10.

Solution thermodynamics Page 1

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Learning objectives
During this experiment you will: Prepare solutions of accurately known concentration; measure temperature
changes precisely; plot a solubility curve; prepare and handle supersaturated solutions; and assess critically your
results. You will also learn one way of determining experimentally the entropy and enthalpy of fusion of a solid.

Outline
There are four parts to the experiment:
1. Determine and plot the experimental relationship between temperature and the amount of solid that will
dissolve in a known amount of water to form a saturated solution (the solubility curve).
2. Determine the heat capacity of a saturated solution, using a simple heattransfer experiment.
3. Measure the temperature change when a supersaturated solution spontaneously recrystallizes.
4. Complete the final calculations.



10. Solution thermodynamics Page 2

1 LINKS TO THE LECTURE COURSE
Relevant lecture courses
Thermodynamics (Michaelmas term, 1
st
year)
States of Matter (Trinity term, 1
st
year)
Relevant topics
Chemical potential, solubility, supersaturation, enthalpy of fusion, ideal solutions.


2 A SUMMARY OF USEFUL INFORMATION AND DEFINITIONS
A saturated solution is one which is at equilibrium in contact with excess solid solute. A supersaturated solution
contains more solute than a saturated one, and cannot be at equilibrium with solid solute.
The mole fraction is defined by x
i
= n
i
/ (n
1
+ n
2
+ n
3
+ ... + n
i
), where n
i
is the number of moles of species i.

The amount of material that will dissolve to give a saturated solution at a specified temperature is related to the
enthalpy of fusion of the solute by the equation:

2
1 1
ln

=
(
(

o
fus
fus
H
x
R T T

The heat capacity of water is 4.2 J g
1
.

3 RELEVANT THEORY AND BACKGROUND INFORMATION
3.1 Introduction
When a saturated solution of a solute is in contact with the solid, the solution and solid phases must be in
equilibrium. Were that not true, either more solid would dissolve, taking the concentration of the solution beyond
saturation, or solid would precipitate out, leaving a solution that was no longer saturated.
It might seem therefore that it would not be possible to prepare a solution in which more material is dissolved than
the amount that would give a saturated solution, but this conclusion is incorrect. With care, we can make a solution
in which the concentration of solute exceeds that of a saturated solution; this can be done by cooling a saturated
solution to below the temperature at which solid should precipitate, yielding a socalled supersaturated solution.
Such solutions are thermodynamically unstable and will attempt to lower their free energy by precipitating out the
excess dissolved material, if possible, to create a solution that is just saturated.
The reason that a precipitate does not always appear when a saturated solution is cooled is that precipitation
requires something that can act as the nucleus for formation of a crystal. In some of your synthetic experiments you
may have been told to gently scratch the interior of a flask that contains a solution of a material you wish to
crystallize. Scratching creates irregularities on the surface of the flask, a few of which may have a similar geometry
to that of crystals of the solute; these imperfections act as initiation points for crystallization. Once the first crystal
forms, largescale precipitation follows. However, if no nucleation points exist (if the flask is clean and smooth and
no dust is present), it may be possible for a solution to be formed that is significantly supersaturated.
10. Solution thermodynamics Page 3

In this experiment you will investigate the thermodynamics of solubility, using supersaturated solutions. These
provide an interesting and convenient way to investigate thermodynamics of dissolution.
3.2 The relevant equations
When a solid is in contact with a saturated solution, the solid and the dissolved material must have the same
chemical potential. The chemical potential of solute i in solution is given by

(soln) ( ) ln = +
o
i i i
l RT x
(1)

In equation (1), (soln)
i
is the chemical potential of the material when it is dissolved, ( )
o
i
l is the chemical potential
when it is a liquid and x
i
is the mole fraction. Equating the chemical potential of solid and solute:

2 2 2 2
( ) (soln) ( ) ln
o o o
s l RT x = = +
(2)

where, by convention, the solute is given the subscript 2. It follows that

O O O
2 2 2 2,FUS
RTlnx = (s) - (l) = - G
(3)

Using the GibbsHemlholtz equation

2
2
2
=

| |

|
\ .

