Spectrochimica Acta Part A 55 (1999) 1585 – 1612

Direct proportionality of the hydrogen bonding energy and

the intensification of the stretching n(XH) vibration in
infrared spectra
A.V. Iogansen
Ap. 41, 16 /18 Shcherbako6skaya Str., Moscow, Russia

Received 16 December 1996; accepted 16 December 1998

Abstract

The direct proportionality of the intensification DA 1/2 of the infrared (IR) proton stretching vibration (n(XH)) band
in the XH···Y hydrogen bond and its enthalpy, − DH=12.2 DA 1/2, suggested by an ‘additive’ model of the effective
charges of the XH and H···Y bonds, is discussed. Its universal validity is illustrated over a 200-fold energy range
(0.3–60 kJ mol − 1) for a large number of different XH···Y hydrogen bonds of different associates, from the great
diversity of dimers to the continuous three-dimensional network of liquid water and ice. The contrasting behaviors
of the ns-band intensification and its frequency shift, Dn, are compared. © 1999 Elsevier Science B.V. All rights
reserved.

Keywords: Hydrogen bonding energy; IR spectra; Intensity; Proton stretching vibration

1. Introduction the absolute intensity of the ns-band, the quantity

Over three decades ago the author revealed an
intriguing universal direct proportionality be-
tween the enthalpy of formation of a hydrogen
bond (HB) and the intensity enhancement (inten-
sification) of the proton stretching vibration (ns or
n(XH)) band in infrared (IR) spectra. The incre-
ment on hydrogen bonding of the square root of

Translated from Russian by Dr M. Rozenberg, edited by
Professor Y. Marcus, Department of Inorganic and Analytical
Chemistry, The Hebrew University of Jerusalem, Jerusalem
91904, Israel. Tel.: + 972-2-6585319; fax: + 972-2-6585319.
E-mail address: ymarcus@vms.huji.ac.il (Y. Marcus)
DA 1/2, is considered as the measure of the inten-
sity enhancement. All subsequently reported data
only improved the quality of this relationship, as
shown below. The proportionality has since then
not only remained valid, but became more sub-
stantiated and fruitful. Unfortunately, this propor-
tionality has not been adequately propagated in
the literature, and, it is desirable—albeit a bit late
—to fill this gap. The present review is the first in
English, and the first and only one that is de-
voted entirely to the proportionality DH 8 DA 1/2.
This proportionality has already been reviewed
(in Russian) [1] within the context of other mani-
festations of the HB in IR spectra, and, needless

1386-1425/99/$ - see front matter © 1999 Elsevier Science B.V. All rights reserved.
PII: S 1 3 8 6 - 1 4 2 5 ( 9 8 ) 0 0 3 4 8 - 5
1586 A.V. Iogansen / Spectrochimica Acta Part A 55 (1999) 1585–1612

to say, on a narrower experimental basis. The

updated experimental data shown below include,
besides the band intensification, also the fre-
quency shifts Dns, although the latter are discussed
only with respect to the intensification of the
ns-band, to illustrate the contrasting behavior of
Dns and DA 1/2.

2. The model for intensification of the ns-band

Fig. 1. IR and Raman spectra of the binary mixture of
deuterochloroform with triethylamine (0.81:0.19) in the range
In the following the ‘intensity’ is the short name of the n(CD) band [1].
of the integral molar absorption coefficient A=
2.303(cl) − 1 − log T(n) dn. That is, it is the area the IR spectra, as is shown in Fig. 1. On the
of an absorption band with the ordinate being the opposite side of the HB strength scale the IR
optical density D = −ln T (T is the transmit-
spectra are not so directly informative. Extremely
tance) and the abscissa being the wavenumber (n,
broadened and Fermi-disturbed bands are ob-
in cm − 1), related to unit concentration (c, in mol
served in these cases as a background under a
dm − 3) and unit layer thickness (l, in cm), and
series of narrow skeletal bands (Fig. 2). However,
divided by 104. This yields A in ‘practical units’
the skeletal bands, being narrow, do not create
(104 cm mmol − 1) that are used below and omitted
if no ambiguity results. insurmountable difficulties regarding the measure-
The extreme increases of the intensity of the ment of the ‘background’ of wide HB bands, and
ns-bands take place in the HB formation Reaction the intensities of the latter can be estimated better
1: than appears from first sight.
The choice of the proper measure of the inten-
XH +Y “ XH···Y (1) sification of the ns-band plays the key role in
4
and reach 50 · 10 cm mmol −1
in the strongest attempts to relate the IR intensity to the strength
HBs. The resulting intensity is an order of magni- of the HB. The traditionally employed relative
tude larger than the greatest intensity of the ns- intensification is useless, because the intensities of
bands of chemical bonds XH and three to four
orders of magnitude larger than the change
caused by any other intermolecular interaction.
The effective charge, (#m/#r), corresponding to
the most intense of the ns-bands, is twice the
elementary charge, but such large effective
charges of molecular vibrations by themselves are
not unique (see [1]). However, only in the case of
the ns vibration are such charges augmented by
the greatest possible vibrational amplitude due to
the lightest atom, hydrogen, hence producing an
IR absorption of a unique strength. Only this
feature made IR spectroscopy the major method
of HB studies; otherwise very wide, intense, and
complicated ns-bands of strong H-bonds would
not be observable.
Even weak HBs are clearly revealed in the case Fig. 2. IR spectra of adducts of pyridine and acids (4:1) in
of weak ns-bands, which are much intensified in CH2Cl2 [40].
 A.V. Iogansen / Spectrochimica Acta Part A 55 (1999) 1585–1612
Fig. 3. Schematic drawing of H-bonded complex.
the free (non H-bonded) ns(XH), A0, range over
three orders of magnitude. Therefore, the ratio
A/A0 is by no means maximal for the strongest
HBs, but is instead at a maximum for the HB of
acids with the weakest free ns-band. For example,
for the HBs of phenol and chloroform with tri-
ethylamine, the intense n(OH) intensifies 15-fold
and the weak n(CH), at half the energy, intensifies
50-fold relatively to CCl4 solution (relatively to
the gas phase the intensifications are 40- and
600-fold, respectively).
The increment DA = A −A0 is also unsuitable
for different XHs, because of its dependence on
A0 (arising from the cross term of the square of
(#m/#r)). Only for OH-acids, where A0 does not
change strongly for different acids, is DA accept-
ably (although non linearly) correlated with the
HB strength [2,3].
Finally, for A 1/2 8(#m/#r) the initial and final
quantities are separated and the increment
DA 1/2 A 1/2 −A 1/2
0 (2)
excludes the initial vibrator XH and relates the
intensification as a whole to the effect of the base
Y in Reaction 1. It turned out that the choice of
DA 1/2 as the measure of the intensification of the
ns-band served as the ‘key to the doors’ of all
HBs.
Pimentel’s idea [2], that the polarization of the
base is the main reason for the intensification of
the ns-bands, was elaborated in [4] and the addi-
tive model:
(#m/#r)=(#m0/#r0) + (#mH/#rH) (3)
of the effective charges of the XH and H···B
bonds of a binary HB was suggested, schemati-
1587
cally represented in Fig. 3. An essential feature of
the model is that the XH bond retains in an HB
the magnitude (#m0/#r0) of a free XH bond and
the intensification of the ns-band as a whole
derives from (#mH/#rH). This is the direct additive
‘intrinsic’ contribution of the H···Y hydrogen
bond to the total moment of the ns-vibration and
its effective charge (#m/#r). The model was confi-
rmed in [4] for the linear H-bonded complexes of
acetylene and it was suggested there ‘‘…to con-
sider as the main spectral feature of the HB [not
the generally accepted band shift, but] the drastic
increase of the intensity of the stretching vibration
band ns’’.
3. The proportionality −DH8 DA 1/2
Despite the cited conclusion, the HB energy
was not immediately correlated with the intensifi-
cation of the ns-band. The simple proportionality
− DH8 DA 1/2 (4)
appeared only three years later [5], not only from
a lack of experimental data but also from lack of
imagination, and then it was published in the
‘improved’ form −DH = 5.3DG 1/2, where G=
(cl) − 1 − ln T d ln n: A/n0. The author [5] at
first preferred this form on theoretical grounds,
but later he returned to the widely used, hence
more convenient, quantity A, which is, in fact,
theoretically preferable. For harmonic oscillators
with equal masses the quantity A 1/2 is propor-
tional to the (intuitively required) pure electronic
factor, whereas G 1/2 includes also the frequency.
These quantities are nearly proportional to each
other because the frequency changes in lesser de-
gree, and the choice of the better one requires
accurate HB energies of oscillators with maxi-
mally different frequencies (say, HF and HS).
For the refinement of the coefficient of propor-
tionality in Eq. (4), such phenol–base H-bonded
complexes in CCl4 were chosen, that the HB
formation enthalpies for each of them were mea-
sured independently in three to six studies. The
intensities of the n(OH) bands were measured for
the chosen systems if insufficient data were avail-
able. The correlation of all these data produced
1588 A.V. Iogansen / Spectrochimica Acta Part A 55 (1999) 1585–1612

units) with the same non-significant constant term

0.1 (4).
The physical meaning of Eq. (5) is better ex-
pressed, according to Model (3), by the more
general formulation through the effective charge
of the HB:

− DH= 2.37× 1020(mXH) − 1/2(#mH/#rH) (5a)

where the numerical coefficient is for quantities in

Fig. 4. Correlation of − DH and DA 1/2 for systems in Table 1.
Reproduction of fig. 5.1 of [33].
an exact direct proportionality (see Fig. 4), which
did not change when new DH values, published
after 1969, were included. A linear regression of
all the data from Table 1 gave the direct
proportionality
− DH = 12.2(2)DA 1/2 (5)
where − DH is in kJ mol − 1 the number in paren-
thesis is the uncertainty of the last digit, the
standard deviation of the fit is s = 0.4 kJ mol − 1
and the correlation coefficient is R = 0.999. The
coefficient in (5) is exactly the same as found
earlier (Fig. 4, but note the change in the enthalpy
SI units (mass in au).
The necessary conditions for the validity of
Relationship 5 are:
(c1) the states of the system in the measure-
ments of A and − DH are identical,
(c2) uniformity of the HB in each combined
state, and
(c3) the calculation of − DH and A must be
performed exclusively per mole of the HB.
In the case of multi-protic acids, XHn, the calcula-
tion per 1/n mole is necessary, if permissible ac-
cording to other conditions. The other system
states, including the temperature, are not stan-
dardized (of course, at fulfillment of condition
(c1).). To apply Relationship 5 to isotopically
exchanged XD groups the quantity DA 1/2 should
be multiplied by (mXD/mXH)1/2 = 1.37 for the OD
vibrator.

Table 1
Experimental data for selected H-bonded complexes of phenol with bases in CCl4 used for the evaluation of Proportionality 5

No. Base Spectroscopic data Enthalpy (averaged)

Aa Dn b Ref. −DH c Ref.

1 Triethylamine 17.0 810 [8] 38.1(4) [72,30,73,74]

2 Dimethylsulfoxide 11.1 474 [8] 28.0(8) [75–77]
3 Dimethylformamide 10.9 384 [7] 26.0(4) [78,76,30]
4 Tetrahydrofuran 8.03 300 [6] 22.5(5) [72,76,30,21]
5 Methylethylketone 8.47 242 [7] 23.3(14) [20,79]
6 Acetone 7.45 243 [7] 20.5(4) [72,73,76,80,81]
7 Ethyl acetate 7.29 173 [7] 19.7(7) [72,20,79]
8 Acetonitrile 6.4 194 [8] 18.4(13) [72,76,25]
9 Diphenyl ether 3.3 133 [6] 9.06 [21]
10 Benzene 2.5 54 [6]d 6.5 [21]

a
A, intensity in 10−4 cm mmol−1.
b
Dn, band shift in cm−1.
c
−DH, in kJ mol−1.
d
Corrected to 100% complex formation; observed A=2.2.
 A.V. Iogansen / Spectrochimica Acta Part A 55 (1999) 1585–1612 1589

Table 2
Enthalpy changes calculated by Eq. (5) and measured by PB-calorimetry for n-butanol dissolved in neat liquid bases. Experimental
data: IR-spectroscopy from [10] and PB-calorimetry from [9]

No. Liquid base Experiment Calculation

Aa Dn b −DH c, (I) −DH c, (II) II–I

1 Triethylamine 7.3 394 23.1 24.9 1.8

2 Pyridine 6.31 318 18.7 22.6 (3 9)
3 Dimethylsulfoxide 5.8 259 19.5 21.2 1.7
4 Dimethylformamide 4.76 194 17.3 18.5 1.2
5 Tetrahydrofuran 3.59 156 12.8 15.0 2.2
6 Diethyl ether 3.23 137 12.4 13.8 1.4
7 Dioxane 3.27 136 13.0 14.0 1.0
8 Ethyl acetate 2.74 93 10.2 12.1 1.9
9 Benzene 0.88 29 2.1 3.4 1.3
mean 1.6(4)

a
A, intensity in 10−4 cm mmole−1.
b
Dn, frequency shift in cm−1.
c
−DH, in kJ mol−1.

