Heat

of Hydration

Pre-lab Assignment
1. Identify the purpose of this experiment and record it in your lab notebook.
2. Write out the procedure in your lab notebook.
3. Define the following terms: adiabatic, endothermic and exothermic.
4. Calculate the molar mass of the 6 salts youll be using in this lab and record in your notebook.

Introduction

Many salts form hydrates when crystallized from an aqueous solution. The crystal
structure of the hydrate contains water molecules bound in specific lattice sites. As a
consequence, hydrates exhibit well-defined stoichiometries between the ions and water
molecules of which they are composed. Some examples of hydrates are Na2SO410H2O,
MgSO47H2O, CuSO45H2O and BaCl22H2O. In terms of nomenclature, a barium chloride
dihydrate crystal contains two water molecules for each barium atom.

Hydrates are generally stable at room temperature. Their formation from aqueous
solution is driven by the enhanced bonding that can be attained in the hydrate crystal relative
to that of the anhydrous salt. Consequently, energy is required to release the water from the
hydrate. The enthalpy difference between the hydrate and its anhydrous salt is referred to as
the heat of hydration, Hhyd. The notation refers to the change in enthalpy between the final
and initial states of a physical or chemical process. The process is represented, for barium
chloride, as




BaCl2 (s) + 2H2O (l) > BaCl22H2O (s)


(1)

The task of measuring the enthalpy change for the process represented in equation (1) can be
accomplished in several ways. One could heat the hydrate to release the waters of hydration,
collect the evolved water vapor, condense the water, and cool down the anhydrous salt. The
heat absorbed or evolved from each step would have to be measured and finally tallied
together. An alternative, and experimentally simpler approach, is to measure the enthalpy
change associated with making identical aqueous solutions of the hydrate and the anhydrous
salt, respectively. These processes are represented in equations (2) and (3):



BaCl22H2O (s) + nH2O (l) > BaCl2 (aq) + (2+n)H2O (aq)
(2)



BaCl2 (s) + (2+n)H2O (l)
> BaCl2 (aq) + (2+n)H2O (aq)
(3)

We can add equation (3) to the reverse of equation (2) to get equation (1). Both equation (2)
and (3) represent the dissolution of the respective solid salt to create an aqueous solution. The
enthalpy difference between the solution state and that of the pure components is called the
heat of solution, Hsoln.


Using Hess' law, one can determine the heat of hydration for barium chloride as:




Hhyd = Hsoln(BaCl2) - Hsoln(BaCl22H2O)


(4)

To use expression (4), the solution states for both the hydrate and the anhydrous salts must be
identical. The value of the molar heat of solution is dependent on the concentration of the
aqueous solution formed. This is a consequence of concentration dependent ion-ion, water-ion
and water-water interactions. Some values of Hsoln(25 C) are given below. The dilution refers
to the initial moles of water used per mole of salt.

Table 1: Heat of Solution of Various Salts
Salt
Dilution
Hsoln (25 C), kJ/mol
BaCl2 (anhydrous)
400
-8.67
CuSO45H2O
400
11.51
MgSO47H2O
400
16.11


As is convention, positive values of Hsoln indicate that the dissolution process is
endothermic. One would expect the aqueous solution to cool down after the salt has been
added. Some of the kinetic energy of the solution is used to weaken the overall bonding in the
system. In the case of anhydrous barium chloride, the solution will heat up during the
dissolution process. The lowering of the potential energy of the bonds that are formed is
compensated by an increase in the kinetic energy of the solution.

The energy changes associated with the dissolution process are readily measured using
a solution calorimeter. The calorimeter consists of a Dewer flask containing a known mass of
solvent, a delivery mechanism for the salt, and a sensitive thermometer. Since the Dewar flask
is thermally insulated, the heat evolved (or absorbed) by the solution process goes directly into
heating (or cooling) the resulting solution. For an ideal adiabatic calorimeter (meaning no heat
is transferred to or from the surroundings), the 1st Law of Thermodynamics says that






qsoln + qcal = 0






With some substitutions, we get
nHsoln + mcpT = 0



(5)

where m and cp represent the mass and specific heat of the resulting solution, respectively. The
temperature change, T, can then be related directly to the heat of solution. In practice,
however, some heat (qsurr) is lost to (or gained from) the exterior of the Dewar flask. Equation
(5) must now be modified to read






nHsoln + mcpT = qsurr



(6)