H
T
G
T
T
(4)
it can be shown that

2
2
ln

| |
|
\ .
o
fus
p
H
x
T RT
(5)
The integrated form of equation (5) is

2
1 1
ln

=
(
(

o
fus
fus
H
x
R T T
(6)
This equation relates the amount of solute in a saturated solution to the temperature and to the enthalpy of fusion
of the solute
1
. It assumes that the solution behaves ideally which, in the current experiment, is approximately true.

4 PROCEDURE
The overall aim of the experiment is to determine the enthalpy and entropy of solidification of sodium acetate
trihydrate (SAT). You will do this in two different ways: firstly, you will determine the solubility curve for SAT in
water; subsequently, you will determine the heat capacity of saturated solutions of SAT and use this information to
interpret data from crystallization of supersaturated solutions.

1
The reason why the enthalpy of fusion appears is that in both melting and dissolution energy has to be supplied to disrupt the
intermolecular forces in the solids in order to break up the solid.
10. Solution thermodynamics Page 4

4.1 Preparation
If the glassware that you use is not clean the experiment may fail, so check it before you start and ask for a
replacement if any of the flasks to be used are damaged or dirty.
You will need some cold demineralized water during the first part of the experiment, so get that ready now.
Measure exactly 10 cm
3
demineralized water into a 50 cm
3
conical flask and store it in ice to cool down.
You will also need two supersaturated solutions which must be prepared in advance as follows: Weigh out
accurately about 20g of SAT. Tip the solid into a clean and dry 50 cm
3
conical flask, then add 10 cm
3
of
demineralized water. Warm the mixture by placing it on the surface of a hotplate, with regular swirling (do not stare
at the halogen hotplate!). Swirl the liquid gently, since if you splash solid into the neck of the flask it will be hard to
get it down into the liquid again. Take the flask off the hotplate frequently and check whether solid remains. Once
the last trace of solid has gone, set the flask aside where it will not be disturbed, cover the top with a watch glass
and leave it to cool down to room temperature; this is your supersaturated sample A. Carry out the same procedure
with a second sample, containing about 30g of solid (supersaturated solution B). You will return to these samples
later in the experiment.
4.2 Solubility curve
In the first part of the experiment you will obtain the solubility curve, which shows how much solid can be dissolved
at a particular temperature. The procedure for doing this is quite simple: you will add solid to some water, then heat
the mixture and record the temperature at which the last of the solid dissolves. Once all the solid has disappeared,
further solid is added and the process repeated.
Measure the temperature of the 10 cm
3
sample of cold water that you set aside earlier. If it is 5
o
C or below, remove
the flask from the ice and add to it an accurately weighed portion of SAT, of mass around 10g. Place a digital
temperature probe in the solution and swirl the liquid to dissolve the solid; your aim is to measure the temperature
at which dissolution is just complete. Use a beaker of hot water or a hot plate to promote dissolution if necessary.
At the point at which the last of the solid dissolves record the temperature of the solution. Now add a further
accuratelyweighed 1g portion of solid, continue swirling and warming and again record the temperature at which
the last of the solid disappears. Continue, adding further portions of about 2.5g, 3g and finally another 3g portion.
The temperature at which the final portion of solid dissolves should be around 4550 C.
Before proceeding further, process the data from this part of the experiment. First draw a solubility curve, showing
how the amount of SAT that dissolves to give a saturated solution varies with temperature. Next, calculate the mole
fraction for each solution. Taking account of equation (6), prepare a suitable plot and determine the enthalpy and
temperature of fusion of SAT.
4.3 Heat capacity of SAT solutions
The next step is to measure the heat capacity
2
of a saturated solution of SAT. To do this you will immerse a cold
saturated solution of SAT in warm water. By measuring the cooling of the water you can determine how much heat
is transferred to the solution, and by measuring the rise in temperature of the solution you can determine its heat
capacity.
From your solubility curve, estimate how much solid is required in 15 cm
3
water to prepare a saturated solution at
around 280K. Measure out about 1g more than the required weight, add all the solid to 15 cm
3
water and mix until