One-to-one correspondence of the Expressions A further evaluation of Proportionality 5 was

5 and 5a takes place in the usual cases of
1. negative (#mH/#rH) and
2. positive (#m0/#r0).
Case (i) follows from the dissociation of the H-
bonded complexes into neutral molecules and case
(ii) from the monotonous intensification of the
nXH bands in a liquid phase. The weak HBs of
fluoroform are the only hitherto noted exception.
In this case the intensity A passes through zero
and the calculations are ambiguous; up to the
inversion one needs to take −DA l/2 and beyond it
the sum (A 1/2
0 +A
1/2
) [1].
The accuracy of Relation 5 was at once very
impressive (see Fig. 4); the standard deviation of
−DH was one half of that of the then reported
dispersion of the experimental −DH values em-
ployed (Table 1). Subsequent to the measurements
in CCl4 solutions, the intensities A were measured
in undiluted bases [6 – 8], and later the precision
data of PB-calorimetry evolved [9], among them
four of the already studied systems (numbers 53–
56 in Table 4). As seen, the PB calorimetry data
for three of the systems agree closely with those
calculated by means of Proportionality 5 (the
discrepancy is 0.25 compared with the uncertainty
of the measurements of 0.38 kJ mol − 1). There is
only a small difference in the case of the more
polar dimethylformamide.
based on calorimetric − DH data for the HB of
butanol [9] with a series of bases. These systematic
and relatively accurate data (to 9 0.3 kJ mol − 1)
stimulated spectral measurements [10] for some of
these systems. Precisely the same coefficient of
proportionality was obtained in [10] from these
data, shown in Table 2 (excluding pyridine): −
DH = 12.1DA 1/2 − 1.5. The small constant term
originated from an underestimation of each of the
eight experimental − DH values by a constant
quantity 1.6(4) kJ mol − 1, which is independent
from the HB energy (see Table 2). The latter is
regarded as a systematic error of PB-calorimetry,
namely as an excessive correction for a non-spe-
cific interaction with a model substance, 1-
chlorbutane in this case. Thus Proportionality 5
unexpectedly changed from a relation to be
checked to a means for the testing of PB-calori-
metric experiments. The revealing of the small
constant term in PB-calorimetric −DH data is
one more demonstration of accuracy of Relation-
ship 5.
It should be emphasized here that Proportional-
ity 5 is not one more among many other correla-
tions, but the first and only exact interrelation of
two major characteristic parameters of the inter-
molecular HB: the electric (IR) and the energetic.
1590 A.V. Iogansen / Spectrochimica Acta Part A 55 (1999) 1585–1612

This was demonstrated above with the series of
binary H-bonded complexes with phenol and bu-
tanol, and, as shown below, operates ‘universally’
in hundreds diverse systems with all kinds of HB.
However, before this we will discuss another as-
pect of the ‘additive’ model.
4. The intensity of the intrinsic vibrations of
molecules that are partners in hydrogen bonding
The H-bonded complex formation reaction (Eq.
(1)) influences also the intensities of some skeletal
(Q-) vibrations of molecules that are partners in
the H-bonded complex. The manifestation of a
Q-vibration is especially noticeable in the spectra
of a symmetrical linear partner, which is forbid-
den by the selection rules. It was observed, in
particular, for the stretching n(C-C) vibration in
heterodimers of acetylene – acetone [11] and for
the Fermi-doublet of CO2 – HCl (in a matrix) [12].
A disturbance of the electronic symmetry of the
partner-molecule under the influence of the HB
was taken as a reason for this. However, this is
impossible, the HB being too weak, and this effect
is not electronic, but mechanical. The Q-vibration
inevitably touches on the HB itself and its (#mH/
#rH) is so large that even a small oscillation of the
HB yields an appreciable contribution to the in-
tensity of the Q-vibration. Thus, the intensity of
each Q-vibration changes in the H-bonded com-
plex to that extent, to which it affects the H···Y
distance as a result of displacements of either the
H atom (for an RX – H vibration) or a pro-
tonophilic atom Y (for a Y – R vibration). In
other cases the vibrations of the weakly bound
partners do not interact.
The preceding considerations are formalized in
a simple theory [13] which yields the intensity
changes of all Q-vibrations in H-bonded com-
plexes for a specified geometry of the H-bonded
complex and known forms of the vibrations of
partner-molecules. The only empirical parameter
of the theory is the (#mH/#rH) of the ‘additive’
model (Eq. (3)). This parameter also specifies the
intensity of the intermolecular vibration n(XY) of
the H-bonded complex [13], but the latter does
not contain any new information and differs only
by the mass factor.
The example in Fig. 5 illustrates the changes of
the two n(CC) vibrations of diacetylene; the
forbidden n2(g), and the allowed n5(u); in the
H-bonded complex the first is almost three times
stronger than the second. Such an inversion of
intensities, otherwise not understandable, is due
to the change of the sign of (#m/#Q5) owing to the
large contribution of the HB, and can be calcu-
lated quantitatively [1]. If a weaker protonophil is
used, the selection rules can be completely in-
verted to forbid an active antiphase n5 and to
allow an inactive in-phase n2, the activity of the
latter appearing in spectra only as a result of a
contribution from the intermolecular HB.
The aforesaid relates also to the carbonyl group
C = O···H that is adjacent to the HB, the
n(CO) vibration changing considerably the O···H
distance and, consequently, the intensity of the
strong n(CO) band. The theoretical increase of the
n(CO) intensity from 4.0 to 5.6 in dimeric
RCOOH agrees with that observed [13], when
calculated with a C= O···H angle of 120° and
(#mC = O/#r)\ 0. This result signifies that in the
CO-group the HB does not affect noticeably its
intrinsic electronic structure, and the observed
intensification of the n(CO) band as a whole
derives from the contribution of the intermolecu-
lar O···H bond. This neither confirms nor rules
Fig. 5. The bands of the forbidden (n2) and the allowed (n5)
stretching vibrations n(C C) of diacetylene in the IR spec-
trum of its solution in CCl4 before (l) and after (2) addition
into the solution of the base N-methylpyrrolidone [1].
 A.V. Iogansen / Spectrochimica Acta Part A 55 (1999) 1585–1612
out the commonly known fact that the frequency
of the n(CO) vibration decreases on HB forma-
tion. The analogous calculations for N- and P-ox-
ides have not been conducted so far.
5. The experimental data
The intensities of the stretching vibrations ns of
free XH groups, which are given in Table 3, are
required for the calculations of Table 4; they
cover the range 0.004 – 3 (in units of 10 − 4 cm
mmol − 1). The supplementary Table 3a demon-
strates by the example of phenol the changes of
the n(OH) band parameters in ‘inert’ solvents and
the monotonic intensification of n(OH) in the
liquid phase. The quantities DA 1/2 and Dn of this
typical strong band are approximately propor-
tional, but only in the liquid phase and only up to
shifts of Dn : 100 cm − 1 (see below, part 7). As
seen in Table 3a, CCl4 and C2Cl4 with similar
properties are in the middle of the list of ‘inert’
solvents. ‘Free’ phenol in CCl4 (or C2Cl4) forms
an HB with CCl4 (or C2Cl4) as with a base
according to Reaction 1, with −DH = 4.8 kJ
mol − 1 relative to the really free molecules in the
gas phase. The same interaction of a stronger
electrophil, for example CF3COOH, reaches 9 kJ
mol − 1, diminishing the − DH of dimerisation of
RCOOH from 30 to approximately 20 kJ mol − 1
in CCl4 ([14]). The solvent has no marked influ-
ence on the centrosymmetric dimer (RCOOH)2.
The formation of HBs with CCl4 [15,16] is
clearly demonstrated in the IR spectra of the
simple hydrides HCl and HBr. Because of the
small moments of inertia, the ns-band involves the
hundreds of cm − 1 broad band of the free rotating
XH molecules with a narrow band of H-bonded
complexes XH···CCl4 protruding in the middle,
involving  20% of the XH molecules [16]. This
non-uniformity in the HBs (contrary to condition
(c2) for the applicability of Relation 5 ought to be
kept in mind for calculations by means of Expres-
sion 5).
In the case of H2O, which tends to self-associa-
tion and polymerization, the well known nas and
ns bands of the heterodimer HOH···CCl4 domi-
nate in the spectra, but being weak and broad are
1591
observable only as a background in thick layers of
CCl4. The opposite picture is observable in the
case of H2S, where the broad band dominates,
and the narrow one originates from only  2% of
the molecules. It is not difficult to understand the
similarity of the spectra of H2S as a compressed
gas and in CCl4 [17], considering that narrow
bands in the gas are from the homodimers
(H2S···HSH) [18,19] and in solution from het-
erodimers (HSH···CCl4).
The main body of the HB data is tabulated in
Table 4, which contains the experimental intensi-
ties A (together with Dn) and the spectral energies
− DH, calculated from them using Proportional-
ity 5, as well as the experimental − DH data. The
complementary Table 5 gives the temperature de-
pendence of these quantities for ice and water
from 16 to 360 K. The frequency shifts are evalu-
ated from a CCl4 solution (Table 3) to a band
maximum if the band is symmetrical or to its
center of gravity if the band is Fermi-disturbed on
HB formation.
Table 4 is based on all reliable data from which
it was possible to compose pairs of A and −DH,
measured under the same conditions. Two thirds
of the ca. 150 systems in Table 4 deal with HBs of
the OH groups, only three with those of SH and
so far the HF groups are absent (but no doubt
they too will obey Expression 5).
The majority of the enthalpy values recorded in
Table 4 are from the temperature dependence of
spectrophotometrically measured equilibrium con-
stants evaluated by means of the van’t Hoff equa-
tion. Their uncertainty is usually 9 2 to 9 5 kJ
mol − 1 (down to 91 kJ mol − 1 in high precision
work) [20,21]. However, time and again it was
pointed out that results of different studies often
disagree to a much larger extent. For example,
− DH/2 of the dimerization of caprolactam was
reported to be 11 [22] and 22 [23], compared with
the calorimetric result 17.6 kJ mol − l. The recent
result of −DH =17 kJ mol − 1 for the pyrrole–
acetonitrile H-bonded complex with a reported
error 10% [24] is twice the older value of 8.2 kJ
mol − 1 [25], and so on. Because of this, as far as
possible compatible results from well qualified
sources and the more reliable calorimetric data
were used, as employed above in Table 1.
1592 A.V. Iogansen / Spectrochimica Acta Part A 55 (1999) 1585–1612

Table 3
Intensities and frequencies of the ns stretching bands of monomeric XH groups in CCl4

No. Electophil (acid) XH Aa nb Ref.

