You are on page 1of 11

Chemical Physics 7 (1975) 30-40

0 North-Holland Publishing Company



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-
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 alcohol mixtures 3L

dependent on the addition of traces of bases or acids and an A-60 Vsrian standard spectrometerl, both
(1O-6-1O-5 molell-I) [lO,ll]. equipped with a Varian model-4340 variable temper-
The temperature dependence of c* in a 2: 1 etha- ature accessory. The HA-100 spectrometer was used
nol:water mixture was studied by Schneider and in the field-locked mode, while the A-60 spectro-
Reeves 161. meter is stabilized by an internal field-frequency lock
Chemical shifts and relaxation times were recent- system. The measurements at 220 MHz were per-
ly studied by Oakes [!2] in water-rich ethanol-water formed on a HR-220 Varian spectrometer8.
mixtures in an attempt to ascertain the relative im- The chemical shifts were measured by using cldoro-
portance of water-alcohol interaction terms due form as external reference in coaxial tubes as well as
respectively to the hydroxyl and the hydrocarbon the methyl and methylcne proton signals of ethyl al-
function of the latter. cohol, as internal refcrcnces. The chemical shifts were
Exchange broadening of spin-spin triplets was evaluated within the limits of +-0.005 ppm, by ap-
studied in ethanol-rich mixtures by Paterson [13] by plying the side-band method [ 16.171 in repeated
using an extension of the McConnel method for ki- measurements. When evaluated with respect to the
netic analysis of molecular processes [ 141 . external reference, the chemical shifts were corrected
A first conclusion drawn from these studies is the for the different diamagnetic volume susceptibilities
need for a detailed parallel study of chemical shifts of the sample and refcrencc, by using a method de-
and lineshapes over the entire composition range of scribed elsewhere [ 181.
the two cosolvents. No systematic studies have been A standard densimeter DhlfL-02 (Anton Paac KC,
reported so far, which elucidate (a) the dependence Graz) was used to determine the density of the solu-
of c* on the working frequency;(b) the dependence tions, as required when evaluating tile volume suscep-
on temperature of the chemical shifts of the ethanol tibilities of the mixtures. Density measurement er-
and water hydroxyl groups in the various intervals of rors, combined with those due to oscillations of the
the mixture composition. temperature control system, were estimated to be
Such studies were undertaken in the present work*. It 5 X low4 g/cm3. Our density measurements on
The results are treated in terms of the possrble differ- water-ethanol solutions, at 2OC, are in agreement
ent mechanisms of molecular aggregation dominating with those reported by I.C.T. [ 191.
in the various alcohol concentration regions. The temperature of each NMR measurement was
tested by using methanol or ethylene glycol standard
samples, previously call&rated against a Cu-constantan
2. Experimental thermocouple, placed into an open sample tube in-
serted in the probe. The combined errors of tempera-
Ethanol (EtOH) 99.8% pure, analytical grade, was ture measurements were estimated at + lC.
purchased from Merck AC Darmstadt and used with- An IBM 7040 Computer* was used for best-fitting
out any further purification. Bidistilled water was procedures. for numerical calculations of line shapes
purchased from Carlo Erba and successively filtered in the studies of proton exchange phenomena, etc.
and deionized by means of a three-cartridge Super-Q
System purchased from the Millipore Corporation.
The ethanol-water solutior?s were prepared volume- 3. Results
trically and determined by means of burettes with a
0.05 ml precision. Combined errors on the composi- The chemical shifts of the hydroxyl groups in
tions were estimated to be less than 0.5%. water-ethanol systems, measured at 100 MHz and
The same samples were used for the measurements
at different PMR working frequencies. The spectra t NMR facilities of the Biological Chemistry and Physics Lab-
were recorded under slow passage conditions and well oratories of the lstituto Superiore di SYwid.
* By kind permission of the Technisch Chemisches Laborato-
below the r.f. saturation levels, by means of a HA-100 rium - Eidgenoessische Technis&e Hochschule - Ziirich
* In use at the Physics Laboratories of the Istituto Superiore
* This work has been partially reported elsewhere [ 151. di Sani&
32 A. Gxcin et d/PMR studieson water-ethyl ak&~l mixtu~

