Enthalpies of solution of naphthalene, N,N-dimethyl-1-naphthylamine,

and 1,s-bis(dimethy1amino)naphthalene in 16 organic solvents

DANIELFIGEYS,'MAEGORZATA
KOSCHMIDDER,~ L.
AND ROBERT BE NO IT^
De'partement de chimie, Universite' de Montre'al, C.P. 6128, Succ. "A", Montre'al (Qut.), Canada H3C 357
Received May 8, 199l4

DANIEL FIGEYS, MAEGORZATA KOSCHMIDDER, and ROBERT L. BENOIT. Can. J. Chem. 70, 1586 (1992).
The enthalpies of solution of naphthalene, N,N-dimethyl-1-naphthylamine,and 1,8-bis(dimethy1amino)naphthalene
(proton sponge) were determined at 298.15 K in 16 organic solvents (n-hexane, cyclohexane, carbon tetrachloride,
chloroform, 1,2-dichloroethane, benzene, chlorobenzene, dimethyl sulfoxide, N,N-dimethylformamide, ethyl acetate,
1,4-dioxane, anisole, nitrobenzene, benzonitrile, methanol, ethanol). Additional determinations were made with ben-
zene. Useful linear relationships are observed between the molar enthalpies of solution of the four compounds in the
solvents. The molar enthalpies of solution were correlated with the solvatochromic paramete= of the solvents. The presence
of N(CH3), groups on naphthalene does not significantly contribute to the solute-solvent interactions.
Can. J. Chem. Downloaded from cdnsciencepub.com by 121.52.158.246 on 02/12/21

DANIEL FIGEYS, MAEGORZATA KOSCHMIDDER et ROBERT L. BENOIT. Can. J. Chem. 70, 1586 (1992).
OpCrant i 298.15 K, on a determine les enthalpies de solution du naphtalkne, de la N,N-dimkthyl-1-naphtylamineet
du 1,8-bis(dim6thylamino)naphtalkne (Cponge i protons) dans 16 solvants organiques (n-hexane, cyclohexane, tktrachlorure
de carbone, chloroforme, 1,2-dichloroethane, benzkne, chlorobenzkne, dimCthylsulfoxyde, N,N-dimkthylformamide,
acetate d'kthyle, 1,4-dioxane, anisole, nitrobenzkne, benzonitrile, mCthanol et ethanol). On a effectut des mesures sup-
plkmentaires dans le benzkne. On a observe des relations 1inCaires utiles entre les enthalpies molaires de solution des
quatre composCs dans les solvants. I1 existe une correlation entre les enthalpies molaires et les paramktres solvatochro-
miques des solvants. La presence de groupes N(CH3), sur le naphtalkne ne contribue pas d'une f a ~ o nsignificative aux
interactions solutCs-solvants.
[Traduit par la rkdaction]

Introduction thylamine (Aldrich, 99%) was used as received and naphthalene

For personal use only.