I II III IV V

1 CF3COOH 2.2(2) 3500 [82–84]

2 CCl3COOH 1.5(3) 3535 [84]
3 CHCl2COOH 1.4(1) 3535 [40,84]
4 CH2ClCOOH 1.3(2) 3534 [40,55,84]
5 CH3COOH (gas) (0.5) 3585 [85]
5 CH3COOH 1.22 3534 [40,55,84,86]
6 C6H5COOH 1.65 3537 [55,86]
7 (CF3)3COH 1.5 3575 [87]
8 (CF3)2CHOH 1.17 3619, 3581 [87]
9 CF3CH2OH 0.76 3620 [87]
10 (CCl3)3CHOH 1.94 3581 [88]
11 (CHCl2)2CHOH 1.64 3592 [88]
12 CCl3CH2OH 0.82 3599 [88]
13 (CH2Cl)2CHOH 1.60 3592 [88]
14 Phenol: see Table 3a
15 p-nitrophenol 1.79 3595 [89]
16 p-chlorophenol 1.36 3610 [90,91]
17 p-fluorophenol 1.15 3615 [89]
18 C6Cl5OH 1.5 3525 [92]
19 C6H11COOH 0.59 3550 [93]
20 n-butanol (gas) 0.142 3670 [94]
21 t-butanol (gas) 0.084 3642 [63]
21 t-butanol 0.41 3617 [63]
22 i-propanol 0.45 3627 [88,95]
23 Methanol (gas) 0.21 3682 [96]
23 Methanol 0.43 3644 [96]c
24 H2O 2×0.38 3707, 3615 [36,39]
25 DOH (gas) 0.22 3707.47 [36,39]
25 DOH 0.35 3660.5 [36,39]
26 Imidazol 1.1 3478 [97]
26 Imidazol (in CHCl3) 1.3 3466 [97]
27 Pyrazol 1.3 3472 [97]
27 Pyrazol (in CHCl3) 1.4 3470 [97]
28 3,5-dimethylpyrazol 1.1 3472 [97]
28 -%%- (in CHCl3) 1.2 3465 [97]
29 Indole 1.1 3490 [57]
30 Pyrrole 0.92 3497 [57]
31 Diphenylamine 0.48 3435 [98]
32 N-methylaniline 0.39 3438 [98]
33 Dibenzylamine 0.06 3330 [99]
34 Piperidine 0.02 3350 [99]
35 Dimethylamine 0.01 3350 [99]
36 Methylamine 2×0.038 3401, 3341 [100]
37 o-caprolactam 0.52 3427 [98]
38 HNCS 2.99 3470 [101]
39 (CH3)B10Cl10C2H 1.0 3036 [102]
40 HCCH (gas) 1/2×0.72 3289 [4]
40 HCCH 1/2×1.04 3263 [4]
41 RCCH (gas) 0.41 3335 [103]
41 RCCH 0.62 3313 [104]
42 RCCH 0.048 3018 [105,106]
43 Cl3CD 0.018 2254 [26,27]
44 C6H5SH 0.05 2580 [96]
45 C2H5SH 0.01 2577 [17]
46 H2S 2×0.07 2593 [17]
47 ClH (gas) 0.34 2881 [16]
47 ClH 0.86 2831 [16]
a
A, intensity in 10−4 cm mmol−1.
b
n, frequency in cm−1.
c
Average from 14 values in supplement to [33].
 A.V. Iogansen / Spectrochimica Acta Part A 55 (1999) 1585–1612 1593

Table 3a
Intensities and frequencies of the n(OH) band of phenol in liquids, −DH being calculated with Rule 5 (supplement to No. 14 in
Table 3)

No. Liquid Aa DA 1/2b nc −DH d Ref.

1 None (gas) 0.43 −0.39 3652 −4.8 [36,96,107]

2 Perfluorocarbons 0.64 −0.25 3643 −3.0 [108]
3 Paraffins 0.80 −0.16 3623 −2.0 [96]
4 Cyclohexane 0.86 −0.12 3616 1.5 [96,108]
5 Tetrachloromethane 1.10 (0) 3612 (0) [96,108]e
6 Tetrachloroethylene 1.09 0 3610 0 [96,75,108]
7 Hexachlorobutadiene 1.12 0.01 3608 0.1 [108,109]
8 Carbon disulphide 1.24 0.06 3594 0.7 [96,109]
9 Trichlorethylene 1.63 0.23 3600 2.8 [96]
10 Chloroform 1 48 0.17 3597 2.1 [96,108]
11 Dichlormethane 1.79 0.29 3583 3.5 [96,108]
12 o-dichlorbenzene 1.63 0.23 3584 2.8 [108]
13 Chlorobenzene 2.00 0.37 3575 4.5 [96]
14 1,2-dichloroethane 2.15 0.42 3563 5.1 [96,108]
15 Benzene 2.23 0.44 3557 5.4 [6,96,108]

a
A, intensity in 10−4 cm mmol−1.
b
DA 1/2, intensification in 10−2 (cm1/2 mmol−1/2).
c
n, frequency in cm−1.
d
−DH, enthalpy in kJ mol−1.
e
Average of 10 values in supplement to [33].

In the intensity data there are no such dis-
crepancies as in DH and the data from diverse
sources generally agree very well. For example,
the A value for n-butanol in Table 3 is the mean
value of four studies from different years [10].
Despite the complete change of IR spectral instru-
mentation over 26 years, the results in two sets of
measurements of A of the H-bonded complexes
Cl3CD···Y are practically the same [26,27] (see
Table 6). The measurements in Moscow and
Vladivostok of A in the H-bonded complexes of
fluoroalcohols (Table 4) agreed within 10%.
The experimental enthalpies of H-bonding of
volatile electrophils, such as HCl, C2H2 and
RCCH, were obtained with the then new PB-gas-
chromatographic method with volatile liquid
phases [28,29]. This method is similar, in princi-
ple, to the PB-calorimetry method [30,9]. The
enthalpy of the XH···Y hydrogen bond is the
difference between the heats of vaporization of
XH from two liquids; protonophilic Y (provided
there is an adequate association of XH with Y),
and a neutral liquid, for example, a paraffin. The
heats of vaporization are measured by the gas-
chromatographic method with the unique tech-
nique of ‘hermetic columns’ [31], which permits
the application of ordinary liquids as a stationary
phase, including volatile ones, such as acetone.
The method was designed for small-sized
molecules XH and for such cases it is advanta-
geous, compared with others [32]. In general, re-
sults from gas-liquid chromatography (GLC) on a
liquid phase with a variable concentration of a
base ([32]) agree with those of the usual tempera-
ture-dependent spectrophotometric determination
of DH. The fraction of ‘free’ XH and an associa-
tion constant are determined by both methods,
but in GLC it is done directly by the volatility of
XH, because the bonded XH are not volatile and
the H-bonded complexes are absent in the gas
phase. In the spectrophotometric method the as-
sociation constant is determined with a concentra-
tion of ‘free’ XH in the liquid, which is a more
difficult and therefore less accurate measurement
to make. GLC is especially convenient and accu-
rate in the cases of the smallest molecules, such as
HCl (which are very inconvenient for spectropho-
tometric measurements).
 1594
Table 4
Enthalpies of HBs of diverse systems in CCl4 solutions or as marked, calculated from the intensification of the ns band and experimentally from calorimetry or the
temperature derivative of the equilibrium constant

No. Acid Base Solvent, mediaa Spectroscopic data Enthalpy data, −DH d

Ab Dn c Ref. Calcd. by Eq. (5) Exptl. Ref.

I II III IV V VI VII VIII IX X

O–H···Y bonds

A.V. Iogansen / Spectrochimica Acta Part A 55 (1999) 1585–1612

1 CF3COOH Pyridine-N-oxide CH2Cl2, C6H6 44.0 2300 [110] 66 67 [111]
2 CCl3COOH Dimethylsulphoxide 23.4 1235 [94] 45 44(3) [111,94]
3 CCl3COOH Tetrahvdrofurane 20.0 1015 [94] 41 45 [111]
4 CCl3COOH Dibutylether 18.5 905 [94] 38.5 39 [111]
5 CHCl2COOH Pyridine 42.7 2100 [40] 66 66 [112]
6 CHCl2COOH Dimethylsulphoxide 21.8 1135 [94] 43 41(2) [111]
7 CH2ClCOOH Pyridine 22(2) 1240(50) [40,55] 43(4) 43(1) [111,113]
8 CH2ClCOOH Dimethylsulphoxide 17(2) 1095 [55] 36.5 36(2) [111]
9 CH3COOH Pyridine 19,7(10) 1000(50) [40,55] 40.1 40 [113]
10 C6H5COOH Pyridine 23.0 1025(5) [40,55] 43 44 [113]
11 C6H5COOH Dimethylsulphoxide 18.3 805 [55] 37 37 [113]
12 RCOOH RCOOH (dimer) None (gas) (10.6) – – (31.0) 31.4(8) [2,114]
13 RCOOH RCOOH (dimer) 10.6 – [86] 26 23.2 [2,115,116]
14 Pentachlorphe- 2,4,6-(CH3)-C5H2N 41.8 1840 [117] 64 58 [118]
nol
15 Pentachlorphe- Pyridine 23.0 925 [117] 43 40 [118]
nol
l6 Pentachlorphe- Dimethylsulphoxide 14.8 580 [117] 31.8 31.4 [118]
nol
17 Pentachlorphe- Acetone 9.3 300 [117] 22.2 22.2 [118]
nol
18 Pentachlorphe- Acetonitrile 7.5 215 [117] 18.4 18.4 [118]
nol
19 Pentachlorphe- Dimethylsulphate 4.4 94 [117] 10 11 [118]
nol
20 (CF3)3COH Pyridine 22.8 1130 [87] 43.1 43.1 [44]
21 (CF3)3COH Dimethylsulphoxide 17.4 795 [87] 36.0 39.7 [44]
22 (CF3)3COH Dimethylacetamide 17.3 775 [87] 36.0 37.2 [44]
23 (CF3)3COH Dimethylformamide 15.8 735 [87] 33.5 36.0 [44]
24 (CF3)3COH Acetonitrile 9.7 363 [87] 23.0 26.8 [44]
25 (CF3)2CHOH Triethylamine 18.0 1185 [87] 39 42 [44]
26 (CF3)2CHOH Pyridine 15.6 740 [87] 35 36(2) [44]
27 (CF3)2CHOH Dimethylsulphoxide 12.4 545 [87] 29.7 30.0 [44]
Table 4 (Continued)

No. Acid Base Solvent, mediaa Spectroscopic data Enthalpy data, −DH d

Ab Dn c Ref. Calcd. by Eq. (5) Exptl. Ref.

I II III IV V VI VII VIII IX X

O–H···Y bonds

28 (CF3)2CHOH Tetrahydrofurane 9.08 405 [87] 23.4 26.2 [44]

A.V. Iogansen / Spectrochimica Acta Part A 55 (1999) 1585–1612

29 (CF3)2CHOH Dioxane 8.36 350 [87] 22.2 22.0 [44]
30 (CF3)2CHOH Tetramethylensulphone 6.90 205 [87] 18.8 20.5 [44]
31 CF3CH2OH Triethylamine 15.4 856 [87] 36.8 36.8 [44]
32 CF3CH2OH Pyridine 11.4 546 [87] 30 5 27(1) [44]
33 CF3CH2OH Hexamethapol 10.3 460 [87] 28.5 33.1(12) [44]
34 CF3CH2OH Dimethylsulphoxide 8.54 382 [87] 25 24(2) [44]
35 CF3CH2OH Dimethylacetamide 9.07 310 [87] 25.5 25.5(17) [44]
36 CF3CH2OH Tetrahydrofuran 6.83 275 [87] 21.3 21.8(4) [44]
37 CF3CH2OH Acetone 5.68 180 [87] 18.4 18(4) [44]
38 CF3CH2OH Acetonitrile 4.40 150 [87] 15.1 18(2) [44]
39 (CCl3)2CHOH Acetonitrile 11.0 211 [88] 23 5 22.6 [88]
40 (CHCl2)2CHOH Acetonitrile 8.33 174 [88] l 9.6 19.8 [88]
41 CCl3CH2OH Acetonitrile 5.60 145 [88] 17.8 l 79 [88]
42 (CH2Cl)2CHOH Acetonitrile 6.35 102 [88] 15.3 14.2 [88]
43 Phenol Triethylamine PB/C7H16 16.2(8) 820 [8] 38.1(12) 38.1(4) [72,78,73,74]
44 Phenol Pyridine PB 16.0 680 [8] 36.0 30.7 [9]
45 Phenol Pyridine 14.7 580 [8] 33 31 [30]
46 Phenol Dimethylsulphoxide PB 14.1 553 [8] 32.6 30.2 [9]
47 Phenol OP[N(CH3)]3 – – – – 37.7 [111]
48 Phenol OP(C4H9)3 14 590 [7] 33 33.9 [111]
49 Phenol OP(CH3)3 13.5 535 [7] 31.8 31.0 [78]
50 Phenol OP(OC4H9)3 9.4 355 [7] 24.7 25.5 [111]
51 Phenol Ether 8.2 281 [6] 22.2 22 6 [21,119]
52 Phenol n-butylaldehyde PB 7.5 226 [7] 20.5 19.5 [21]
53 Phenol Dimethylformamide PB 11.2 383 [7] 28.0 28.7 [9]
54 Phenol Tetrahydrofurane PB 8.94 320 [6] 23.6 24.1 [9]
55 Phenol Ether PB 8.44 282 [6] 22.6 22.8 [9]
56 Phenol Dioxane 7.68 284 [6] 21.2 21.4 [9]
57 Phenol Tetramethylenesulphone 7.3 196 [33] 20.1 20.5 [77]
58 Phenol Mesitylene 2.77 80 [120] 7.5 8.0 [120]
59 m-chlorphenol Diphenylsulphoxide 14.5 (338) [8] 33.0 33.5 [8]
60 p-chlorphenol Diethylsulphone 6.62 177 [8] 18.0 21.3 [8]
61 p-chlorphenol Dimethylsulphate 5.82 83 [8] 16.1 15.4 [8]

1595
62 p-chlorphenol (4) chalix-sulphonates 5.4(3) 115(8) [8] 15.1(8) 15(2) [8]
 1596
Table 4 (Continued)

No. Acid Base Solvent, mediaa Spectroscopic data Enthalpy data, −DH d

Ab Dn c Ref. Calcd. by Eq. (5) Exptl. Ref.