I I I I I i I

240 -

230 -

220 -


200 -

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

1 1

I __





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


tures at 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-

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
Fig 2. PMRspectra recorded at 100 MHzand 20C, for dependence parallels that of the ethanol hydroxyl
ethanol-water solutions at different ethanol mole fractions_ within roughly 5%.
The signals correspond, in order of the increasing resonance
The chemical shifts of methyl and methylene
field, to the ethanol hydroxyl. water and meahylene protons
Atf = 0.149. the ethanol hydroxyl and water protons appear groups, with respect to external chloroform, obtained
as a single signal. at 60 MHz and 20C. are reported in fg- 5. These
resonances are gradually shifted towards higher fields,
examined, water and ethanol hydroxyl protons gave as the ethanoI concentration increases, undergoing
rise to two separate resonances when the temperature overall shifts of about 0.09 and 0.13 ppm. respective-
wag lowered sufficiently. Complete coalescence of ly. On the other hand, measurements performed at
these signals is observed atf= 0.424. when t > +20DC, various concentrations, with varying temperature
atf= 0.235 when t > OC and at f= 0.073 when t > between about -20 and +70C, show that the chern-
-20C. The ethanol hydroxyl triplet structure is re- ical shirts of the all@ groups are practically temper-
solved at f = 0.632 when z < +30C, at f = 0.424 when 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 ;
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
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

Av of-C&
i_+J-CJT b = 367.4

365 I I


Av OF-cfi!;


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

1.0 -

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

oh- f


I I I ,
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 studies on wafer-ethyl alcohol mixtures 37

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



0 t = 0.632

34- l
- 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 alcohol mixtures 39

time dependent Bloch equations 1351. The model Acknowledgement

was applied to two exchanging sites, namely the etha-
nol hydroxyl and the water protons. This model We thank Mr. M. Grignoli for his technical as.&+
predicts that the linewidths are independent of the tance and for recording some spectra. We thank also
working frequency for very high or very low ex- Professor C. Casinovi for the use of the Varian HA
change rates. The linewidth increases with the work- 100 spectrometer.
ing frequency at intermediate exchange rates if the We are particularly indebted to Professor C. Ne-
two resonances are collapsed in one single signal. methy for frequent discussions and critical revision
However the linewidth decreases with increase in of the manuscript. We wish to acknowledge alsu the
working frequency if two maxima are resolved. These stimulating interest of Dr. L. Radics during the pro-
expectations agree with the experimental evidence in gress of this work.
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 References
with increase in concentration, probably not only
because of varying eschange rate and proton popula- 111 D. Eisenberg and W. Kauzmann. The structure and prop-
tion, but also because of decrease in water relsation erties of water (Otford University Press. Oxford. 1969).
times [ 121. However, the exchange rate is sufficient- [2] G. Nimelhy. Ann. 1st. Sup. Saud 6 <1970)491.
131 C. NCmethy md F. Podo, Jerusalem Symp. QEIII~U~
ly slow to make the linewidths quite sensitive to the Chem. and Biochem. 5 (1973) 715.
working frequency. [4 \ F. Franks and D J.G. Ives. Quart. Rev. Chem. Sac. 20
An estimation of the exact concentration (c*) at (1966) 1.
which the ethanol peak is first resolved from the 151J.A. Pople, W.G. Schneider and HJ. Bernstein. High
water signal appeared difficult. This is especially so resolution nuclear magnetic rcsomnce (McGraw-Hi&
New York, 1959).
because the shape of the OH signal is very sensitive [6] W.C. Schneider and L.W. Reeves. Ann. N.Y. Aad. Sci.
even to small amounts of impurities in the solution, 70 (1958) 858.
besides the fact that the ethanol signal is much weaker (7 J A. Abragam, Principles of nuclear magnetism (Oxford
than that of water. For the same reasons, it is difli- University Press, New York, 1961) p. 114.
cult to detect possible differences in c* at the two [8] L. Weinberg andJ.R Zimmerman&J. Chem. Phys. 23
(1955) 748.
working frequencies of 60 and 100 MHz. [9] hl. Ageno and P.L. lndovina, Proc. Nstl. Acad. Sci. 57
When the ethanol concentration is increased above (1967) 1158.
f= 0.7, a decrease of the exchange rate is suggested [lo] Z. Luz, D. Gill and S. Meiboom, J. Chem. Phys. 30
by the decrease of the water signal linewidth. This is (1958) 1540.
supported by the line shape of the ethanol hydroxyl [ll) J.R. Kuppenand NJ?. Carriker, J. Magn. Res.5 (1971)
triplet. The latter indicates a mean proton lifetime 7 [12] iTbakes, J. Chem. Sot., Faraday Trans. II 69 (1973)
between successive exchanges [36] of about 0.1 s at 1311.
f= 0.8; in extremely dilute water solutions 7 is of the (131 W.G. Paterson, Canad. J. Chem. 41 (1963) 714.
order of 1 s or more. [141 H.M. McConnell, J. Cbem. Phys. 28 (19.58) 430.
At 0.30 5 fS 0.75, the experimental evidence [lS] A. Coccia. P.L.. lndovina, F. Podo and V. Viti. Studi
strutturali me&ante RMN in misaele acqua etanolo.
(fip. 3b) is just opposite the predictions, so that in Rapporti dei Labontori di Fisica delllst. Sup. San&.
this range the exchange phenomena between ethanol ISS71/6,ISS71/7. ISS71/8. 15. 18.22 maggio 1971;
and water hydroxyl protons cannot be described any- A. Coccia. P.L. lndovina, F. Podo and V. Viti. BOIL Sot.
more by means of this two-sites exchange model. It. Fis. 87, 11 ottobre 1971.
Even though this model is consistent with the be- [16) J.T. Arnold and ME. Packard. J. Chcm. Phys. 19 (1951)
haviour of the resonance signals in the two extreme [ 171 M. Huggins, G.C. Pimentel and J.N. Shoolery. J. Chem.
concentration ranges, it can be concluded that at in- Phys. 23 (1955) 1244.
termediate mixing ratios it fails to shed light upon [ 181 F. Podo and V. Viti, Studio di misccle aqua-atone
these solutions. e acqua-DMSO con h RMP ed altre tecniche chimico-
fisiche. Rapporti dei Laboratori di Fisica defllst. Sup.
dt Sanid. 1% 69/33,5 setrembre 1969.
40 A. Coccia et oL/PMR studies on worrr-ethyl almhol mixtures