(Aldrich, 99%) was recrystallized from ethanol. Benzene

The unusual structure of the aromatic diamine 1.8-bis-
(dirnethy1amino)naphthalene (proton sponge, PS) confers to
its conjugated cation, PSH', a nonspecific solvation. This
property has been used to formulate an extrathermodynamic
assumption leading to valuable single-ion enthalpies of
transfer between solvents (1). To assess the validity of the
assumption, we had to ascertain the absence of specific in-
teractibns between PS as a solute and the solvents, such as
H-bonding between protogenic solvents and the -NMe2 group
of PS. We therefore determined the standard molar en-
thalpy of solution of PS in a wide range of organic solvents.
We present here the corresponding calorimetric data and their
analysis in terms of solute-solvent interactions. To this-ef-
fect we looked for correlations between the molar enthalpy
of solution of PS and the solvatochromic parameters of the
solvents (2). We also considered another approach related
to that of Fuchs and Rodewald (3), who studied the differ-
ence between the molar enthalpy of solution of substituted
aromatic solutes and that of the parent compound. Thus we
also determined the standard molar enthalpy of solution of
N,N-dimethyl- 1-naphthylamine (DMNA) and that of naph-
thalene (NA) in the same series of solvents. The solvents used
were selected so that their solvatoc~rom~c would
cover a wide of values. ~h~ poor solubility of NA and
p s , however, imposed some restrictions on our choice of
solvents.
Experimental
Proton sponge (Aldrich, 99%) was purified according to the
procedure of de Groat and Si*ema (4). N,N-Dimethyl-l-naph-
'present address: Department of Chemistry, University of
Alberta, Edmonton, Alta., Canada T6G 2G2.
'on leave from: Technical University, Gdarisk, Poland.
3 ~ u t h oto
r whom correspondence may be addressed.
4Revision received December 18, 1991.
(99.9% +), chlorobenzene (99.9%+), nitrobenzene (99%). ben-
zonitrile (99%), ethyl acetate (99.9%+), 1,2-dichloroethane
(99.8%), 1,4-dioxane (99.8%), anisol (99%), n-hexane (99% +),
and carbon tetrachloride (Spectrograde) were supplied by Aldrich.
Dimethyl sulfoxide (99.9%) was obtained from BDH, ethanol
(anhydrous) from Anachemia. N,N-Dimethylformamide (reagent
grade), cyclohexane (Spectrograde), and chloroform (spectro-
grade) were from ACP and methanol (spectrograde) from American
Chemicals. Chloroform was treated with 4A molecular sieves and
distilled.
The enthalpies of solution were measured at 298.15 2 0.01 K
with an LKB model 8721-1 isoperibol calorimeter as previously
described (1); the nu1 detector was connected to a digital-analog
circuit and a Zenith computer. The amounts of compounds dis-
solved in 0.100 dm3 of solvent were obtained from the weights of
the 0.001 dm3 reaction ampoules. Two different types of am-
poules were used, either a glass one whose neck was closed with
Parafilm for unreactive solvents, or a small Teflon cylinder tightly
closed with thin glass caps at both ends (5). The calorimetric mea-
surements were made at different final solute concentrations, 0.001-
0.02 mol dm-3.
Results and discussion
The molar enthalpies of solution were calculated from a
linear regression correlation of the heat change against sol-
ute concentration. The uncertainties quoted are the standard
deviations of the slopes. The enthalpy values obtained for
each of the compounds are taken to be equal to the infinite
dilution values A,,JI: because no concentration dependence
was observed in the low concentration range studied, 0.001-
0.02 mol dm-'. The standard molar enthal~iesof solution
at 298.15 K are listed in Table 1 for naphthalene, N,N-di-
methyl-l-naphth~lamine,and proton sponge. Our results for
the solution of NA in dimethylformamide and methanol are
in good agreement with previous values (3).
We note that the three sets of A,,JI: values for NA,
DMNA, and PS in Table 1 vary within a narrow range of
 FIGEYS ET AL. 1587

TABLE1. Standard molar enthalpies of solution of naphthalene, proton sponge, N,N-dimethyl-1-naphthyalmine,and benzene at
298.15 K

(NA) A s o t f J ~(PS) A,,~H; (DMNA,l) A,,,H; (Bz,~)

Solvent n.0 ( J 112 cm3/2)
ASOIH;

(kJ mol-I) (kl mol-I) (kl mol-I) (kl mol-I)

n-Hexane -0.08 14.9 21.2 + 0.2 18 2 1.5 4.94 + 0.09 3.3lbsC

Cyclohexane 0 16.8 22.3 + 0.4 21.4 + 0.2 6.3 + 0.1 3.81b
Carbon tetrachloride 0.28 17.6 18.6 + 0.5 16.3 + 0.3 1.11 + 0.07 0.54~
Chloroform 0.58 19.3 15.4 + 0.2 10.9 + 0.5 -4.4 2 0.1
1,2-Dichloroethane 0.81 20.3 18.1 + 0.2 17.6 + 0.5 1.14 + 0.06
Benzene 0.59 18.7 17.8 + 0.4 15.9 + 0.6 0.86 + 0.02 0
Chlorobenzene 0.71 19.8 17.7 + 0.2 14.1 + 0.5 -0.71 + 0.05 0.06 ? 0.02
Dimethylsulfoxide 1.OO 26.6 19.7 + 0.3 23.1 + 0.5 5.2 + 0.1
N,N-Dimethylformamide 0.88 24.1 16.3 + 0.3 19.2 + 0.3 1.14 + 0.01
Ethylacetate 0.55 18.2 17.0 ? 0.1 18.6 2 0.2 1.45 + 0.07
1,4-Dioxane 0.55 20.5 16.8 + 0.5 19.0 + 0.1 1.6 + 0.1
Anisole 0.73 19.7 16.7 ? 0.5 16.0 2 0.1 -0.08 + 0.05 0.16 + 0.02
Can. J. Chem. Downloaded from cdnsciencepub.com by 121.52.158.246 on 02/12/21

Nitrobenzene 1.01 22.6 18.6 + 0.2 18.2 + 0.1 1.14 ? 0.03 1.07 2 0.07
Benzonitrile 0.90 22.7 17.8 ? 0.4 16.3 + 0.1 0.00 ? 0.01" 0.15 + 0.01
Methanol 0.60 29.3 19.1 + 0.3 20.7 + 0.5 4.30 + 0.06
Ethanol 0.54 26.0 18.8 2 0.2 20.5 + 0.6 4.18 + 0.07
"Reference 2 .
bReference 7.'In n-heptane.
dEstimated error.