I II III IV V VI VII VIII IX X

O–H···Y bonds

63 Methanol Triethylamine 6.8 398 [121] 23.8 25.1 [122]

A.V. Iogansen / Spectrochimica Acta Part A 55 (1999) 1585–1612

64 Methanol Pyridine 5.2(4) 280(6) [3,123,124] 19.7(12) 17.6 [125]
65 Methanol (3) CH3-pyridines 5.12(3) 306(6) [124] 19.5(1) 17.4 [124]
66 Methanol (5) (CH3)2-pyridines 5.17(3) 326(9) [124] 19.7(1) 20.5 [124]
67 Methanol 2,4,6-trimethylpyridines 5.35 346 [124] 20.1 22.5 [124]
68 Methanol 2-Cl(Br)-pyridine 3.2(1) 198 [124] 13.8(4) 11.3 [124]
69 Methanol 3-Cl(Br)-pyridine 3.9(1) 242(1) [124] 15.9(4) 13.0 [124]
70 RCH2OH Dimethylformamide 4.16 160 [3] 16.5 15.9 [3]
71 RCH2OH Acetone 2.96 112 [3] 12.6 12.6 [3]
72 RCH2OH Benzophenone 2.46 88 [3] 10.9 11.3 [3]
73 RCH2OH Ether 3.72 146 [96,126] 15.3 15.7 [126]
74 RCH2OH Dioxane 3.03 126 [3] 12.8 12.3 [3]
75 n-butanol Pyridine 5.72 286 [10] 21.0 20.9 [127]
76 n-butanol Acetone 3.32 126 [10] 14.2 15.5 [128]
77 n-butanol Acetonitrile PB 2.68 98 [10] 11.9 – –
78 n-butanol Acetonitrile 2.28 89 [10] 10.3 10.5 [128]
79 n-butanol n-butanol-d neat liquid 6.1 311 [10] 22 – –
80 t-butanol Pyridine 4.74 260 [3,123] 18.5 17.3 [3]
81 t-butanol Dimethylsulphoxide C2Cl4 5.1 181 [75] 19.7 18.7 [75]
82 t-butanol Dimethylformamide C2Cl4 3.92 143 [3] 16.3 16.4 [3]
83 t-butanol Ether C2Cl4 2.60(6) 120 [121] 11.8(2) 11.0 [126]
84 t-butanol Dioxane C2Cl4 2.40 118 [3] 11.0 12.3 [3]
85 t-butanol Acetone C2Cl4 2.76 101 [3] 12.3 12.3 [3]
86 t-butanol Ethylacetate C2Cl4 2.53 75 [3] 11.6 11.8 [3]
87 t-butanol Benzophenone C2Cl4 2.10 77 [3] 10.0 11.2 [3]
88 t-butanol (CH3)2NCN C2Cl4 2.63 100 [75] 11.9 9.8 [75]
89 t-butanol (CH3)3CN C2Cl4 1.66 67 [75] 7.9 7.9 [75]
90 t-butanol C6H5CN C2Cl4 1.74 60 [75] 8.3 6.7 [75]
91 t-butanol CH2CHCN C2Cl4 1.61 55 [75] 7.7 9.5 [75]
92 t-butanol CH3CN C2Cl4 1.72 63 [75] 8.2 8.2 [75]
93 t-butanol ClCH2CN C2Cl4 1.44 47 [75] 6.8 6.7 [75]
94 t-butanol CCl3CN C2Cl4 0.9 21 [75] 3.7 3.0 [75]
95 t-butanol t-butanol-d Crystal, 290K 5.80 322 [63] 21.3 – –
96 t-butanol t-butanol-d Neat 300K 4.82 257 [63] 18.7 – –
Table 4 (Continued)

No. Acid Base Solvent, mediaa Spectroscopic data Enthalpy data, −DH d

Ab Dn c Ref. Calcd. by Eq. (5) Exptl. Ref.

I II III IV V VI VII VIII IX X

N–H···Y bonds

97 Imidazole Polymer CHCl3 13.6 526 [97] 31 30.3 [129]

A.V. Iogansen / Spectrochimica Acta Part A 55 (1999) 1585–1612

98 Imidazole Pyridine PB 10.6 396 [97] 26 18.5 [129]
99 Imidazole Dimethylsulphoxide 7.6 262 [97] 21 18.8 [129]
100 Imidazole Dimethylformamide PB 8.0 286 [97] 21 18.8 [129]
101 Imidazole Acetonitrile PB 4.5 136 [97] 12 11.1 [129]
102 Pyrazole Dimethylsulphoxide 7.9 285 [97] 21 25 [130]
103 SCNH Di-iso-propylether 21.88 576 [101] 35.5 32.4 [131]
104 SCNH Nitromethane 7.60 157 [101] 12.5 13.2 [132]
105 SCNH Mesitylene 6.91 139 [101] 10.9 9.6 [132]
106 Pyrrole Triethylamine C2Cl4 8.76 430 [57] 24.4 24.7 [43]
107 Pyrrole Pyridine 7.12 295 [57] 20.9 20.9 [43]
108 Pyrrole Dimethylsulphoxide 6.6 265 [57] 19.7 17.6 [43]
109 Pyrrole Acetonitrile 2.75 77 [57] 8.4 8.2 [25]
110 o-caprolactam o-caprolactam (dimer) 4.8 286 [133] 17.9 17.1 [134]
111 Diphenylamine Dimethylformamide PB/CCl4 3.4 132 [98]e 14 15.1 [135]
112 Diphenylamine Dioxane PB/CCl4 2.4 91 [98]e 10 9.6 [135]
113 N-methylaniline Pyridine 3.18 124 [98]e 14 15.8 [136]
114 N-methylaniline N-methylaniline 1.6 26 [98]e 8.0 8.3 [136,137]
115 N-methylaniline N,N-dimethylaniline 1.25 25 [98]e 6.3 7.7 [136]
116 N-methylaniline Benzene -¦- 1.14 15 [98]e 5.4 6.4 [136]
C–H···Y bonds

117 B10Cl10C(CH3)CH Dimethylformamide 7.2 269 [102,138] 20 5 22.2 [138]

118 B10Cl10C(CH3)CH Dimethylformamide PB 12.6 396 [102,138] 33 5 – –
119 B10Cl10C(CH3)CH Tetrahydrofuran 5.7 191 [102,138] 17.2 18.8 [138]
120 B10Cl10C(CH3)CH Tetrahydrofuran PB 10.4 306 [102,138] 30.5 – –
121 B10Cl10C(CH3)CH Acetonitrile 3.4 74 [102,138] 10.9 13 4 [138]
122 B10Cl10C(CH3)CH Acetonitrile PB 5.1 88 [102,138] 16 – –
123 HCCH; RCCH Hexamethapol 2.3 130 [4,139] 10 10.0(5) [28,140]
124 HCCH; RCCH N-methylpyrrolidon 1.9 100 [4,139] 8.0 9.0(4) [28,140]
125 HCCH; RCCH Acetone 1.3 47 [4,139] 5.4 5.0(6) [28,140]
126 HCCH; RCCH Dioxane 1.1 50 [4,139] 4.2 4 2(4) [28,140]
127 CCl3D Triethylamine 1.15 77 [26,27] 16 3 16.7 [141]

1597
 1598
Table 4 (Continued)

No. Acid Base Solvent, mediaa Spectroscopic data Enthalpy data, −DH d

A.V. Iogansen / Spectrochimica Acta Part A 55 (1999) 1585–1612

Ab Dn c Ref. Calcd. by Eq. (5) Exptl. Ref.

I II III IV V VI VII VIII IX X

O–H···Y bonds

128 CCl3D Diethyl ether 0.30 10 [26,27] 8.1 9.6 [142]

129 CCl3D Acetone 0.29(2) 0 [26,27] 7.5 7.3 [143]
Cl–H···Y and S–H···Y bonds

130 ClH Di-n-butylether CCl4/C7H16 8.0 530 [52] 24.2 24.7 [28,144]
131 ClH -%%- PB 8.4 530 [52] 25.1 25.1 [144]
132 ClH Diethylketone PB 7.9 400 [52] 23.4 23.4 [144]
133 ClH Nitrocyclohexane PB 3.5 160 [52] 12.6 12.1 [144]
134 ClH Mezitylene PB 2.9 119 [52] 10.5 10.0 [28,144,145]
135 ClH Benzene PB 2.6 73 [146] 9.2 8.3 [145]
136 Thiophenol Pyridine 1.32 140 [147] 11.3 10.0 [148]
137 Thiophenol Dimethylformamide (0.7) 55 [147] (7) 7.5 [148]
138 Thiophenol Benzene 0.165 20 [147] 2.2 2.1 [148]

a
Blank lines represent CCl4 solutions; PB: pure base; CH2Cl2/C6H6 represent different solvents in columns V/IX.
b
A, intensity in 10−4 cm mmol−1.
c
Dn, frequency shift in cm−1.
d
−DH, enthalpy in kJ mol−1.
e
Observed A values in [98] reduced to full complexation, corrections amounting from 5% for pyridine to 40% for benzene.
Table 5
The ns of HOD in liquid water and in ice at different temperatures and the −DH of condensation

A.V. Iogansen / Spectrochimica Acta Part A 55 (1999) 1585–1612

No. T, K n(OH) n(OD) −DH c

State Aa Dn b n(OH)/n(OD) Ref. State Aa Dn b Ref. Eq. (5) Lit.d −RT

Gas 0.22 (3707.47) 1.3612 [149,150] Gas (2723.66) [149]

1 358 Neat D2O 3.64 267 1.360 [151] Neat H2O 1.89 194 [151] 17.3(3) 17.7
2 333 4.03 282 1.362 [151] 2.07 209 [151] 18.4(4) 18.4
3 298 4.44 307 1.360 [151] (2.24) 224 [151] 19.6(1) 19.5
3a 298 4.32 306 1.357 [39] 2.32 217 [39]
4 273 4.62 322 1.358 [39] 2.54 231 [39] 20.6(1) 20.2
5 273 D2O ice 6.04 396 1.355 [39] H2O ice 3.10 280 [39] 24.1(3) 23.2
6 248 6.21 404 1.354 [39] 3.21 295 [39] 24.4(2)
7 200 6.39 417 1.354 [39] 3.40 294 [39] 25.1(0)
8 150 6.64 425 1.354 [39] 3.60 300 [39] 25.8(2)
9 100 6.95 437 1.3535 [39] 3.66 308 [39] 26.4(2)
10 50 D2O ice 7.13 442 1.3531 [39] H2O ice 3.93 311 [39] 27.2(6)
11 16 7.56 443 1.3527 [39] 3.99 311 [39] 27.8(1)
(ex) (0) (7.50) (444) (1.3522) [39] (4.05) (311) [39] (27.8)

a
A, intensity in 10−4 cm mmol−1.
b
Dn, frequency shift in cm−1.
c
−DH-enthalpy in kJ mol−1.
d
Handbook value, [152].

