N o r m a n Friedman
Harford Community College
Eel Air. Maryland 21014
I Hydrogen Bonding and Heat of Solution
A typical experiment demonstrating heat of solution1 in-
volves mixing e q u a l volumes of water and e t h y l alcohol and
noting t h e increase i n t e m p e r a t u r e of the solution. A modifi-
cation of t h i s experiment i s presented that clearly illustrates
the role of hydrogen bond formation and its effect upon the
heat of solution. T h e heat of solution produced b y mixing two
hvdroeen bonded liquids, i.e. C2H50H-H20,
can b e considered
to originate from t h e difference between an energy consuming
process a n d a n energy releasing process, illustrated in eqn.
H-bond breaking H-bond formation
energy consuming energy releasing
(1)
The exothermic heat uf ~olutionfor miring an alcohol and water re-
sults from the energy releasing pv- being peater than the energy
consuming process.
Dimethyl sulfoxide (DMSO) and dimethyl farmamide (DMF)2 are
water-soluble aprotic substances, neither being hydrogen bond donors
but are hydrogen bond acceptors. If the hydrogen bonded alcohol in
eqn. (1)is replaced by either DMSO or DMF, i t is not unreasonable
to expect that the heat of solution should be more exothermic since
the energy consuming process does not require H-bond breaking
between molecules of the aprotic solvent whereas these solvents do
participate in H-bond formation with water acting as the donor
molecule. This is strikingly confirmed by observing the following
temperature changes upon mixing equal volumes (25 ml each) of:
CZHsOH-H20,AT = +I0C; DMF-H1O, AT = +16OC; DMSO-H?O,
-.
A T = +?R0C~
. -...
An additional system of interest is formamide-water which exhibits
a temperature decrease of -2%. Formamide can act as bath a by-
dro& bond donor and acceptor and the endothermic nature of this
&tion orocess arises from the energy .. consuming process being
~ ~
greater than the energy releasing process. Apparently the strength
of the intermolecular hydrogen bonding in pure iormamide ispeater
than the intermolecular hydrogen bonding in formamide.water.
The dramatic nature of these heat effects can be demonstrated by
using the DMSO-HPOsystem as the heat source in place of concen-
trated HzSO-Hz0 in an ether tube a ~ p a r a t u s . ~
The above solvent systems are also suitable for a freshman level
laboratory experiment and, if desired, AH (rather than AT) iseasily
248 1 Journal 01Chemical Education
calculated with the inclusion of specific heat data and the heat ca-
pacity of the calorimeter.
Experlrnental
The calorimeter used is a standard student-type device consisting
of an aluminum cup and stirrer, a wooden or plastic cover, and a 0-
50°C thermometer with scale divisions of 0.2'C. A Stvrofoarn CUD mav
~~ ~~~
also he used except w ~ r hDMF as it rapidly dissolv& the cup. kqudl
volumes of each solvent pair r25 or hO ml are convenient quantit~esl
should he used. Have all equrpment and materials at the same tem-
perature before mixing. After mixing, record the temperature a t 30
s intervals for 5 min with continual stirring of the solution. The
maximum temperature increase is obtained by plotting a time-tem-
perature curve and extrapolating to the time of mixing.
Calculations
The observed increase in temperature of the solution depends on
1)the weight of eaeh liquid, 2) their specific heats, and 3) the beat
absorbed by the calorimeter. In this experiment, the heat capacity
of the calorimeter used was 7.0 ealloC. An illustrative calculation of
A H for the DMSO-H20 system follows, where AT = + 2 3 T
h e a t absorbed b v water
h e a t absorbed heat absorbed
b y DMSO by calorimeter
1.2 Kcal 3.3 Kcal
AH- -
2 7 g Or mole
-
Discussion
In this experiment entropy effects are assumed t o be of similar
magnitudeand small (compared to AH) so that noappreciable error
is introduced when comparing values of AH or AT.
It is recommended that the calorimetric studies he performed using
equal volumes of substances as described and not equal moles. I t is
observed in the latter case that the temperature increase is some
3-5OC less than reported, even though larger volumes of substances
are used. Correspondingly, the calculated values of AH are less than
expected. These "inconsistencies" have been attributed to a n in-
complete reaction which is avoided when water is in excess and DMSO
or DMF is the limiting reagent.
Alyea, H. N., "TOPS inGeneralChemistry," 3rd Ed., J. CHEM.
EDUC., Easton, PA, 1967, p. 113.
CAUTION: Avoid contact of DMSO and DMF with skin, or the
breathing of rts vapors!
'Alyea. H. N , and Dutton, F H., "Tested i)emonstrations in
Chemisrry,".l.C'HEM. EDIIC., Easton, PA, 1965.p. 17 k7.2.