Calorimetry: Enthalpy of Solution and Enthalpy of Hydration

Performed 11/2/16
Submitted 11/16/16

Abstract
This experiment focused on using a bomb calorimeter to experimentally determine the heats of solutions
of the following salts: KCl, KNO3, CaCl2.LiNO3, and NH4NO3. The heats of solutions, in kJ/mol, were
determined to be 17.41 ± 0.11, 35.42 ± 0.096, -42.53 ± 0.099, -2.14 ± 0.098, and 26.26 ± 0.10,
respectively. These values were utilized to calculate the enthalpies of hydration for each of ions. Those
values, in kJ/mol, were -333, -318, -1573, -532, and -118 for K+, NO3-, Ca2+, Li2+, and NH4+, respectively.
Introduction
In this lab, we will study the enthalpy changes associated with dissolving an ionic solid in water. When an
ionic solid is placed in water, the dissolving process could either lead to an increase or decrease in
temperature. This is a result of the difference in energy required to break the ionic and the energy required
to form the ion-dipole interactions in the solution. Therefore, looking at the dissolution of a soluble salt,
which we know will be a spontaneous process, the enthalpy of hydration or the energy released in
forming the ion-dipole interactions, must be greater the lattice energy, the energy associated with
breaking up the solid lattice. However, we must not that the spontaneity of a dissolution process does not
only rely on the enthalpy term; the spontaneity of a process is determined by the change in free energy,
which is related to both enthalpy and entropy, as described in equation (1).
∆G = ∆H − T∆S (1)

While many spontaneous dissolution reactions are exothermic, an endothermic dissolution reaction can
still be spontaneous if the TΔS term is large enough. We will remember to keep this mind when
considering a spontaneous dissolution that results in a negative temperature change.
We will be directly measuring the heat of solution corresponding to several salts using a constant
pressure, adiabatic calorimeter. The temperature change will be monitored as the solid mixes with the
solvent. The energy released or absorbed by this process is the heat of solution. We can describe the heat
of solution as corresponding to the following process:

MX(s) → M + (aq) + X − (aq) (2)

Furthermore, the lattice enthalpy of a solid is the energy required to form gaseous ions:
MX(s) → M + (g) + X − (g) (3)
Finally, the heat of hydration is the energy change associated with dissolving gaseous ions:
M + (g) + X + (g) → M + (aq) + X + (aq) (4)
We can combine equation (3) and (4) and notice that the resulting expression is the same as equation (2).
Using Hess’ Law, we can conclude that ΔHsolution= ΔHlattice energy + ΔHhydration. Thus, if we know the lattice
dissociation enthalpy, we can calculate for the heat of hydration. These calculations will be carried out in
the discussion section of this report.
Procedure
The experimental procedure of this experiment was followed as outlined in the laboratory handout1 with
the following modifications: batch duration was changed to 450 seconds.
Results
See attached spreadsheet. The first KCl trial was not included in later calculations due to insufficient
leadout time.
Discussion
As stated in the introduction, a bomb calorimeter was utilized to measure the temperature change
associated with the heat of solution of a particular solid. We were able to measure this quantity based on
the temperature change of the solution. All calorimeters have a heat capacity, or an amount of energy
required to change internal temperature by 1°C. The heat capacity of the calorimeter was determined
through its own calibration process. Thus, we can easily find the amount of energy released from the
reaction as heat. We simply multiply the heat capacity by the temperature change; the calculation is
carried out for the dissolution of LiNO3:
cal
qsolution = Cp ∆T = (27.5400 ) (0.0154241°C) = 0.425 cal = 1.78 J (5)
°C
Thus, this the heat released when that particular amount of LiNO3 was dissolved in water. To find the
molar heat of solution, we must divide the heat released or absorbed to dissolve the salt by the number of
moles of the salt. Following the calculation above, we have:
q 1.78 J 68.9 g J kJ
∆Hsolution = = × = 1793 = 1.79
n 0.0684 g mol mol mol
This is the experiment heat of solution for LiNO3. The same calculation was carried out for the remaining
salts, per trial (see attached spreadsheet). It is important to note that an uncertainty was attributed to the
software’s measurement of the calorimeter’s heat capacity and the temperature change. The uncertainty
was determined to be ± 0.0000005 °C for the temperature change and ± 0.00005 cal/°C for the heat
capacity. The error in q was determined in following way:

∆x = √b 2 (∆a)2 + a2 (∆b)2
where Δx is the propagated uncertainty in q, a and b are the measured quantities (heat capacity and
temperature) and Δa and Δb are their respective measurement uncertainties. Similarly, we determined the
measurement uncertainty in the mass measurements to be ± 0.0005 g. Thus, the error in ΔH was
propagated through the propagated error in q and the measurement uncertainty in of the mass as such:

1 a2
∆x = √ 2 (Δa)2 + 4 (∆b)2
b b

Where Δx is the propagated uncertainty in the heat of solution, a is q (found in the manner shown in
equation (5) ), b is the mass of the salt, and Δa and Δb are their respective uncertainties.
The calculated heat of solutions for each salt along with their literature values 2,3 are summarized in Table
1.