1599
 1600
Table 6
Spectroscopic data for solutions of chloroform-d in bases, enthalpies calculated from the IR data, and calorimetric heats of equimolar mixing of chloroform with base, Q(1:1)a

A.V. Iogansen / Spectrochimica Acta Part A 55 (1999) 1585–1612

No. Base Dn b Ac −DH d Ke a (1:1) Q(1:1)f

Observed Ref. Corrected IR calc. IR calc. Obs. Ref. Obs.–calc. %

1 Neat liquid CDCl3 (2253) 0.024(2) [26,27] – 0

2 CCl4 0 0.017(1) [26,27] −0.4 −0.2 −0.08 [142] 0.1
3 Benzene 5 0.081(9) [26,27] (0.1) (2.7) – (0.3) (0.4) 0.38 [153] (0) (0)
4 Dioxane 4 0.24(2) [26,27] 0.39 6.90 0.34 0.51 1.76 2.05 [142] 0.29 14
5 Ether 10 0.30(0) [26,27] 0.38 7.74 0.40 0.52 2.01 2.5 [142] 0.50 20
6 Dibutyl ether 15 0.23 [26] 0.37 7.57 0.28 0.40 1.51 1.76 [142] 0.25 14
7 Di-iso-propyl ether 11 0.35 [26] 0.50 9.20 0.34 0.48 2.21 2.84 [142] 0.63 22
8 Tetrahydropyrane 9 0.33 [26] 0.42 8.24 0.33 0.46 1.90 2.51 [142] 0.61 24
9 Tetrahydrofurane 9 0.35(3) [26,27] (0.42) (8.24) – (0.55) (2.3) 2.84 [142] (0.5) 18
10 1,8-cineol 22 0.55 [26] 0.65 10.9 0.57 0.52 2.83 3.51 [142] 0.68 19
11 Acetone 0 0.27(2) [26,27] 0.33 7.03 0.46 0 54 1.90 1.97 [143] 0.07 4
12 Cyclohexanone 4 0.32 [26] (0.38) (7.74) – (0.55) (2.2) 2.59 [154] (0.4) 15
13 Pyridine 34 0.50(3) [26,27] (0.63) (10.7) – (0.5) (2.7) 2.01 [141] (−0.7) −35
14 Tributylamine 75 0.38 [26] 0.85 12.8 0.19 0.30 1.92 1.84 [141] −0.06 −3
15 Triethylamine 76 0.80(6) [26,27] 1.15 16.0 0.37 0.45 3.61 3.64 [141] 0.03 1

a
In parenthesis: interpolated values.
b
Dn, frequency shift in cm−1.
c
A, intensity in 10−4 cm mmol−1.
d
−DH, enthalpy in kJ mol−1.
e
K, equilibrium constant in l mol−1.
f
Q(1:1), heat of equimolar mixing in kJ mol−1.
 A.V. Iogansen / Spectrochimica Acta Part A 55 (1999) 1585–1612
In the range of weak HBs, quite a number of
heats of equi-molar mixing, Q(1:1) of chloroform
with different bases were determined, but with
unknown degrees of association, a(1:1). The in-
tensities of the n(CD) band in some of these bases
are also known at small and not accurately spe-
cified chloroform concentrations, but not for the
1:1 mixtures. Nevertheless, the association con-
stants, estimated from the displacement of the
d-vibration by the HB [26], permit us
1. to extrapolate the observed intensity A of the
n(CD) band towards complete association and
to calculate the enthalpy (−DH) of the
CCl3CH···Y hydrogen bond, and
2. to calculate the degree of association a(1:1)
and to obtain the spectral heat of mixing
Q(1:1,IR)= −DH(IR) a(1:1), to be compared
with the calorimetric Q(1:1).
The results are shown in Table 6, which presents
most of the data of the original table 5.9 from
[33].
When it is impossible to distinguish free and
bonded XH because the Dn shifts are very small,
the heat of HB can be estimated from the appar-
ent intensity, A0 , according to the approximate
analog of Eq. (5):
Q H(kJ mol − 1) :12DA0 1/2(104 cm mmol − 1)1/2
(6)
where the unknown mean value of the root ŽA  1/2
is knowingly incorrectly replaced by the root of
the mean value ŽA1/2, i.e. by the root of the
directly observed apparent molar intensity A0 of
the XH band. There is no need for an interpreta-
tion of the spectra beside an assignment of the ns
band to the particular XH (and the calculation
per mole of XH). The error from the replacement
of the mean values can be estimated tentatively
from A/A0 and a.
The ‘spectral calorimetry’ by means of Expres-
sion 6, which is insensitive to the nonspecific
interactions, approximately separates ‘H-interac-
tion heat’, Q H, that is the change of −DH and
the degree of association a, from the total heat
effect. For example, there is nothing besides ‘H-
interaction heat’ in the processes shown in Fig. 7.
However, on the dilution of N-methylaniline with
CCl4 another interaction (disruption of aromatic
1601
stacking) is relatively important, its heat effect
amounting to 1–1.5 kJ (mol amine) − 1 [34].
The n(CH) bands of neutral CH-groups inten-
sify in a liquid phase far less then those of XH,
namely, with a characteristic value DA =0.03
units per CH-bond. This arises because the orien-
tation of the interacting molecules is random and
it is not the moments which are summed, as in
directed HBs, but their squares [33,35]. Ascribing
formally this intensification of the n(CH) bands to
HB formation, with A0 = (0.1–0.5) in the gas
phase, the energy (−DH) of this interaction can
be estimated as 0.3–0.5 kJ mol − 1. The changes of
A(CD) of benzene-d6 and cyclohexane-d12 in pro-
tonophilic liquids are also completely negligible
[33].
6. Results and discussion
6.1. The uni6ersality of Proportionality 5
The universality of Proportionality 5, which is
also known as ‘the intensity rule’ [1], is confirmed
by all the experimental data, which are given in
Tables 1, 2 and 4–6. The general picture is clearly
demonstrated in Fig. 6, constructed from the data
of these tables. The HBs of XH, OH, NH, CH,
and SH electrophils (from the strong hydrogen
halides to the weak chloroform) with pro-
tonophils (from the strong amines and oxides to
the weak benzene and CCl4) from experiments
quoted in the tables are presented.
The ‘intensity rule’ Eq. (5) is true for different
associates:
1. for isolated H-bonded complexes XH···Y in
solutions and in undiluted bases, the latter
being the most numerous,
2. for cyclic dimers in the gas phase and in
solutions,
3. for polymeric chains (or cycles) of HBs in
associated liquids and crystals, and
4. for the continuous spatial network of the HBs
in liquid water and ice from 300 to 17 K
(Table 5).
Rule 5 is equally true for both diverse X and Y in
HBs of XH···Y in a constant environment and for
a particular HB (for example, OH···O of water) in
1602 A.V. Iogansen / Spectrochimica Acta Part A 55 (1999) 1585–1612

Fig. 6. Comparison of the calculated, by Relation 5, and observed − DH for various H-bonded systems.

