Professional Documents
Culture Documents
Thermodynamics of The Ionization of
Thermodynamics of The Ionization of
This research-centered investigation of in O.l°C units are used for all temperature measure-
a series of acid-base equilibria involves the use of some ments. The temperature changes for the neutralization
of the important basic equations and concepts of tber- reactions are found from a plot of the time-temperature
r n o d y ~ ~ : i ~ ~Sillre
~ . r ~ .this
~ . stndy rorr14ntv. .:r\.ernl : ~ r w s data using the extrapolation method. The heat
of hr+vwr ~ ~ h r n ~" i,~i r riur vi~lrtillv
. .+nitt,~l
ior nsc 3s one transfer (Q) and the enthalpy of neutralization ( A H N )
of the concluding laboratory investigations in a first- are calculated. For the purposes of this investigation,
year course. A basic thermodynamic study of the the enthalpies of dilution of the reactants and the
acetic acid-water, chloroacetic acid-water, dichloro- products are assumed to he negligible or to cancel.
acetic acid-water, and trichloroacetic-water system On this basis, it is assumed that the experimentally
has been described,' and can be modified to meet the determined enthalpy of neutralization is equal to t,he
requirements of a first-year college chemistry course. standard enthalpy of neutralization (AHNO).
The ionization of acetic acid, chloroacetic acid, Since the enthalpy change for a reaction depends only
dichloroacetic acid, and trichloroacetic acid in aqueous upon the initial and final states of the system, the
solutions can be represented by the equilibria: neutralization of each of the acid solutions can he
HOA(aq) = OA-(ilq) + Ht(aq) divided into two steps. First, any molecules of undis-
sociated acid which exist in the solution of the acid a t
the time of mixing become dissociated. Second, the
hydrogen ions resulting from the dissociation of the
The students are asked to determine the effect of the acid are neutralized by the hydroxide ions. The
structure of the acid on the equilibria and to discuss standard enthalpy of neutralization of hydrogen ions
the observed effects in terms of standard free energy, by hydroxide ions can be ohtained experimentally by
enthalpy, and entropy changes. studying the neutralization of hydrochloric acid with
Data for calculating the equilibrium constants are sodium hydroxide a t different concentrations. For
ohtained by titrating an aliquot of each of the acids this investigation a literature value of -13.34 kcal/
with a sodium hydroxide solution. The pH of the mole3 was used as the standard enthalpy of neutraliza-
solution of the acid is measured with a pH meter after tion of hydrogen ions. The standard enthalpy of
the addition of each portion of titrant. Each of the ionization for each of the acids can he calculated using
equilibrium constants is then calculated from a graph of Hess' Law. If the assumption is made that none of the
pH versus volume of sodium hydroxide added to the acid is ionized before neutralization, the standard
acid solution using the half-titration m e t h ~ d . ~The enthalpy of ionization (AHI'') is given by:
equilibrium constants are used to calculate the standard
free energy of ionization (AGIO)of each of the four acids: AHr"' = AHN' + 13.34 kcal/mole
AGIO = -RT In K However, the fraction of each acid (x) that was not
ionized before neutralization can be calculated from the
The second phase of the investigation involves the equilibrium constant. The standard enthalpy of
calcnlation of the enthalpies of neutralization of each of ionization ( a H l O )calculated on the basis of the actual
the four acids from experimental data. Timetempera- number of molecules of acid which dissociated at the
ture data are obtained on stoichiometric quantities of time of neutralization is given by:
1.00 M sodium hydroxide and 1.00 A t 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 Since the standard free energy of ionization has been
period of ahout 5 min. The sodium hydroxide solution calculated for each of the acids and the standard
and the acid solution are mixed together in a Ther- enthalpy of ionization has been calculated, the sbndard
molcup which serves as a calorimeter, and time-tempera- entropy of ionization of each of the acids can be cal-
ture data are collected for the reaction mixture for a 10 culated :
min post-mixing interval. Thermometers graduated
Teaoher's Guide, "Investigating Chemical Systems," Webster Representative student data for AGIO, AHI", and
Division, MeGrera-Hill Book Co.,Inc., New York, 1963, p. 3 2 1 .
' REILLEY,C. N., AND SAWYER, D. T., "Experimentsfor Imtru-
mental Methods,"McGraw-HillBook, Co.,Inc., New York, 1961, HALE,J. D., IZATT, R. M., AND J. J., .I. Phys.
CHRISTENSBN,
p. 23. Chem., 67,2605 (1963).
AGro, AHI", and TASIo for the Ionization of Acetic and Chloroacetic Acids
-
1.00M 1.00M 0.50M 1 .OOM
Acetic Chloroacetic Diehloroacetic Trichloroeoetic
acid acid acid acid
K 2.2 X lo-" 1.6 X 3.6 X 2.0 X lo-'
% Ionized 0.47 3.9 24 36
AGI (kcal/mole) 6.36 3.82 1.96 0.94
AHxD(kcal/mole) -13.9 -15.6 -15.4 -15.4
AH1"'- (kcal/mole) -0.6 -2.3 -2.1 -2.1
AHroL(kcnl/rnole) -0.6 -2.4 -2.8 -3.3
TASlo (kcd/mole) -7.0 -6.2 -4.8 -4.2
B a e d on the assumption that none of the aoidvias dissooi&d beforeneutralization.
6 Based on the calculated fraction of aoid that was not dissociated before neutralization.