approximately 7 kJ mol-I (excluding the CHCI, values) in Line b:

spite of the widely different properties of the solvents as can
PI A,,P; (DMNA,l)
For personal use only.

be assessed from their solvatochromic parameters (2). The

solvents' parameters of interest for our set of solutes are: ti,, = (1.24 + 0.07) A,,,H; (NA) - (19 + 1.3)
the Hildebrand solubility parameter, II*, a measure of the
solvents dipolarity/polarizability, and a, the hydrogen-bond withN = 6, r = 0.994, s.d. = 0.22.
donor ability. The values of ti, and II* are listed in Table 1; The correlations between the molar enthalpies of solution
the values of a are 0 except for chloroform (0.44), metha- of PS and NA are not as good. We find
nol (0.93), and ethanol (0.83), and the values of ,a, (a po- Line a:
larizability correction) are l for the aromatic solvents, 0.5
[3] A,,,H (PS) = (1.2 k 0.2) A,,,H; (NA) - (5 2 4)
for the chloro solvents, and 0 for the other solvents. The
A,,,H; values for DMNA are consistently some 15-20 kJ withN = 9 , r = 0.866,s.d. = 1.5.
mol-' more exothermic than those for NA and PS. This is Line b:
because at 298.15 K DMNA is a liquid while NA and PS are
both solids. As a matter of fact, if we subtract the enthalpy [41 O, (PS)
AsOlH = (1.0 + 0.3) A,,,H (NA) + (2 2 5)
of fusion of NA (+ 18.0 kJ mol-I) (6), the calculated values with N = 6, r = 0.889, s.d. = 0.85.
of the enthalpy of solution of supercooled liquid NA in the Finally, for benzene we obtain
various solvents are now within a few kJ mol-' of the cor- Line a:
responding values for liquid DMNA.
[51 AS0,HO,(Bz,l)
Correlation between enthalpies of solution
The plot of the molar enthalpies of solution of DMNA in = (0.78 k 0.07) A,,,H; (NA) - (14 k 1)
the 16 solvents against those of NA in the same solvents
shows some interesting features. If we attempt to use all the with N = 9, r = 0.972, s.d. = 0.37.
These correlations are clearly of practical interest. For
data the correlation is rather poor (r = 0.85, s.d. = 1.5) but
example, for the solvent water, from a value of A,,,H;
if we divide the solvents into two groups we obtain two es-
(NA) = + 29.9 kJ mol-I (6) and eq. [4] we calculate
sentially parallel lines:
Line a:
+
A,,,H; (PS) = 32 kJ mol-I to be compared with the ex-
perimental 30 + 5 kJ mol-' (1). However, the significance
of these correlations is unclear since the two groups of sol-
[ 1I A,,,H; (DMNA, 1) vents do not form well-defined families. Furthermore, the
= (1.21 + 0.09) A,,,H; (NA) - (21 + 1.5) experimental uncertainties on the enthalpies do not account
for the scatter of the points.
with N = 9, r = 0.982, s.d. = 0.5, where N is the number Corrdations between enthalpies of solution and solvent
of solvents in the correlation; r denotes the correlation coef- parameters
ficient; s.d. is the standard deviation of the estimate. The nine The enthalpy of solvation of a solute, i.e., its transfer from
solvents include n-hexane and cyclohexane, and the aro- the gas phase to the solvent, can be taken to include a nurn-
matic and chlorosolvents (excluding CHCI,). For the re- ber of additive enthalpy contributions that correspond to the
maining six solvents we have creation of a cavity in the solvent, the solute-solvent dis-
 1588 CAN. J . CHEM. VOL. 70, 1992
persion and polar interactions, the structural changes pro-
duced by the solute in the solvent, and specific interactions,
such as H-bonding, between the solute and the solvent.
Clearly, isolating the different contributions will lead to a
better understanding of solute-solvent interactions and var-
ious approaches have been tried to solve the problem (7).
Recently, considerable success has been achieved in corre-
lating a large number of physicochemical properties and
reactivity parameters to solute and solvent properties through
linear relationships (2). We have applied multiple linear
regression analysis to correlate our molar enthalpies of so-
lution, and other derived enthalpies, to the solvatochromic
parameters of the solvents listed in Table 1.
We obtained for solid NA and PS, and liquid DMNA the
following equations where all the coefficients are statisti-
cally significant at the confidence level of 95% according to
Can. J. Chem. Downloaded from cdnsciencepub.com by 121.52.158.246 on 02/12/21
Student's t-test.
[6] A,,,H~(NA) = (1.28 + 0.05) 6,
where N = 16, R 2 = 0.9950, s.d. = 1.5.
A,,,HL (PS) = (1 .19 + 0.06) 6,
[7]
- (10 + 2) n* - (8 + 1) a
where N = 16, R 2 = 0.9946, s.d. = 1.5.
I the solvents permit us to estimate the respective contribu-
For personal use only.
1 where N = 15 (CHCl, excluded), R 2 = 0.847, s.d. = 1.3.
For benzene there is no satisfactory correlation since R 2
