 A. Cocci0 et al./PMR studies on water-ethyl alcohol mixtures 35

I I I I I 1
375

Av of-C&
(Hz)
370
i_+J-CJT b = 367.4

I I I I I
365 I I

23t

Av OF-cfi!;
(Hz)
22!

221

I I I I I I
100 0.25 0.50 0.75 f l.O(

Fig. 5. Chemical shifts of the methyl and melhglene groups in water-ethanol mixtures relative to external chloroform at 60 MHz
and 2OC.

ethanol at infinite dilution. in water (about 10.63 kJ/ with the ethanol alkyl group. In fact several physical
mol at 13C). [27]. On the other hand, under the hy- quantities are generally interpreted as an indication of
pothesis that in this concentration range the average a structure-making* effect on water. induced by the
number of H-bonds is maintained constant when cosolvent [4]. Among others, the partial molar vol-
ethanol is substituted to water, the low-field shift of ume of ethanol mixtures [28) decreases with ethanol
the 0I-J signal should not get over the value of 2.5 Hz. concentration and has a minimum, approximately at
The above hypothesis is justified on the basis of theo- f = 0.08 at 2OC. The viscosity derivative dddf, cal-
retical studies recently carried out by Laiken and culated from the data of I.C.T. (291, at 20C. show
Nemethy [3], who evidenced that the water-water a well-defined maximum, peaked again around f =
and water--ethanol H-bond energies are approximate- 0.08.
ly the same (3.57 kcal/mol). It is therefore concluded One can recognize that in region (b) the behaviour
that the structure-making effects, occurring in is intermediate between regions (S) and (c)_
range (a), are accompanied by a corresponding in- This is attributed balance the opposite
crease in the self-association of water, as detected by actions exerted on the water molecules by thz polar
chemical shift measurements. This effect can be at- and non-polar ethanol
tributed, to a large extent, to the interaction of water supposed that the allcyl
36 A. Coccia et aI.fPMR studies on water-ethyl alwhol mixtures

becoming more and more numerous, begin to hinder
water from organizing into three-dimensional struc-
tures, so that their structure-making power be-
comes progresskly less effective.
The sensitive changes of the OH chemical shift and
line shape indicate that the structural behaviour of
these solutions is quite strongly modified when the
ethanol mole fraction increases above roughly 0.2.
Other experimental evidence supports this conclusion.
The partial molar heat of solution of ethanol Jn water-
ethanol mixtures (311 at f = 25C, strongly negative
atfless than about 0.2, becomes positive at higher
fvalues. At the same temperature, the excess partial
molal entropy for ethanol in water-ethanol mix-
tures [3J ] , is strongly negative at f < 0.2, but its
derivative with respect tof, while always positive,
falls rapidly to low values whenf> 0.2. At 20C the
viscosity [29] reaches its maximum value at about
f = 0.22, and afterwards it faJJs rapidly.
Jn the concentration range (c), the position of the
ethanol hydroxyl signal provides limited information
up to/<0.6: the chemical shift of this peak does not
correspond to a unique magnetic environment. As
shown in Jig. 6, at f< 0.6, this distance between the
two hydroxyl absorption maxima does not seem
proportional to the working frequency. This supports
the hypothesis that exchange occurs between *he two
kinds of protons.
By contrast, at f 2 0.6, the distance between the
hydroxyl signals is proportional to the working fre-
, quency (fig. 6), that is the proton exchange is suffr-
ciently slow to have no effect on the chemical shift.
It is possible that the variation of exchange rate re-
flects structural differences between the mixtures
in the ranges 0.2 <f < 0.6 and 0.6 <f< 0.8. This
conclusion would be supported by the partial molar
heat of solution of ethanol in ethanol-water mix-
tures [3 I] which is slightly positive in this range up
to fabout 0.6, but is negative at higher j-values. On
the other hand the partial molar heat of solution of
water [31] is negative, with a broad maximum lo-
cated in the mole fraction range 0.7 to 0.8. This evi-
dence suggests that in the range 0.2 <f < 0.6 water-
water bonds would be favoured over those between
water and ethanol. but with increase in alcohol con-
centration both types of association are likely to be
equally probable.
The uniform upfield shift of the water PMR signal
(fig. 1) suggests a progressive decrease of the number
of H-bonds in which water participates, with a con-

1.0 -

Qd- . . . Q-
.QQ
u l
0 ?
(u- I
0 : 4 .