different environments, which drastically change
through different interactions with neighbors.
Rule 5 applies (if its conditions are met) not only
to Equilibrium (1) but also to other, more compli-
cated and indefinite changes of the HBs taking
place in solvation, condensation, crystallization
and so on. Both internal and external changes of
the HBs such as replacement of the partner Y and
of the environment, rearrangement, and others,
always produce such correlated pairs of quanti-
ties, −DH and DA 1/2, as required by Rule 5.
The crystallization of water abruptly increases
the intensity of the ns band of HDO by 26(6)%
(Table 4), and, correspondingly, the HB in ice
strengthens, according to Rule 5 by 3.3(3) kJ
mol − 1 (as a mean value from n(OH) and n(OD)).
This agrees with the heat of freezing of water
(2× 3.00 kJ mol − 1 for two HBs per molecule),
confirming the validity of Rule 5 in a crystal of
ice.
Finally, very recently Epstein et al. [36,37] stud-
ied a new type of ‘hydrogen···hydrogen’ HB and
found that Relationship 5 is maintained in this
case too.
Rule 5 holds true in all linear HBs, including
intramolecular ones. On the contrary, the interac-
 A.V. Iogansen / Spectrochimica Acta Part A 55 (1999) 1585–1612
tion in obviously nonlinear groups XH···Y does
not intensify the ns-bands. Linearity of XH···Y is
possible in six-membered and larger cycles, but
becomes difficult in smaller ones. In the series of
v-methoxy-1-alkanols CH3O(CH2)n OH [38] with
n varying from one to four the fraction of spectral
DH represents 0, 15, 50, and 100% out of the total
enthalpy. Neither is there a significant intensifica-
tion of the ns-band in a bound cis-conformer in
the classic case of o-substituted phenols. Thus, it
is possible with Rule 5 to differentiate and classify
intramolecular HBs better than with Dn.
Iogansen and Rozenberg [39] estimated from
the temperature change of A and DH for ice and
water from 170 to 360 K that the proportionality
coefficient of Eq. (5) changes only very weakly
with the temperature, increasing by 0.02(3)% per
degree, that is, the coefficient in Rule 5 is rather
insensitive to temperature.
6.2. The high accuracy of Rule 5
The high accuracy of Rule 5 was already shown
in the calculation of the proportionality coeffi-
cient (see above). Comparable evaluation of the
data in Table 4 makes sense, even though the
accuracy of the data themselves is not sufficient,
because of the diverse nature and extensive set of
data. The mean square root deviation of
DH(IR)− DH(measured) from 180 systems is 1.4
kJ mol − 1 or 7.3% of the mean DH value. This
does not exceed the probable errors of the mea-
sured DH values, and consequently does not deny
the better accuracy estimated from selected, well
established, systems. More interesting and impor-
tant is an almost precise coincidence of the two
mean values of DH(IR) and DH(measured),
which differ by only 0.17 kJ mol − 1 or 0.25% of
the total range of values. It follows that the errors
in all the systems are only random, there being no
systematic deviation of two sets of DH, their
equality being precise. This is the reverse side of
the universality of Rule 5, which can be written
for the sake of convenience of quotation and
clarity as:
DH(IR)= DH(meas.) (7)
where the left hand side is calculated according to
1603
Rule 5, the previously mentioned conditions hav-
ing been met, and the right side is the measured
value.
Unlike the entries in Table 4 and Eq. (7) in the
weaker HBs of chloroform, where the part of the
nonspecific interactions must increase, a system-
atic difference of two sets of heats Q(1:1,IR) and
Q(1:1,meas.) is noticeable, but only for ethers.
Unfortunately, the accuracy of the observed in-
tensities A in Table 6 is somewhat deteriorated
when the molar A is diminished, and a(1:1) de-
creases too, so that Q(1:1,IR) becomes inaccurate,
because of the complicated recalculation to uni-
form states. (Not very complicated measurements
of A(CD) in the 1:1 mixtures where the Q(1:1) are
determined would give directly the more accurate
a(1:1) and Q(1:1,IR).) Nevertheless, it is estab-
lished that in seven ethers Q(1:1,IR) is less than
the calorimetric one by 0.5(2) kJ mol − 1 (2% of
the energy of an HB of medium strength). Other-
wise, the fraction of HB-association in Q(1:1)
represents only 80%, and the rest, 20%, is the
nonspecific interaction (which is specific for
ethers, judging from the other four systems with
chloroform in Table 6).
Differences of the order of 0.5 kJ mol − 1, corre-
sponding to the uncertainties of the best measure-
ments of DH, are not detectable for the HBs of
Table 4. They are noticeable only for weak HBs,
in particular in d-chloroform–base systems, which
are especially convenient for the application of
Rule 5, because of the small A0(CD) and the
absence of isotopic exchange.
6.3. The extent of the 6alidity of Rule 5
The extent of the validity of Rule 5 is wide
indeed. It comprises a 200-fold range of energies,
from the heat of mixing of benzene with chloro-
form (0.3 kJ mol − 1) to near that of the typical
chemical association of strong acids with bases,
which is close to proton transfer and salt forma-
tion (  60 kJ mol − 1). This wide extent required
the double scale of Fig. 6.
The natural upper limit of Rule 5 is proton
transfer that depends on the pK of the acid, the
medium and other conditions, and is not consid-
ered here. The rule cannot be extended beyond its
1604 A.V. Iogansen / Spectrochimica Acta Part A 55 (1999) 1585–1612
logical limit of a symmetrical HB [1,40,41]. In a
conjugate H-bonded complex (ion pair)
X − ···HY + the bonds X – H and H···Y inter-
change the proton, and the assignment of intensi-
ties and the meaning of the rule change. The
calorimetric and spectral DH diverge; the former
continues to increase up to 170 kJ mol − 1 and
becomes the heat of protonation of the base, the
latter decreases in an interionic HB, down to 20
kJ mol − 1 for pyridinium perchlorate, for
example.
A lower limit is practically absent. The calcu-
lated heats of mixing of chloroform with bases
(except ethers) in Table 6 differ from experiment
by 0.15 kJ mol − 1. The calculated and calorimetric
heats of mixing, shown in Fig. 7, differ by not
more than this amount. Finally, the rule gives the
correct sign and a good estimate even for the so
tiny a value as the heat of mixing of CHCl3 with
CCl4 (Table 6).
Fig. 7. Heats of mixing for: (a) chloroform + triethylamine
and (b) piperidine+cyclohexane. Empty circles, data from
calorimetry; filled circles, from Relation 5 [1].
6.4. Indi6idual disagreements of the calculation
and experiment
Individual disagreements of the calculation and
experiment are always emphasized, but are usu-
ally eliminated later with newer DH values. The
H-bonded complex pyridine–phenol is remark-
able in the sense that the spectral result exceeds
the experimental one by 15%. The author [42], as
usual, trusted previously reported experimental
DH data (12 in number!) rather than his own and
the newly formulated Rule 5. Instead of making a
critical analysis the author erroneously ‘explained’
the discrepancy by the coupling of p-electrons of
the N-heterocycle with the ns vibration. This ‘ef-
fect’ was confirmed also for H-bonded complexes
of pyridine with pyrrole and indole [42]. However,
shortly afterwards, the precise agreement of
calorimetric DH measurement of Nozari and
Drago [43] with the spectral DH (No. 107, Table
4) eliminated this ‘effect’. Analogously, the reli-
able calorimetric DH came close to the spectral
one with the same standard deviations for the
H-bonded complexes of phenol. The new HB
enthalpies of pyridine, in particular, with fluoroal-
cohols (Table 4), also obey Rule 5. Thus, the
anomaly of N-heterocycles disappeared, an ‘exal-
tation’ of the intensity is absent and p-electrons of
N-heterocycles are not involved in the ns
vibration.
Calorimetric DH values of nine H-bonded com-
plexes of hexafluoro-2-propanol exceed the spec-
tral values systematically by 6(3) kJ mol − 1 on the
average [44]. However,
1. such excesses are absent for spectrophotomet-
rically obtained DH, and
2. for other fluoroalcohols no such differences
with calorimetric DH (from the same sources)
were found.
These differences were, therefore, related to an
(unclear) systematic error of the usually more
accurate calorimetric DH [44]. There is a peculiar-
ity for undiluted pyridine; all three PB-calorimet-
ric DH values (No. 2, Table 2, Nos. 44 & 98,
Table 4) are less than the spectral DH values by
5(2) kJ mol − 1, and the same is observed for No.
13 in Table 6 (by 3 kJ mol − 1, when recalculated
per H-bonded complex). These discrepancies are
 A.V. Iogansen / Spectrochimica Acta Part A 55 (1999) 1585–1612
presumably related to a Py – Py interaction, which
interferes with the formation of the H-bonded
complex and the (endothermic) DH of which re-
duces the total PB-calorimetric DH. Being insensi-
tive to this interaction, the intensity A(XH) gives,
according to Rule 5, only the DH of the HB
(XH···Py). The latter, in neat pyridine, is some-
what larger than the DH in CCl4 solution (see
numbers 44 and 45 in Table 4), and its diminution
in PB-calorimetry leads to an incidental equality
of the calorimetric DH of the H-bonded complex
phenol–pyridine both in CCl4 solution and in
pure pyridine [30].
6.5. The application of Rule 5
From the practical point of view, Rule 5 repre-
sents the finally found spectral measure of the HB
strength that has been sought from the days of
Badger and Bauer [45]. It is actually equivalent to
the thermodynamic measure, is as reliable as a
direct experiment, and not rarely exceeds its accu-
racy. Needless to say, the accuracy of Rule 5
cannot be superior to that of the calorimetric
enthalpies with which it is calibrated. However, in
view of the universality of this rule the same high
precision of these enthalpies can be kept when
Rule 5 is applied to other systems, where the
accuracy of direct measurements can be lower.
The properly and accurately measured intensities
A will yield the DH to the level of accuracy of the
calibration that is inherent in the coefficient of
Proportionality 5.
To measure the molar intensity of the ns-band is
much simpler and faster than to measure spec-
trophotometrically d log K/dT to yield DH by
van’t Hoff’s expression, or to measure the DH
calorimetrically. Thus it is easier to obtain the DH
of interest by application of Rule 5, in order to
widen or create the necessary series of HBs with
known energies. It appears attractive also for the
reliable estimation of the HB strength where the
thermodynamic methods are inapplicable, for ex-
ample, in glasses and other non-equilibrium sys-
tems, in crystals and, especially, in biochemical
systems.
As an example of the application of Rule 5 may
be cited the expansion of the range of DH, by
1605
which the relationship − DH/kJ mol − 1 =21.8
PjEj (the rule of factors) was proposed [46]. This
relationship expresses DH as a product of two
independent numbers, which characterize the pro-
ton donor i (Pi ) and the electron donor j (Ej )
relative to phenol and diethyl ether, assigned Pi
and Ej = 1, respectively.
6.6. Theoretical studies of hydrogen bonds
Theoretical studies of HBs have not reflected
the intriguing Proportionality 5a nor have they
revealed its manifest generality. No theoretical
‘mechanism’ for Relationship 5 exists, and even in
series of HBs involving a given XH an agreement
of theoretically calculated HB strengths with ex-
periment was not reached [47]. According to the
interpretation of ab initio quantum-chemical cal-
culations, different dominating contributions,
coulombic and polarization, are responsible for
the HB energy and the intensification of a ns
band, respectively. Proportionality 5 excludes
such an interpretation of the calculations, since
otherwise the universal proportionality must be
considered as fortuitous.
It should be noted that when Ratajczak, Or-
wille-Thomas and Rao [48] correlated the corre-
sponding A and DH on the basis of Mulliken’s
theory of charge transfer, they mentioned all the
reports [5–8] about Rule 5. However, they used
them only as a source of experimental data for
their own correlation, and the subject and essence
of the quoted works, namely Proportionality 5,
remained unnoticed. The correlation [48], as
shown in [1], gives the wrong relationship of the
quantities and is significantly not as good as Rule
5.
6.7. Refinement of Rule 5
An attempted refinement of Rule 5 was made
by Perelyigin, who found different coefficients of
proportionality for different ROH···Y HBs [49].
In his work the author leaned upon only his own
results, supposed to be superior to all others,
because they were measured in one laboratory,
and the literature data were ignored intentionally.
Clearly such a ‘refinement’ conceals the errors of
1606 A.V. Iogansen / Spectrochimica Acta Part A 55 (1999) 1585–1612
measurements of DH in the one laboratory. In a
more recent paper [24], the authors of which also
lean only upon their own DH, different coeffi-
cients of Rule 5 were found for each of the eight
groups studied (each group involves five NH···Y
systems). In the lines of these studies one may
expect a publication of a singular coefficient for
each H-bonded complex, allowing any results one
likes to be established.
The ‘reinvestigating correlations’ DH  DA 1/2
of Stolov et al. [50] are also based only on their
own calorimetric data, other results being declara-
tively ignored. These data include 25 systems with
previously unknown HBs, including those of ace-
tonitrile and nitromethane ‘‘with participation of
methyl groups’’. These new HBs have no qualita-
tive spectral indications of HB formation, nor is
anything said about the geometry and stoichiome-
try. (In polar liquids a marked intensification of
the ns of methyl groups was observed, and this
probably deserves an investigation.) However, the
statement about the agreement of the calorimetric
and spectral DHs is wrong, because the DA 1/2
were erroneously calculated in [50,51] per mole of
CH3 groups rather than per mole of XH···Y HB,
as must be done according to the conditions of
Rule 5. The correct calculation increases the spec-
tral DH by a factor of 31/2, and, for example, in
the system acetonitrile – dimethylsulphoxide,
where the calorimetric −DH = 4.2 kJ mol − 1 is
found, the spectral − DH will be 11 kJ mol − 1.
The underestimated DA 1/2 by the factor of 31/2
appear also in a correlation of the group ‘A’ (i.e.
weak HBs and those in water [50]) and are also
erroneous to the extent of the involvement in it of
HBs ‘with participation of methyl groups’. It
should be emphasized that Rule 5 does not
confirm the existence of such HBs, since it is
inapplicable to them because of the absence of the
required XH···Y hydrogen bonds. The hypotheti-
cal bonding of a CH3 group (as a whole) requires
other proofs. An analogous mistake (by a factor
of 21/2) is made in calculations of HBs of water
per mole H2O. The mistaken HB energy was
considered as a ‘strange’ anomaly of water and
‘‘this fact did not find an explanation’’ [50]. The
correct calculation transfers water into group ‘B’
(i.e. strong HBw [50]) and makes the subdivision
into groups ‘A’ and ‘B’ meaningless. Evidently,
the ‘re-investigation correlation’ [50] and Rule 5
are incompatible despite of their use of practically
the same proportionality coefficient.
7. Intensification and displacement of the ns bands
Between DA 1/2 and Dn, the apparently related
spectral parameters of an XH vibrator, there is no
general interrelation resembling that of the seem-
ingly dissimilar properties DH and DA 1/2. This
fact is due to the different significance of the
intensification and the displacement (to lower fre-
quencies) of the ns band. The intensification DA 1/2
as well as the enthalpy DH are the primary and
direct properties of the HB, H···Y, but Dn, on the
contrary, is a secondary, indirect influence of it.
In other words, the shift is due to the interaction
between the two bonds, X–H and H···Y. ‘Addi-
tivity’ of the H···Y in the case of the frequency,
because it could only increase it, would contradict
the experimental evidence of the red-shift that
takes place.
The displacement of the ns band on hydrogen
bonding, unlike its intensification, is
1. different for diverse XHs,
2. essentially non-linear, and
3. less accurate even in the most favorable cases.
7.1. Specificity of the Dn of different XH
Specificity of the Dn of different XH has, appar-
ently, no explanation or general regularity. A
correspondence of the Dn and the intensity A0 is
observed for HBs of the XH involving elements X
of the second period. This is best demonstrated by
the contrasting behavior of the n(CH) of acetylene
and chloroform, electrophils with equal HB
strength and different A0 (Table 3). The intensive
ns of acetylene (and alkynes) displaces properly
(Table 4) but the weak ns of chloroform remains
undisplaced by the H-bonding. Even more differ-
ent is the behavior of intensive and weak n(NH)
bands (Tables 3 and 4), but in this case the
electrophilicity changes simultaneously. In the
third period, however, another correspondence
may be seen. The weak n(SH) bands (Table 3),
 A.V. Iogansen / Spectrochimica Acta Part A 55 (1999) 1585–1612 1607

contrary to the n(CH) of chloroform, displace in

protonophilic liquids by 90 to 140 cm − 1, as do
the acetylenic n(CH) bands (although the HBs of
SH are weaker) [17]. The displacement of the
intensive n(ClH) is also 1.5 times larger than that
of n(OH) [52].
There is, therefore, no general interrelation be-
tween Dn and DH, especially in weak HBs, where
the shift Dn is no longer a criterion for an HB.
For a given enthalpy, say − DH =10 kJ mol − 1, it
can have any magnitude, from 0 to 150 cm − 1 (see
Tables 4 and 6), and in certain cases it may even
be negative, as in Cl3CH···OPCl3, where the fre-
quency increases by 18 cm − 1 [53].