[19] lnternalional Coun- [27 1 International Critical Tables. National Research Coun-
cil ~McGraw-Hill. New York and London. 1929) Vol. cil (McGraw-Hill. New York and London, 1929) Vol.
Il1.p. 116. V. p. 148.
1201 J.C. Hindman. J. Chem. Phys. 44 (1966) 4582. 1281 F. Franks and H.H. Johnson. Trans. Faraday Sot. 58
[21] J. Ronayne and D.H. Williams. Ann. Rev. NMR Spcctry. (1962) 656.
2 (1969) 83. [291 International Criticai Tables. National Research Council.
[22] A.R. Martin and A.C. Brown, Trans. Faraday Sot. 34 (McGraw-Hi. New York and London 1929) Vol. V,
(1938) 742. p. 22.
123) W.G. Schneider, HJ. Bernstein and J.A. Pople.1. Chem. [3Ol N. Laiken and C. Nimcthy, J. Phys. Chem. 74 (1970)
Phys. 28 (1958) 601. 3501.
1241 Wen-Yang Wen and H.G. Hertz, J. Sol. Chem. 1 (1972) [311 G.L. Bertrand, F-l. hlillero. Ching-Hsien Wu and L.C.
17. Hepler. J. Phys. Chem. 70 (1966) 699.
12.51 H-G. Hertz and h1.D. Zeidler, Ber. Bunsenges. Phys. (32) B.R. Hammond and R.H. Stokes. Trans. Faraday Sot. 49
Chem. 68 (1964) 821; (1953) 890.
H.G. Hertz, in: Progress in NMR spectroscopy, eds. [33] V. Sarojini. Trans. Faraday Sot. 57 (1961) 1534.
J.W. Emsley, J. Feeney and L.H. Sutcliffe (Pergamon [ 341 F.X. Hassionand and R.H. Cole, J. Chcm. Phys. 23
Press, London, 1967) Vol. 3, pp. 159-230. (1955) 1756.
[26]D.N.Glew. H.D. Mak and N.S. Rath, in: Hydrogen- [3Sl H.M. McConnell, J. Chem. Phys. 28 (1958) 430.
bonded solvent systems, Proc. Symp.. ed. A.K. Coving- [36) W.G. Paterson, Canad. J. Chem. 41 (1963) 714.
ton f.Taylor and Francis, London, 1968) p. 195;
D.N. Clew, H.D. Mak and N.S. Rath. Chem. Commun.
(1968) 264.