In the Laboratory

Calorimetric Determination of Aqueous Ion Enthalpies

Paul Siders
Department of Chemistry, University of Minnesota–Duluth, Duluth, MN 55812

Formation enthalpies of aqueous ions are discussed
in general and physical chemistry textbooks and can
readily be measured in a physical chemistry laboratory.
A solution-calorimetry experiment to determine enthal-
pies of formation of aqueous Na+ , K+, Cl{, and I{ is de-
scribed below. Other solution-calorimetry laboratory ex-
periments have been published in this Journal. Experi-
ments described by Raizen, Fung, and Christian (1) mea-
sure the enthalpy of reduction of permanganate by
iron(II), and the enthalpy of mixing of ethanol and cy-
clohexane. The experiments of Diogo et al. (2) address
solute–solvent interactions and lattice energies.
Our laboratory uses the Parr 1455 Solution Calo-
rimeter. An insulated Dewar flask is filled with 100 mL
of water or aqueous HCl. The solid sample to be dissolved
is placed on a covered sample dish that rotates in the
solution. The solution’s temperature is measured with a
thermistor. The sample dish can be released into the so-
lution with a push rod.
The calorimeter is controlled and data are recorded
by a computer attached to the calorimeter’s serial port.
The Parr serial port accepts an RJ-45 connector. A
BASIC program gives students a menu with selections
to record, list, and plot data and to send control codes to
the calorimeter (e.g., to start and stop the stirrer). The
program also creates a data file in comma-quote format
for easy import to a spreadsheet. The program was writ-
ten in BASIC for portability among DOS machines; we
have used it on a single-floppy 8088 computer and a
dual-floppy 80386. The BASIC code and pin assignments
for a cable from the calorimeter’s RJ-45 port to a 25-pin
serial port are available from the author.
The calorimeter is standardized by reacting about
0.5 g of tris(hydroxymethyl)aminomethane (“Tris”) with
100.0 mL (a stoichiometric excess) of 0.1000M HCl, as
described in the Parr manual. The enthalpy of neutral-
ization of solid Tris by 0.10 M HCl is 245.76 J per gram
of Tris at 25 °C. A small correction is applied if the reac-
tion temperature is not 25 °C. The enthalpy change of
the neutralization, in joules, is Q p = m[ 245.76 +
1.436(25.0 – T 0.63R) ], where m is the mass of Tris in
grams and T 0.63R is the Celsius temperature at 63% of
the rise. Finally, the heat capacity of the calorimeter,
Cp,cal , is calculated from the relation Qp /∆T = Cp,cal +
Cp,soln , where Cp,soln , the heat capacity of the solution, is
taken to be 4.190 J?K{1?mL{1. The temperature change,
∆T, is calculated at the time at which the temperature
rise is 63% complete. For our calorimeter, C p,cal = 91 J/K.
After standardizing the calorimeter (three repeti-
tions), four reactions are run in duplicate to determine
enthalpies of four aqueous ions. Enthalpies of aqueous
ions are taken relative to the reference choice
∆Hf°( H+,aq) ≡ 0 at infinite dilution (3). The first reaction
involves H+, for which the enthalpy is zero by convention.
H (aq) + NaC2H3O2?3H2O(s) →
+
peratures obtained from dissolution of 1.3584 g of
NaC2H3O2?3H2O in 100.0 mL of 0.2000 M HCl. ∆T is cal-
culated between the regression lines at the point of 63%
temperature change, as suggested in the Parr instruc-
tion manual. The aqueous acetate ion does not enter the
reaction appreciably because the acetic acid is negligi-
bly ionized in the excess HCl. Students are asked to cal-
culate the percent ionization of acetic acid under their
experimental conditions.
The enthalpy of Na+(aq) is calculated from the mea-
sured ∆H1 and tabulated formation enthalpies of sodium
acetate trihydrate and acetic acid. Students then mea-
sure in duplicate the enthalpies of dissolving 0.010 mol
of three salts in 100.0 mL of water in the calorimeter:
NaI, KI, and KCl. The only salt requiring special han-
dling is NaI, which absorbs water with great effect on
heat of solution. We grind NaI, dry it at 160 °C for 2
hours, and thereafter store it in a desiccator. For every
run, students use a spreadsheet to fit linear regression
lines through early and late temperature data, and cal-
culate ∆T at the point of 63% temperature change. For
simplicity, the heat capacity of all aqueous solutions is
taken to be 4.190 J?K{1?mL{1. The three solution enthal-
pies of NaI, KI, and KCl plus the Na+ enthalpy obtained
from reaction 1 along with tabulated enthalpies of the
crystalline salts allow students to calculate enthalpies
of the aqueous ions I{, K+, and Cl{. This experiment has
been done in two 3-hour lab periods. It could be short-
Table 1. Aqueous Ion Enthalpies ∆H °f
(kJ/mol)
Ion Experimental Tabulated (3 )
Na + {241.0 {240.1
I{ {54.5 {55.2
K+ {252.8 {252.4
Cl{ {165.3 {167.2

