H. A. Neidig and R. T.
Yingling
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Thermodynamics of the Ionization of
Lebanon Valley College
Annville, Pennsylvania Acetic and Chloroacetic Acids
This research-centered investigation of
aseries of acid-base equilibria involves the use of some
of the important basic equations and concepts of ther-
modynamics. Since this study correlates several areas
of first-year chemistry, it is ideally suited for use as one
of the concluding laboratory investigations in a first-
year course. A basic thermodynamic study of the
acetic acid-water, chloroacetic acid-water, dichloro-
acetic acid-water, and trichloroacetic-water systems
has been described,1 and can be modified to meet the
requirements of a first-year college chemistry course.
The ionization of acetic acid, chloroacetic acid,
dichloroacetic acid, and trichloroacetic acid in aqueous
solutions can be represented by the equilibria:
HOA(aq) =: OA“(aq) + H+(aq)
[OA-][H+)
[HOA]
The students are asked to determine the effect of the
structure of the acid on the equilibria and to discuss
the observed effects in terms of standard free energy,
enthalpy, and entropy changes.
Data for calculating the equilibrium constants are
obtained by titrating an aliquot of each of the acids
with a sodium hydroxide solution. Tire pH of the
solution of the acid is measured with a pH meter after
the addition of each portion of titrant. Each of the
equilibrium constants is then calculated from a graph of
pH versus volume of sodium hydroxide added to the
acid solution using the half-titration method.2 The
equilibrium constants are used to calculate the standard
free energy of ionization (A(?i°) of each of the four acids:
AGi° = -RT In K
The second phase of the investigation involves the
calculation of the enthalpies of neutralization of each of
the four acids from experimental data. Time-tempera-
ture data are obtained on stoichiometric quantities of
TOO M sodium hydroxide and 1.00 M solutions of each
of the acids (0.50 M sodium hydroxide and 0.50 M
dichloroacetic acid are used because of the limited sol-
ubility of dichloroacetic acid in water) every 30 sec for a
period of about 5 min. The sodium, hydroxide solution
and the acid solution are mixed together in a Ther-
mokup which serves as a calorimeter, and time-tempera-
ture data are collected for the reaction mixture for a 10
min post-mixing interval. Thermometers graduated
Teacher’s Guide, "Investigating Chemical Systems,” Webster
1
Division, McGraw-Hill Book Co., Inc., New York, 1963, p. 32-1.
2
IIeilley, C. N., and Sawyer, D. T., "Experiments for Instru-
mental Methods," McGraw-Hill Book, Co., Inc., New York, 1961,
p. 23.
484 / Journal of Chemical Education
in 0.1 °C units are used for all temperature measure-
ments. The temperature changes for the neutralization
reactions are found from a plot of the time-temperature
data using the extrapolation method. The heat
transfer (Q) and the enthalpy of neutralization (AHN)
are calculated. For the purposes of this investigation,
the enthalpies of dilution of the reactants and the
products are assumed to be negligible or to cancel.
On this basis, it is assumed that the experimentally
determined enthalpy of neutralization is equal to the
standard enthalpy of neutralization (aHn°)-
Since the enthalpy change for a reaction depends only
upon the initial and final states of the system, the
neutralization of each of the acid solutions can be
divided into two steps. First, any molecules of undis-
sociated acid which exist in the solution of the acid at
the time of mixing become dissociated. Second, the
hydrogen ions resulting from the dissociation of the
acid are neutralized by the hydroxide ions. The
standard enthalpy of neutralization of hydrogen ions
by hydroxide ions can be obtained experimentally by
studying the neutralization of hydrochloric acid with
sodium hydroxide at different concentrations. For
this investigation a literature value of —13.34 kcal/
mole2 was used as the standard enthalpy of neutraliza-
tion of hydrogen ions. The standard enthalpy of
ionization for each of the acids can be calculated using
Hess’ Law. If the assumption is made that none of the
acid is ionized before neutralization, the standard
enthalpy of ionization is given by:
AHi°' =
AHy° + 13.34 keal/mole
However, the fraction of each acid (a:) that was not.
ionized before neutralization can be calculated from the
The standard enthalpy of
equilibrium constant.
ionization (Affi0) calculated on the basis of the actual
number of molecules of acid which dissociated at the
time of neutralization is given by:
Since the standard free energy of ionization has been
calculated for each of the acids and the standard
enthalpy of ionization has been calculated, the standard
entropy of ionization of each of the acids can be cal-
culated :
AGi° =
AHi° -
TASi°
Representative student data for AG'i°, AHi°, and
3
Hale, J. D., Izatt, R. M., and Christensen, J. J., J. Phys.
Chem., 67,2605 (1963).
TASi° obtained for each of the acids are given in the in the aqueous solutions of the acids as a result of the
table. These thermodynamic data may be used to presence of carbon-to-chlorine bonds in the substituted
discuss changes in bonding and in structure which occur acetic acids.

AGr°, AHi°, and TASl0 for the Ionization of Acetic and Chloroacetic Acids
1.00.1/ l.OOM 0.50M 1.00M
Acetic Chloroacetic Dichloroacetic Trichloroacetic
acid acid acid acid
K .2 X 10“ .6 X 10- 3 6 X 10“ .0 X 10-
% Ionized 0,47 3.9 24 36
AGi° (kcal/mole) 6.36 3.82 1.96 0.94
A//n° (kcal/mole) -13.9 -15.6 -15.4 -15.4
AHi°'" (kcal/mole) -0.6 -2.3 -2.1 -2.1
AHi°h (kcal/mole) -0.6 -2.4 -2.8 -3.3
TaSi0 (kcal/mole) -7.0 -4.8 -4.2
®
Based on the assumption that none of the acid was dissociated before neutralization.
6
Based on the calculated fraction of acid that was not dissociated before neutralization.

Volume 42, Number 9, September 7 965 / 485