7.2. Spectral measure of the hydrogen bond

strength
As a spectral measure of the HB strength, the
red shift of the ns band was at first supposed to be
the most noticeable manifestation of the HB. The
hope for the tempting validity of the simple Bad-
ger-Bauer rule [45]:
−DH =a(Dn/n) :0.10(Dn) (8)
did not vanish even after the non-linearity of the
function −DH = f(Dn) was revealed [2]. Linear
correlations in the form − DH =aDn +b kept
their popularity despite the fact that each was
only the tangent to the curve −DH =f(Dn), devi-
ating from a proportionality the more the larger
the correlated − DH and Dn are [1].
In the series of H-bonded complexes of phenol
[54] the square-law relationship Dn 8 ( − DH)2, or
with a necessary correction
(DH)2 =1.92[(Dn) −40] (9)
is better adhered to for shifts from 100 up to
850 cm − 1 DH in kJ mol − 1. Such a relationship is
acceptable even up to shifts of 2000 cm − 1 for the
HBs with carboxylic acids [41,55]. To the extent
of the validity of mutual proportionalities of Dn
shifts [56] Relationship 9 was expected to remain
valid also for the HBs of other XHs with intensive
ns, where it was actually confirmed [10,44,57].
The smaller shifts, up to 100 – 200 cm − 1, of
intensive ns-bands change approximately linearly
with the HB energies (Table 3a), but only in the
Fig. 8. Plots of Dn against D0 for triatomic H-complexes of
HF and HCl with Ar (1), Kr (2) and Xe (3). Data from [60].
liquid phase. Isolated H-bonded complexes in the
gas phase have no linear range [1]. In particular,
linearity is absent in the weakest H-bonded com-
plexes of HF and HCl with noble gases, discov-
ered by Rank and co-workers [58,59], where the
range of Dn, which varies from 1.77 to 29.18
cm − 1 [60], is two orders of magnitude less than
usual in HBs in liquids (Fig. 8, but this special
area of high resolution spectroscopy is not
touched upon further here). As it is shown in Fig.
8, constructed with data from the review [60], the
Dn are from the very beginning nonlinear with the
HB energy, as are the Dn of XH bonds of the
second period in liquids at Dn \100 cm − 1. The
quadratic curve of Dn with the energies of the
HBs in the gas phase is followed further up to
shifts of 500 to 700 cm − 1.
7.3. The accuracy of the correlation
− DH = f(Dn)
The accuracy of the correlation − DH = f(Dn)
is lower than that of Rule 5 even in the most
favorable case of HBs of a single XH group. Fig.
9 shows the behavior of Dn and DA 1/2 of the same
set of H-bonded complexes of phenol. The devia-
tions of the Dn data from the curve are larger than
1608 A.V. Iogansen / Spectrochimica Acta Part A 55 (1999) 1585–1612
those of DA 1/2 from the straight line of Rule 5.
This is a natural outcome of employing one point
of a broad distribution (the peak of the band,
defining Dn), which is less accurate than the inte-
gral quantity A, and is more subject to the influ-
ence of random factors, to which the quantity A is
insensitive.
In particular, the thermal, T-broadening of the
ns-bands must create scatter of the Dn quantities,
but this was, apparently, not taken into account
till now. T-broadening is the result of ‘hot’ transi-
tions from vibrational levels of the H-bonded
complex, as it was first proven by Thomas [61,62]
and later confirmed by the unique narrowing of
the ns-bands of isotopically diluted OH(OD)
groups on cooling from 300 to 17 K (for t-bu-
tanol [63], ice [39], and ethanol [64]).
Originating from Thomas’s idea, the ‘deforma-
tional’ model of T-broadening [65,66] implies the
conclusion about unidirectional broadening of the
ns-bands, important for the present discussion.
The band origin of the ns-band, its reported vibra-
tional frequency, is on the low frequency side of
Fig. 9. Plots of Dn (circles) and DA 1/2 (squares) against −DH
for the same H-bonded complexes of phenol + base. Data
from Tables 1 and 4.
the band, the maximum of which is shifted up-
ward, approximately by the bandwidth. For a
given vibrational frequency, but at different
widths of the ns-bands, their peak frequencies (and
Dn) differ by the differences in their widths.
Hence, the shifts Dn of the ns-bands depend not
only on the energy − DH but also on the band-
width, and at being uncorrelated with the Dn
width difference, the scatter of the Dn in Fig. 9 is
inevitable.
In the series of H-complexes of a given base, for
example, of oxirane [67], the proportionality of
broadening and shift can be almost exact (r=
0.997) and hold up to Dn= 740 cm − 1. This pro-
portionality is much better than that suggested by
Huggins and Pimentel (Dn1/2 = 0.72Dn +2.5
cm − 1) [2]. However, for different bases it is far
from being exact [66,67] and can be thought of
only as an approximate relationship between Dn1/2
and Dn. The ratios (Dn1/2/Dn) change from 0.35
(hexamethapol) to 1.1 to 1.4 (oxirane, carbonyl
compounds, nitromethan) [65,66]. One can follow
with the frequency shift more easily and, possibly,
twice as accurately, than with the intensities the
influence of different environments (solvents) on a
specified H-bonded complex with a simple band
contour. Thus, this influence was systematized in
the work of Allerhand and Schleyer [68] and in its
continuations [14,69].
7.4. Fermi-resonance
Fermi-resonance, being inevitable for suffi-
ciently strong HBs [70], progressively increases the
errors of Dn. This only adds to the complexity of
a resonance (n, 2g) following a weaker one, (n, 2d)
[71], forming together the trio of the bands ‘A, B,
C’ of Hadzi. The process continues with the for-
mation of the bands ‘D, E’ in the range of the
skeletal vibrations of the partners (see Fig. 2).
These disturbances of the shifted strong ns-
bands completely obviate such advantages as sim-
plicity and rapidity of Dn shift measurements (as
for the HBs of medium strength). The determina-
tion of the center of gravity (a first moment) of a
complicated ns-band is not much simpler than the
measurement of its area (zeroth moment) and is
not subject to smaller errors, but possibly to even
 A.V. Iogansen / Spectrochimica Acta Part A 55 (1999) 1585–1612
bigger ones. With modern computerized instru-
mentation both measurements can be made
equally simply and fast. Thus the preference by
chemists of the shift Dn over the intensification
DA 1/2, is in our view due to an outdated tradition,
which the above discussed advantages of the DA 1/2
rule must overcome.
8. Conclusion
It was simpler to discover Proportionality 5 than
to understand its nature. Intuition suggested the
rule as a natural correlation of HB properties, but
the universality and accuracy of Rule 5 turn out,
beyond expectation, to be much like an exact
functional dependence. This quasi-functional de-
pendence of the effective charge and energy of the
HB presents an intriguing enigma. The author is
not a theoretician and cannot reveal the underlying
mechanism of the rule nor substantiate it from
more general concepts. The only alternative is that
this review will attract more attention to the
subject, so that some theoretician will explain
Proportionality 5, possibly in a manner as simple
as the relation itself.
Acknowledgements
The author would like to express his apprecia-
tion to Dr Rozenberg for initiating the writing of
this review and translating it from the Russian, and
to Professor Marcus for editing the translation. He
is also very grateful to Drs L.M Epstein and L.A.
Leites, of the A.N. Nesmeyanov Institute of Orga-
noelement Compounds of the Russian Academy of
Sciences (Moscow) for valuable comments.
References
[1] A.V. Iogansen, in: N.D. Sokolov (Ed.), Vodorodnaya
Svyaz (The Hydrogen Bond), Izd. Nauka, Moscow,
1981, pp. 112–155.
[2] G. Pimentel, A.L. McClellan, L. Pauling (Ed.), The
Hydrogen Bond, San Francisco, London, 1960, Russian
translation: Mir, Moscow, 1964, pp. 65–125, pp. 168 –
193.
1609
[3] E.D. Becker, Spectrochim. Acta 17 (1961) 436.
[4] A.V. Iogansen, G.A. Kurkchi, Opt. Spectr. (USSR) 13
(1962) 480.
[5] A.V. Iogansen, Dokl. Akad. Nauk. SSSR. 164 (1965)
610.
[6] A.V. Iogansen, B.V. Rassadin, J. Appl. Spectrosc.
(USSR) 6 (1967) 492.
[7] B.V. Rassadin, A.V. Iogansen, J. Appl. Spectrosc.
(USSR) 10 (1969) 524 Correction.
[8] B.V. Rassadin, A.V. Iogansen, J. Appl. Spectrosc.
(USSR) 10 (1969) 290.
[9] E.M. Arnett, L. Joris, E. Mitchell, et al., J. Am. Chem.
Soc. 92 (1970) 2365.
[10] A.V. Iogansen, B.V. Rassadin, N.P. Sorokina, J. Appl.
Spectrosc. (USSR) 32 (1980) 1089.
[11] C.J. Creswell, G.M. Barrow, Spectrochim. Acta. 22
(1966) 839.
[12] L. Andrews, R.T. Arlinghaus, G.L. Jonson, J. Chem.
Phys. 78 (1983) 63.
[13] A.V. Iogansen, Dokl. Akad. Nauk. SSSR. 184 (1969)
1350.
[14] L.M. Epstein, A.V. Iogansen, Usp. Khim. 59 (1990) 229.
[15] D.N. Schepkin, Opt. Spectr. (USSR) 19 (1965) 709.
[16] A.V. Iogansen, E.V. Brown, Opt. Spectr. USSR. 20
(1966) 42.
[17] V.P. Baeva, A.V. Iogansen, G.A. Kurkchi, N.M. Rodi-
onova, O.P. Jablonsky, J. Appl. Spectr. (USSR) 22
(1975) 683.
[18] M.G. Emerson, D.F. Eggers, J. Chem. Phys. 37 (1962)
251.
[19] J.E. Lowder, L.A. Kennedy, K.G. Subzmann, S.S. Pen-
ner, J. Quant. Spectr. Radiat. Transfer. 10 (1970) 17.
[20] D.L. Powell, R. West, Spectrochim. Acta. 20 (1964) 983.
[21] R. West, D.L. Powell, M.K.T. Lee, L.S. Whatley, J. Am.
Chem. Soc. 86 (1964) 3227.
[22] R.C. Lord, Th.J. Porro, Z. Electrochem. 64 (1960) 672.
[23] M. Tsuboi, Bull. Chem. Soc. Jpn. 22 (1949) 215.
[24] V.E. Borisenko, G.J. Blinkova, L.L. Osipova, J.A. Zav-
jalova, J. Mol. Liq. 70 (1996) 31.
[25] S.S. Mitra, J. Chem. Phys. 36 (1962) 3286.
[26] J. Lascombe, J. Devaure, M.L. Josien, J. Chim. Phys. 61
(1964) 1271.
[27] H. Kleeberg, C. Eisenberg, T. Zinn, J. Mol. Struct. 240
(1990) 175.
[28] A.V. Iogansen, G.A. Kurkchi, O.V. Levina, Gas Chro-
matography 1966, Inst. Petrol, London, 1967, pp. 35–