is only 0.65.
The coefficients of the parameters S,, n*, and a of the
equations make chemical sense in that the cavity term adds
a positive contribution to As0,HLwhile the expected nega-
tive contributions come from both polar interactions and
H-bond interactions between the solutes and the H-bond
donor solvents. Somewhat unexpectedly, the equations have
no constant term; when the multiple regression program was
run with a constant the R2 value dropped to -0.3. Using Si,
which may be preferable to 6, (7), also gave poorer corre-
lations. The equations do not include a term to account for
possible electron donor-acceptor (EDA) interactions of the
solutes with the chloro and aromatic solvents, in part be-
cause there is no simple way to account for such interac-
tions (8). At any rate the linear relationships between the
A,,,H~ values of naphthalene and those of PS and DMNA
would suggest that EDA interactions would only involve the
solute's ll electrons and not the nitrogen lone pair. It may
be that EDA interactions are accounted for, at least in part,
in the n* term. It is somewhat difficult to compare the val-
ues of the coefficients of the parameters for the three sol-
utes. For NA and PS, which are both solids and with similar
enthalpies of sublimation, the coefficients of 6, and a are
nearly the same while those of n* are somewhat different,
but there is a S,,, term that is significant for NA but not for
PS. If we omit S,,, from the NA correlation we obtain:
[9] A,,,H~(NA) = (1.28 + 0.07) 6,
This time the n* coefficients are the same within error for
NA and PS. The closeness of the a coefficients for NA and
PS would imply that H-bonding between the solvents and the
-NMe2 groups plays only a minor role, if any, and that n
electron - hydrogen bond interactions are more important.
TO obtain a comparable equation for solid DMNA we added
18 kJ mol-I, an estimated value of the molar enthalpy of fu-
sion of DMNA, to the values of A,,,H~(DMNA,l) and we
found
[ 101 A,,,H~(DMNA) = (1.40 + 0.05) 6,
where N = 15, R' = 0.996, s.d. = 1.5.
The coefficients of S,, n*, and a are now near those for
solid NA and PS. It is puzzling that eq. [lo] has no constant
term, particularly in view of the fact that current work on the
solution of pyridines leads to equations with constant terms
whose values are related to the physical state of pyridines,
whether gaseous, liquid, or solid. At any rate the terms in
eq. [6], [7], [9], and [lo] should be regarded as measuring
the differences between the solute-solvent interactions
formed and the solute-solute interactions disrupted (9).
Within these limitations the correlations between the molar
enthalpies of solution and the solvatochromic parameters of
tions of cavity, polar, and H-bonding terms. For example,
for naphthalene the positive cavity contribution would vary
between 20 and 40 kJ mol-' and would be counterbalanced
by the negative contributions of 0-10 kJ mol-' each for polar
and H-bonding terms. The correlations have also a good
predictive value. Thus for the solution of NA in the solvent
water, we calculate from the solvatochromic parameters and
eq. [6] A,,,HL = +34 kJ mol-I, to be compared with a
t 2 9 . 9 kJ mol-' experimental value (6). For the solution of
PS in pyridine we calculate + 19 kJ mol-' while a recent
experiment gave + 17.35 kJ mol-'.
We also looked at correlations between the enthalpy of
solvation (gas to solvent) and the solvatochromic parame-
ters of the solvents, but the standard deviations were too high
for good predictive value. Similarly, the correlations be-
tween the heats of transfer of the solutes (taking cyclohex-
ane as reference solvent) and the differences between the
solvatochromic parameters were not satisfactory. Taking
naphthalene as the parent compound for PS and correlating
the differenes between the heats of transfer of both solutes
(3) also lead to no meaningful results. Finally the compari-
son of correlation, eqs. [7], [9], between A S o I H(NA)
~ and
A,,,H~(PS), and the solvatochromic parameters on the one
hand, and the direct linear relation between A , , ~ H(PS) ~
and A,,,H~(NA), eqs. [3], [4], on the other hand shows that
these relations are not strictly compatible and this may
account for the fact that the linear relation between
A,,,H~(PS) and A,,,H~(NA) is only approximate.
Acknowledgements
A grant and a scholarship (D.F.) from the Natural Sci-
ences and Engineering Research Council of Canada are
gratefully acknowledged. The authors thank Professor M.
D'Amboise for his advice on the use of some statistical
methods.
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