oh- f

a2-

I I I ,
0.0
Q25 050 0% I IDo

Fig. 6. Chemical shift dilference between hydroxyl signals of waterandethanolin w;lter-ehd mixturesat 2OC: (0) 100 MHz,
(x) 60 MHZ.
 A. Cocch et aI./PMR
sequent breakdown of the structures peculiar to pure
water. In the range 0.2 SfS 0.8 where a threefold
decrease. of the concentration of water molecules
curs, the observed overall shift of about 0.38 ppm
is small as compared with the upfield shift experienced
by the water signal when the temperature increases
[Xl], for example 0.76 ppm from 20 to 1OOOC. More-
over, the excess partial molal entropies of both water
and ethanol indicate that addition of either compo-
nent has a structure forming influence in the water-
ethanol system, even in the 0.2 to 0.8 range [31] _
Thus one should conclude that a large number of
ethanol-water bonds are formed while the water-
water bonds are broken.
Throughout the range (d), the constant chemical
shift of the water signal suggests that the water mole-
cules are engaged in the same type of aggregation
mechanism. The very strongly negative partial molar
heat of solution of water in water-ethanol mixtures
[31] suggests the presence of particularly stable ag-
gregates.
Evidence that water is bonded to ethanol mole-
cules in ethanol-rich solutions is provided by measure-
ments of diffusion in ethanol-water mixtures: the
radius of water molecules is smaller when diffusing
in pure water than in pure alcohol 1321. Dielectric
relaxation measurements were interpreted suggesting
that water molecules cross-link alcohol polymers at
these ethanol concentrations [33,34].
Chemical shift and fine structure of the ethanol
signals, compared to those of pure ethanol, indicate
that the solvent effect and the H-bonding character
seen by the ethanol hydroxyl protons in the range
f 2 0.8 are essentially maintained equal to those seen
in pure ethanol. Measurements of chemical shift ver-
sus temperature and of linewidth at 20C further
support this idea, as will be discussed later (section
4.3).
4.2. Temperature dependence of the hydroxyl
chemical shifts
At low fvalues the chemical shift of the single
hydroxyl signal shows the same thermal behaviour
as that of pure water in the range -20 to +8OC
(fig. 4). This indicates that the ethanol-water inter-
actions do not alter the thermal behaviour of the
structures peculiar to pure water.
studies on wafer-ethyl alcohol mixtures 37
Measurements on solutions at intermediate concentra-
tions support the idea of substitution of the pure
oc- water structures with aggregates which display a be-
haviour intermediate between that of ethanol and
water respectively.
The temperature dependence of the ethanol hy-
droxyl signal in ethanol-rich mixtures indicates. as
previously said, that the ethanol hydroxyl proton
sees surroundings which are similar, both in H-bond-
ing character and in solvent effects, to those peculiar
to pure alcohol.
The chemical shift has a positive second derivative
with respect to temperature in pure water. This dertv-
ative is negative instead for both the ethanol hydroxyl
signal above room temperature and for the water sib-
nal in ethanol-water mixtures at f = 0.925 and 0976.
Such evidence suggests that the water molecules like-
ly partake in the same type of molecular aggregation
as that in which pure ethanol participates.
The behaviour of the chemical shift of the solution
with f = 0.632 parallels that of pure ethanol below
room temperature, where proton exchange does not
influence the chemical shifts. But in this case, the
existence of aggregates different from those of the
mixtures at f > 0.8 is suggested by the chemical shift
difference between the water and ethanol signals
(fig. 7).
Finally, it can be suggested that in a detailed anal-
ysts one should distinguish extremely dilute solutions
from the rest of the range. This proposal is supported
by the dependence on concentration of the chemiti
shift difference between hydroxyl signals.
4.3. Ethanol-rich mixtures
At low concentration of water in ethanol, it seems
necessary to propose an association me&a&m which
is capable of explaining at the same time: (a) the pres-
ence of the plateau in the plot of the chemical shift
of water over a wide region y-2 0.8); (b) the quite
abrupt change in the slope of the same plot occurring
around 0.8; (c) the persistence of the triplet fme
structure of the ethanol hydroxyl signal even at c >
60C.
It was proposed by Franks and lves 14) that at
these concentrations the water molecules are able to
cross&& Pcohol polymers, in a cooperative process,
without water-water H-bonds.
38 A. Coccia ef al./PMR studies on water-ethyl alcohol mixtures

50
.
.

46
;r+<;q:

0 t = 0.632

34- l
,+-*y*
\
-
- I = 0.424
+ I = 0.235

L I I I I I , I I I I I I
-60 -40 -20 0 20 40 60 t (Cl

Fig. 7. Chemic4 shift difference between hydroxyl signals of water and ethanol in water-ethanol mixtures as a function of tem-
perature at different concentrations. hleasurements at 60 MHz.