46.
[29] G.A. Kurkchi, A.V. Iogansen, Zh. Fiz. Khim. 41 (1967)
158, 583.
[30] E.M. Arnett, T.S. Murthy, P. Schleyer, L. Joris, J. Am.
Chem. Soc. 89 (1967) 5955.
[31] G.A. Kurkchi, A.V. Iogansen, Dokl. Akad. Nauk.
SSSR. 145 (1962) 1085.
[32] A.V. Iogansen, G.A. Kurkchi, Phys. Chem. Appl. of
Gas-Liquid Chromatography, Khimiya, Moscow, 1973,
pp. 122 – 186 in Russian.
1610 A.V. Iogansen / Spectrochimica Acta Part A 55 (1999) 1585–1612
[33] A.V. Iogansen, The intensities of IR spectra and hy-
drogen bonds, Doctor of Science Dissertation, Moscow
State University, Moscow, 1969.
[34] A.V. Iogansen, G.A. Kurkchi, B.V. Rassadin, J. Appl.
Spectr. USSR. 11 (1969) 1054.
[35] E.V. Brown, Opt. Spectr. (USSR), Supplement. 3
(1967) 267.
[36] E.S. Shubina, N.V. Belkova, A.N. Krylov, E.V.
Voronsov, L.M. Epstein, D.G. Gusov, M. Nieder-
mann, H. Berke, J. Am. Chem. Soc. 118 (1996) 1105.
[37] E.S. Shubina, N.V. Belkova, L.M. Epstein, J.
Organomet. Chem. 536 (1997) 17.
[38] L.P. Kuhn, R.A. Wires, J. Am. Chem. Soc. 86 (1964)
2161.
[39] A.V. Iogansen, M. Rozenberg, Opt. Spectr. (USSR) 44
(1978) 87.
[40] S.E. Odinokov, A.A. Mashkovsky, V.P. Glazunov,
A.V. Iogansen, Spectrochim. Acta. A32 (1976) 1355.
[41] S.E. Odinokov, Doctor of Science Dissertation,
Moscow State University, Moscow, 1983.
[42] G.A. Kurkchi, J. Appl. Spectr. USSR. 6 (1967) 829.
[43] M.S. Nozari, R.S. Drago, J. Am. Chem. Soc. 92
(1970) 7086.
[44] A.V. Iogansen, G.A. Kurkchi, V.M. Furman, V.P.
Glazonov, S.E. Odinokov, J. Appl. Spectr. USSR. 33
(1980) 460.
[45] R.M. Badger, S.H. Bauer, J. Chem. Phys. 5 (1937)
839.
[46] A.V. Iogansen, Teor. Exp. Khim. 7 (1971) 302, 312.
[47] N.D. Sokolov, J. Mendeleev. Chem. Soc. (USSR) 17
(1972) 299.
[48] H. Ratajczak, W.J. Orwill-Thomas, C.N.R. Rao,
Chem. Phys. 17 (1976) 197.
[49] I.S. Perelygin, J. Appl. Spectr. (USSR) 26 (1977) 718.
[50] A.A. Stolov, M.D. Borisover, B.N. Solomonov, J.
Phys. Org. Chem. 9 (1996) 241.
[51] A.A. Stolov, M.D. Borisover, B.N. Solomonov, D.I.
Kamalova, S.V. Isosimova, L.S. Pominov, Zh. Fiz.
Khim. 67 (1993) 2341.
[52] A.V. Iogansen, G.A. Kurkchi, O.V. Levina, J. Appl.
Spectr. (USSR) 18 (1973) 676.
[53] N.P. Resaev, K. Szczepaniak, Opt. Spectr. (USSR) 16
(1964) 43.
[54] A.V. Iogansen, B.V. Rassadin, J. Appl. Spectr.
(USSR) 11 (1969) 828.
[55] S.E. Odinokov, A.V. Iogansen, A.K. Dzizenko, J.
Appl. Spectr. (USSR) 14 (1971) 418.
[56] L.J. Bellamy, H.E. Hallam, R.L. Williams, Trans.
Faraday. Soc. 54 (1958) 1120.
[57] A.V. Iogansen, G.A. Kurkchi, V.M. Furman, J. Appl.
Spectr. (USSR) 21 (1974) 1036.
[58] D.H. Rank, R.S. Rao, T.A. Wiggins, J. Chem. Phys.
37 (1962) 2511.
[59] D.H. Rank, P. Sitaram, W.A. Glickman, T.A. Wig-
gins, J. Chem. Phys. 39 (1963) 2673.
[60] G.T. Fraser, A.S. Pine, J. Chem. Phys. 85 (1986) 2502.
[61] R.K. Thomas, Proc. Roy. Soc., London. A325 (1971)
133.
[62] R.K. Thomas, Proc. Roy. Soc., London. A344 (1975)
579.
[63] A.V. Iogansen, M. Rozenberg, J. Struct. Chem.
(USSR) 30 (1989) 92.
[64] M. Rozenberg, A. Loewenschuss, Y. Marcus, Spec-
trochim. Acta. A53 (1997) 1969.
[65] A.V. Iogansen, Izv. Akad. Nauk. SSSR., Ser. Fiz. 53
(1989) 1741.
[66] A.V. Iogansen, Opt. Spectr. (USSR) 63 (1987) 1186.
[67] A.V. Iogansen, B.V. Rassadin, N.P. Sorokina, Theor.
Exp. Chem. 24 (1988) 461.
[68] A. Allerhand, P. Schleyer, J. Am. Chem. Soc. 85
(1963) 371.
[69] A.V. Iogansen, Dokl. Akad. Nauk. SSSR. 297 (1987)
1151.
[70] A.V. Iogansen, Opt. Spectr. (USSR), Supplement. 3
(1967) 228.
[71] S.E. Odinokov, A.V. Iogansen, Spectrochim. Acta.
A28 (1972) 2343.
[72] D. Epley, R.S. Drago, J. Am. Chem. Soc. 89 (1967)
5770.
[73] S. Singh, C.N.R. Rao, Can. J. Chem. 44 (1966) 2611.
[74] L. Bellon, Compt. Rend. 254 (1962) 3346.
[75] M.C.S. Lopes, H.W. Thompson, Spectrochim. Acta.
A24 (1968) 1367.
[76] H. Fritzsche, Ber. Bunsenges. Physik. Chem. 68 (1964)
459.
[77] R.S. Drago, B. Wayland, R.L. Carlson, J. Am. Chem.
Soc. 85 (1963) 3125.
[78] M.D. Joesten, R.S. Drago, J. Am. Chem. Soc. 84
(1962) 3817.
[79] Z. Yoshida, N. Ishibe, Spectrochim. Acta. A24 (1968)
893.
[80] L. Lamberts, J. Chem. Phys. 62 (1965) 1404.
[81] J.W. Boettoher, R.S. Drago, J. Phys. Chem. 78 (1974)
429.
[82] M. Kirszenbaum, J. Corset, M.L. Josien, J. Phys.
Chem. 75 (1971) 1327.
[83] S.D. Christian, T.L. Stevens, J. Phys. Chem. 76 (1972)
2039.
[84] I.S. Perelygin, A.M. Aphanas’eva, J. Appl. Spectr.
(USSR) 19 (1973) 500.
[85] D. Jaffe, Spectrochim. Acta. 43A (1987) 1393.
[86] J. Venograd, R.A. Spurr, J. Am. Chem. Soc. 79 (1957)
5844.
[87] A.V. Iogansen, G.A. Kurkchi, V.M. Furman, V.P.
Glazunov, S.E. Odinokov, J. Appl. Spectr. USSR. 33
(1980) 302.
[88] L.K. Khayretdinova, I.C. Perelygin, Opt. Spectr.
(USSR) 26 (1969) 62.
[89] A.W. Baker, H.O. Kerlinger, A.T. Shulgin, Spec-
trochim. Acta. 20 (1964) 1467.
[90] P.J. Stone, H.W. Thompson, Spectrochim. Acta. 10
(1957) 17.
 A.V. Iogansen / Spectrochimica Acta Part A 55 (1999) 1585–1612
[91] T.D. Flynn, R.L. Werner, B.M. Graham, Aust. J.
Chem. 12 (1959) 575.
[92] S.E. Odinokov, A.A. Mashkovsky, Z.A. Tarankova, J.
Appl. Spectr. (USSR) 37 (1982) 403.
[93] L.A. Dement’eva, G.A. Kurkchi, J. Appl. Spectr.
(USSR) 16 (1972) 482.
[94] A.A. Mashkovsky, V.P. Glasunov, S.E. Odinokov, J.
Appl. Spectr. (USSR) 20 (1974) 852.
[95] H.H. Perkampus, F.M.A. Kerim, Spectrochim. Acta.
A24 (1968) 2071.
[96] A.R.H. Cole, L.H. Little, A.J. Michell, Spectrochim.
Acta. A28 (1965) 1169.
[97] G.A. Kurkchi, A.V. Iogansen, Zh. Fiz. Khim. 65
(1991) 654.
[98] A.V. Iogansen, G.A. Kurkchi, B.V. Rassadin, J. Appl.
Spectr. (USSR) 11 (1969) 1054.
[99] R.A. Russell, H.W. Thompson, J. Chem. Soc. (1955)
479.
[100] P.J. Krueger, D.W. Smith, Can. J. Chem. 45 (1967)
1605.
[101] S. Detony, D. Hadzi, R. Smerkalj, et al., J. Chem. Soc.
A (1970) 2851.
[102] L.A. Leites, L.E. Vinogradova, N.A. Ogorodnikova,
L.I. Zakharova, J. Appl. Spectr. (USSR) 16 (1972) 488.
[103] G.A. Kurkchi, A.V. Iogansen, Opt. Spectr. (USSR),
Supplement. 3 (1967) 126.
[104] J. Morcillo, J.F. Biarge, J.M.V. Heredia, J. Mol.
Struct. 3 (1969) 77.
[105] C.C. Robinson, S.A. Tare, H.W. Thompson, Proc.
Roy. Soc. A269 (1962) 492.
[106] J. Rossi, A. Levi, C.H. Hausler, Can. J. Chem. 46
(1968) 2103.
[107] K.U. Ingold, Can. J. Chem. 40 (1962) 111.
[108] L.G. Zelenskaya, A.V. Iogansen, J. Appl. Spectr.
(USSR) 16 (1972) 108.
[109] K.U. Ingold, D.R. Taylor, Can. J. Chem. 39 (1961)
481.
[110] V.P. Glasunov, A.A. Mashkovsky, S.E. Odinokov, J.
Appl. Spectr. (USSR) 22 (1974) 696.
[111] E.N. Gurianova, I.P. Goldshtein, T.I. Perepelkova,
Usp. Khim. 45 (1976) 1568.
[112] V.P. Glasunov, A.A. Mashkovsky, S.E. Odinokov, J.
Appl. Spectr. (USSR) 23 (1975) 469.
[113] S.E. Odinokov, A.V. Iogansen, J. Appl. Spectr.
(USSR) 14 (1971) 1076.
[114] A.D.H. Clague, H.J. Bernstein, Spectrochim. Acta. A25
(1969) 593.
[115] A.L. Smoljansky, Opt. Spectr. (USSR) 13 (1962) 475.
[116] G. Allen, J.G. Watkinson, K.H. Webb, Spectrochim.
Acta. 22 (1966) 807.
[117] S.E. Odinokov, A.A. Mashkovsky, Z.A. Tarankova, J.
Appl. Spectr. (USSR) 37 (1982) 403.
[118] A.A. Mashkovsky, A.A. Nabiullin, S.E. Odinokov, J.
Appl. Spectr. (USSR) 37 (1982) 623.
[119] J.M. Spencer, R.A. Heckman, R.S. Harner, S.L.
Shoop, K.S. Robertson, J. Phys. Chem. 77 (1973)
3103.
1611
[120] Z. Yoshida, N. Ishibe, Bull. Chem. Soc. Jpn. 42 (1969)
325.
[121] G.M. Barrow, J. Phys. Chem. 59 (1955) 1129.
[122] E. Hirano, K. Kojcma, Bull. Chem. Soc. Jpn. 39 (1966)
1216.
[123] J. Brandmuller, K. Seevogel, Spectrochim. Acta. 20
(1964) 453.
[124] H.H. Percampus, F.M.A. Kerim, Spectrochim. Acta.
A24 (1968) 2071.
[125] D. Neerink, L. Lamberts, Bull. Soc. Chim. Belge. 75
(1968) 473.
[126] J. Motoyama, C.H. Jarboe, J. Chem. Phys. 71 (1967)
2723.
[127] T.J.V. Findlay, A.D. Kidman, Aust. J. Chem. 18
(1965) 521.
[128] S. Murakami, R. Fujihiro, Bull. Chem. Soc. Jpn. 39
(1966) 722.
[129] J.N. Spencer, J.E. Gleim, C.H.H. Plevins, et al., J.
Phys. Chem. 83 (1979) 2615.
[130] N. Marriagi, A. Cornu, R. Rinaldi, Ann. Phys. Biol.
Med. 7 (1973) 576.
[131] T.M. Barakat, M.J. Nelson, S.M. Nelson, A.D.E.
Pullin, Trans. Farad. Soc. 62 (1966) 2674.
[132] T.M. Barakat, M.J. Nelson, S.M. Nelson, A.D.E.
Pullin, Trans. Farad. Soc. 65 (1969) 41.
[133] L.A. Dement’yeva, A.V. Iogansen, G.A. Kurkchi, Opt.
Spectr. (USSR) 29 (1970) 868.
[134] M. Laznewski, J. Mokrzan, Z. Phys. Chem. 235 (1967)
260.
[135] H.C. Flett, J. Soc. Dyers. Colour. 68 (1952) 59.
[136] K.B. Whetsel, J.H. Lady, J. Phys. Chem. 69 (1965)
1596.
[137] L. Abello, G. Pannetier, Bull. Soc. Chim. France
(1967) 3756.
[138] L.E. Vinogradova, L.A. Leites, J. Appl. Spectr.
(USSR) 23 (1975) 260.
[139] G.A. Kurkchi, A.V. Iogansen, Opt. Spectr. (USSR),
Supplement. 3 (1967) 128.
[140] G.A. Kurkchi, A.V. Iogansen, Russ. J. Phys. Chem. 41
(1967) 563.
[141] M. Tamres, S. Searles, E.M. Leighly, J. Am. Chem.
Soc. 76 (1954) 3983.
[142] S. Searles, M. Tamres, J. Am. Chem. Soc. 73 (1951)
3704.
[143] K.W. Morkom, D.N. Travers, Trans. Farad. Soc. 61
(1965) 230.
[144] A.V. Iogansen, G.A. Kurkchi, O.V. Levina, Zh. Fiz.
Khim. 43 (1969) 2910 – 2915.
[145] H.C. Brown, J.J. Melchiore, J. Am. Chem. Soc. 87
(1967) 2619.
[146] J. David, H. Hallam, Trans. Farad. Soc. 65 (1969)
2883.
[147] P.J. Puranik, V. Kumar, Proc. Ind. Acad. Aci. 58A
(1963) 29.
[148] R. Mathur, E.D. Becker, R.B. Bradley, N.C. Li, J.
Phys. Chem. 67 (1963) 2190.
1612 A.V. Iogansen / Spectrochimica Acta Part A 55 (1999) 1585–1612

[149] W.S. Benedict, N. Gailar, E.K. Plyler, J. Chem. Phys.
24 (1956) 1139.
[150] J.E. Lowder, J. Quant, Spectr. Rad. Transf. 11 (1971)
153.
[151] H.R. Wyss, M. Falk, Can. J. Chem. 48 (1970) 607.
[152] Spravochnik Khimika, 3rd ed., vol. I, 1971, Khimiya,
Leningrad (St. Petersburg, in Russian).
[153] M. Tamres, J. Am. Chem. Soc. 74 (1952) 3375.
[154] M. Tamres, S. Searles, J. Am. Chem. Soc. 81 (1959)
2100.