Table 1. Experiment and literature values of the heats of solutions for each salt in the experiment.

Salt ΔH solution (kJ/mol) Experimental ΔH solution (kJ/mol) Literature

KCl 17.41 ± 0.11 17.22
KNO3 35.42 ± 0.096 34.89
CaCl2 -42.53 ± 0.099 -82.9
LiNO3 -2.14 ± 0.098 -2.51
NH4NO3 26.26 ± 0.10 25.69

Using the heat of solution values, we were able to calculate the sum of the heat of hydrations for both ions
in the salt. As stated in the introduction, ΔHsolution= ΔHlattice energy + ΔHhydration. While this is true, there is a
heat of hydration associated with both the anion and cation in the lattice. Nonetheless, solving for the sum
of the heat of hydrations of the ions will allow to calculated the ionic heat of hydrations if we have a little
bit more information. Since we know that the enthalpy of hydration of Cl- is -364 kJ/mol and we know the
lattice energies of each salt, we can solve for the enthalpy of hydration of K+ as such:
ΔHsolution = ΔHlattice energy + ΔHhydration

ΔHsolution − ΔHlattice energy = ΔHhydration

ΔHhydration = ΔHhydration (K + ) + ΔHhydration (Cl− )

ΔHsolution − ΔHlattice energy − ΔHhydration (Cl− ) = ΔHhydration (K + ) (6)

kJ kJ kJ kJ
17.41 − 715 − (−364 ) = −334
mol mol mol mol
Now, the enthalpies of hydration can be calculated for potassium and chloride salts. Subsequently, the
enthalpies of hydration for the remaining ions in nitrate salts could then be calculated. Table 2
summarizes these calculations.
Table 2. Enthalpy of hydration for each ion in the experiment.

Ion ΔH hydration (kJ/mol)

K+ -333
NO3- -318
Ca2+ -1573
Li+ -532
NH4+ -118

Looking at the data in Table 2, there seems to be a general trend occurring; smaller ions seems to have a
greater enthalpy of hydration over larger ions, while ions with a greater magnitude of charge have a much
greater enthalpy of hydration. This makes sense theoretically, since ions with a greater charge would be
more strongly attracted to water molecules and they would form stronger, more energetically favorable
interactions. Moreover, among ions with the same charge, the smaller ions, with a higher charge density,
will form tighter bonds than their larger counterparts.
While most of our heat of solution values were within a few percentage points from the literature values,
there are still sources of error that may account for the failure to bracket the literature value within the
uncertainty range. For one, the literature values correspond to measurements taken at 25°C. While our
temperatures were likely close to this value, it would be difficult to ascertain this. For exothermic
reactions, a higher temperature would mean a lower heat of solution, since solubility would decrease,
while the opposite is true at lower temperatures. For endothermic reactions, an increase in temperature
would result in a higher heat of solution, since solubility would increase. Furthermore, we cannot be
certain that the bomb calorimeter was completely adiabatic. A small amount of heat transfer may still be
occurring between the calorimeter and the surroundings. This would affect the change in temperature but
would not have been accounted for in our judgment of uncertainty of the change in temperature given to
us by the software. Finally, it is worth it to note that the heat of solution of CaCl2 was significantly
different than the literature value. Since the values for the heat of solution had a relatively low standard
deviation, it may not be plausible to say that systematic error was the cause of this discrepancy. It may be
that the salt was not actually anhydrous, but rather had absorbed moisture from the air over time. This is
likely to lead to a variety of errors (i.e. the mass wouldn’t reflect 1 mmol of the salt, the salt would
dissolve to a lesser extent, etc.) that could have synergized into a very large difference.

References
1. Heat of Solution: Ionic Solids, Tufts University, Chemistry Department 2003
2. Parker, V. B., Thermal Properties of Uni-Univalent Electrolytes, Natl. Stand. Ref. Data Series — Natl.
Bur. Stand.(U.S.), No.2, 1965.
3. Heat of solution data - UPM http://webserver.dmt.upm.es/~isidoro/dat1/heat of solution data.pdf
(accessed Nov 15, 2016).