In order to explain the points (a),(b) and (c). it polymer length is 5-7 molecules [4] , there would
can be suggested that, at f> 0.8, the water molecules be still only 1 or 2 water molecules per alcohol poly-
can even participate in the formation of the linear or mer at water mole fraction 0.2. In the framework of
cyclic structures characteristic of pure ethanol. The this interpretation the abrupt change undergone by
existence of this kind of aggregation can be justified the chemical shift slope would indicate that around
qualitatively by considering that when a water mole- this concentration the energy term arising from co-
cule is inserted into the interior of an alcohol poly- operative water-water interactions becomes prev-
mer, the system can attain a larger entropy. The two alent with respect to the mentioned entropy con-
ethyl groups next to the water molecule would in tribution.
fact experience relatively less steric hindrance, result-
ing in a larger flexibility of the chain around it. On 4.4. Linewidth measurements
the other hand, the insertion of water molecules into
alcohol polymers should also prevent them from Proton exchange in water-ethanol solutions is
forming many water-water H-bonds. In fact it fol- demonstrated by the dependence on the working
lows from steric considerations that no further en- frequency of the chemical shift difference between
tropy would be gained by the addition of a second the resonance maxima of the water and ethanol hy-
water molecule next to the first one. On the con- droxyl groups in samples with 0.3 <f< 0.6 (fig. 6).
trary, when two water molecules are inserted in two The existence of proton exchange is further supported
different sites along the alcohol polymer the system by the dependence of the slope of the EtOH hydroxyl
can attain a larger entropy. Therefore water-water and the methylene signals on the concentration and
pairs would not be particularly favoured up to a by the dependence on working frequency of the line-
water concentration corresponding to about two width of the hydroxyl signals whenf< 0.75.
water molecules per polymer_ In this way, in the Line shapes and linewidths experimentally meas-
rangef> 0.8, water molecules would be able to par- ured in this work were compared with those predicted
ticipate in the alcohol structures without contributing by an adiabatic exchange model, derived by McConnel
essentially new structural features. Since the average by means of the introduction of damping terms in the
 A. Coccia er aL/PMR studies on wafer-ethyl
time dependent Bloch equations 1351. The model
was applied to two exchanging sites, namely the etha-
nol hydroxyl and the water protons. This model
predicts that the linewidths are independent of the
working frequency for very high or very low ex-
change rates. The linewidth increases with the work-
ing frequency at intermediate exchange rates if the
two resonances are collapsed in one single signal.
However the linewidth decreases with increase in
working frequency if two maxima are resolved. These
expectations agree with the experimental evidence in
water-rich y-5 0.30, fig. 3a) and ethanol-rich mix-
tures cf> 0.75, fig. 3b).
In the water-rich mixtures, the Linewidth increases
with increase in concentration, probably not only
because of varying eschange rate and proton popula-
tion, but also because of decrease in water relsation
times [ 121. However, the exchange rate is sufficient-
ly slow to make the linewidths quite sensitive to the
working frequency.
An estimation of the exact concentration (c*) at
which the ethanol peak is first resolved from the
water signal appeared difficult. This is especially so
because the shape of the OH signal is very sensitive
even to small amounts of impurities in the solution,
besides the fact that the ethanol signal is much weaker
than that of water. For the same reasons, it is difli-
cult to detect possible differences in c* at the two
working frequencies of 60 and 100 MHz.
When the ethanol concentration is increased above
f= 0.7, a decrease of the exchange rate is suggested
by the decrease of the water signal linewidth. This is
supported by the line shape of the ethanol hydroxyl
triplet. The latter indicates a mean proton lifetime 7
between successive exchanges [36] of about 0.1 s at
f= 0.8; in extremely dilute water solutions 7 is of the
order of 1 s or more.
At 0.30 5 fS 0.75, the experimental evidence
(fip. 3b) is just opposite the predictions, so that in
this range the exchange phenomena between ethanol
and water hydroxyl protons cannot be described any-
more by means of this two-sites exchange model.
Even though this model is consistent with the be-
haviour of the resonance signals in the two extreme
concentration ranges, it can be concluded that at in-
termediate mixing ratios it fails to shed light upon
these solutions.
alcohol mixtures 39
Acknowledgement
We thank Mr. M. Grignoli for his technical as.&+
tance and for recording some spectra. We thank also
Professor C. Casinovi for the use of the Varian HA
100 spectrometer.
We are particularly indebted to Professor C. Ne-
methy for frequent discussions and critical revision
of the manuscript. We wish to acknowledge alsu the
stimulating interest of Dr. L. Radics during the pro-
gress of this work.
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