Na (aq) + HC2H3O2(aq) + 3H2O(l); ∆H1

+
(1)
The enthalpy of reaction 1 is measured directly by
reacting solid sodium acetate trihydrate with excess hy-
drochloric acid in the calorimeter. Figure 1 shows tem- Figure 1. Dissolution of NaC2H3O 2?3H2O in HCl.

Vol. 74 No. 2 February 1997 • Journal of Chemical Education 235

In the Laboratory
ened by reducing the number of ions for which enthalp-
ies are determined.
In order to compare student data with tabulated val-
ues at 25 °C, the dissolutions should be run near 25 °C.
This is accomplished by filling the calorimeter with water
or HCl solution that has been warmed in a water bath.
Another possible difficulty in comparing results to
literature values is that the final ion molalities in this
experiment are about 0.1—far from infinite dilution. En-
thalpies might be corrected to infinite dilution using a
simple equation based on the Debye–Hückel limiting law:
lim ∆Hdissolution as m → 0 = ∆Hdissolution (m) + ∆H dilution (2)
where
1/
∆Hdilution ≈ {S (m) 2 (3)
For 1:1 electrolyte in water at 25 °C, the proportion-
ality constant S is approximately 2.01 kJ?mol{1?molal{1/2
(4, 5). However, eq 3 is applicable (with constant S) only
up to about 0.01 m. Data at higher concentrations are
discussed by Whalen (5) and by Young and Seligmann
(6). Enthalpies of dilution from 0.10 m to zero are {0.26
and {0.32 kJ/mol for NaI and KCl, respectively (7). Suf-
236 Journal of Chemical Education • Vol. 74 No. 2 February 1997
ficient data to reliably correct all four solution enthalp-
ies to zero concentration are not available, so concentra-
tion effects are neglected in this experiment.
Aqueous ion enthalpies calculated from enthalpies
of solution measured in the lab are given in Table 1,
along with literature values. Errors less than 2% were
easily obtained. The simple experiment described above
yields accurate results and reinforces the discussion of
aqueous ion enthalpies in the physical chemistry lecture
class. A detailed laboratory write-up is available from
the author.
Literature Cited
1. Raizen, D. A.; Fung, B. M.; Christian, S. D. J. Chem. Educ. 1988,
65, 932–933.
2. Diogo, H. P.; Minas da Piedade, M. E.; Moura Ramos, J. J.; Simoni,
J. A.; Martinho Simoes, J. A. J. Chem. Educ. 1993, 70, A227–A233.
3. Atkins, P. W. Physical Chemistry, 5th ed.; Freeman: New York, 1994.
4. Moelwyn-Hughes, E. A. Physical Chemistry, 2nd ed.; Pergamon:
Oxford, 1961; Chapter 18.
5. Whalen, J. W. Molecular Thermodynamics: A Statistical Approach;
Wiley: New York, 1991; p 79.
6. Young, T. F.; Seligmann, P. J. Am. Chem. Soc. 1938, 60, 2379–2383.
7. Lange, E.; Robinson, A. L. Chem. Rev. 1931, 9, 89–116.