This heat transfer can be minimized if the solution temperature equals that of the surroundings.
If the calorimetry experiment is started with the temperature of the "reactants" equal to the

temperature of the surroundings, qsurr = hT. Here, h is the heat transfer coefficient for the
calorimeter. Under these conditions, one can define a calorimeter constant, C = mcp - h, that
can be used to determine the heat of solution from the temperature change in the calorimeter.
Substituting hT in for qsurr (as mentioned above) and combining like terms:






-nHsoln = (mcp - h)T

= CT


(7)

The calorimeter constant ,C, is generally determined using a calibration standard appropriate
for the solution of interest.

In this experiment, we will be using a crude calorimeter made of two nestled Styrofoam
cups. To calibrate our calorimeters (and hence obtain a calorimeter constant), we will use the
literature value for the heat of solution (Hsoln) of either copper (II) sulfate pentahydrate or
magnesium sulfate heptahydrate from Table 1 above and equation (7).

Experimental Procedure

In this experiment you will determine the heat of hydration for each of the following
salts: calcium chloride, copper (II) sulfate and magnesium sulfate. To do this, you will determine
the heat of solution for both the hydrate and the associated anhydrous salt using a Styrofoam
cup calorimeter. Each measurement will be performed in duplicate and the results averaged.

Reagents
Calcium chloride (anhydrous) - CaCl2
Calcium chloride Dihydrate - CaCl22H2O
Copper (II) sulfate (anhydrous) - CuSO4
Copper (II) sulfate pentahydrate - CuSO45H2O
Magnesium sulfate (anhydrous) - MgSO4
Magnesium sulfate heptahydrate - MgSO47H2O
Deionized Water

Equipment
Styrofoam cup calorimeter
Electronic Balance
Digital thermometer

Measurement
1. Add approximately 100 g of deionized water to the Styrofoam cup calorimeter using
the balance, and record the exact mass with all significant figures in your notebook.
Allow the temperature to equilibrate to room temperature.
2. If not already a powder, carefully grind one of the salts using a mortar and pestle.
Weigh out approximately 5 grams and record the mass.
3. When the temperature of the calorimeter with water is steady, record it. Add the salt
to the water in the calorimeter with rapid stirring using the thermometer.
4. Watch the temperature of your water solution for a while immediately after adding
3

the salt. You may want to write down temperature readings every few seconds to see
the trend. Record the maximum temperature change (Tfinal Tinitial, before adding salt) during
the process.
5. Rinse the cup and thermometer with DI water and dry with a paper towel.
6. Repeat the run a second time for this same salt.
7. Repeat the procedure (in duplicate) for each of the salts listed above to obtain
mass/temperature data. There should be 12 runs total.

Analysis
1. Make a table of the data for all of the salts, like that below.
Salt
CaCl2

CaCl22H2O

CuSO4

CuSO45H2O

MgSO4

MgSO47H2O

Mass salt
g

Moles salt

Tinitial
C

Tfinal
C

T
C

qsoln
J

Hsoln
J/mol

Ave. Hsoln
J/mol

2. Calculate the calorimeter constant, C, for your Styrofoam calorimeter. Use the
temperature change observed for the solvation of either copper (II) sulfate
pentahydrate or magnesium sulfate heptahydrate (one or the other), the literature
value of Hsoln from Table 1, the number of moles (n) of salt used for the measurement
and equation (7). Calculate two C values (one for each trial) and average them.
3. Using the average C for your calorimeter, calculate qsoln for each run in J. Then,
calculate the molar heat of solution (Hsoln) for each salt, as an average of the two
trials performed.
4. Determine the molar heat of hydration (Hhyd) for the 3 salts using the enthalpy of
hydration equation given above (4).

Before you leave lab, turn in the carbon copies from your notebook.

For next week, write up your discussion. This should repeat the purpose of the experiment,
summarize the results and observations and your interpretation of these results. Be sure to
address the following points:
1. Describe some other possible sources of heat transfer in this system (besides the water
in the calorimeter).
2. Compare your experimentally determined heat of solution of copper (II) sulfate
pentahydrate and magnesium sulfate heptahydrate to the literature values reported in
Table 1. If they are the same, why? Why might they be different?
3. Characterize the heat of hydration (Hhyd) of each salt as endo- or exothermic.