2
The heat capacity is the quantity of heat required to raise the temperature of a specified amount of material by 1K. Heat capacities are
generally specified for 1 mole of material, but may also be given per gram, so dont neglect the units!
10. Solution thermodynamics Page 5

you are confident the solution is saturated; a small amount of solid should remain undissolved. If all the solid
dissolves, add a little more and shake.
Using a measuring cylinder, measure out 10cm
3
of this solution into a cold finger (metal test tube) and insert a
digital temperature probe. While waiting for the reading to stabilize, measure out 20 cm
3
of water with a
temperature 1220 K higher than that of your SAT solution. Pour the water into a 50 cm
3
beaker and place a second
digital temperature probe into the water. Add a small stirring bean to the beaker, place on a magnetic stirrer and
turn on the stirrer.
Record the temperatures of the two liquids. When the temperatures are constant
3
(constant does not mean the
temperatures are identical!) clamp the cold finger in the beaker of water so that as much as possible of it is in
contact with the water and immediately resume recording the temperature of both water and solution. Take
readings of both liquids every 15 seconds until the temperatures stabilize. This should take no more than a few
minutes. Note the final temperatures.
Repeat with a second sample of saturated SAT solution at an initial temperature of around 290 K, equilibrating it
with water that is again 1220 K higher in temperature. Finally perform a third experiment in which 10 cm
3
of
demineralised water at a temperature around 290K in the cold finger is equilibrated with a sample of water 1220 K
warmer.
4.4 Precipitation from supersaturated solutions
In this part of the experiment the aim is to determine the temperature change that occurs when a supersaturated
solution crystallizes. Supersaturated solution A should still be a clear liquid with no solid. Gently place the flask on
the bench. Measure and record room temperature on the digital thermometer, then tip the flask a little and
carefully insert the temperature probe into the solution at its deepest. This will probably induce immediate
crystallization. If it does, swirl the liquid gently and continuously until the temperature settles; assume that the
initial temperature of the solution was room temperature.
If no crystals form, wait for the temperature to stabilize and record it, then induce crystallisation by gently agitating
the flask (do not scratch the inside of the flask to induce crystallization if you do this, no subsequent student will
be able to use the flask). Precipitation of solid should occur readily, releasing heat. (If even gentle swirling does not
yield any solid, add a small crystal of SAT; provided that the solution really is supersaturated, precipitation will start
immediately.) Continue to record the temperature every 30s until it stabilizes. Hence determine the temperature
rise upon crystallization.
Repeat the experiment with your supersaturated solution B. No swirling will be required for this solution, so just
insert the probe and immediate start recording the temperature.
4.5 Closing down
Wash out all the equipment you have used, discarding waste solution in the sink. Wash all items twice with
demineralized water and return to the tray for the experiment.

5 FINAL CALCULATIONS AND REPORT
Step 4.3:
First calculate the heat capacity of the cold finger as follows:

3
As the temperature of at least one liquid will be different from room temperature, the temperatures will drift with time. Once the liquids
have equilibrated with the temperature probes, this drift should be ignored.
10. Solution thermodynamics Page 6

a) Calculate the amount of heat transferred out of the warm water in your third experiment.
b) Now calculate how much of that heat was used to heat up the water in the cold finger; this value should be
less than the value from part (a).
c) The heat lost by the warm water that was not absorbed by the cool water has been used to warm up the
cold finger. Use this value and the temperature change of the cold finger to calculate the heat capacity of the cold
finger.
Now that you know how much heat is required to warm the cold finger through 1K you can calculate the heat
capacity of the SAT solutions.
a) For each of the two experiments calculate the amount of heat transferred into the cold finger + contents.
b) Calculate how much of this heat is absorbed by the cold finger and hence how much is available to heat the
SAT solution. Thus calculate the heat capacity of the SAT solution.
c) Average your results to get a mean value for the heat capacity of the SAT solution.

Step 4.4:
a) Using the heat capacity calculated earlier, calculate the heat required to warm the solution to its final
temperature.
b) Now calculate the number of moles of SAT that have crystallized out and hence determine the enthalpy of
fusion. (Bear in mind that, no matter how solid the final mixture may look, it consists of solid plus saturated solution,
so not all the solid has crystallized. Use your solubility curve to determine how much SAT has solidified and how
much remains in solution.)
Comment in your report on the level of agreement between the two values for the enthalpy of fusion you have
obtained. Estimate the error in each method and comment on the sources of error and any approximations you can
identify.
Answer the following questions in your report:
Question 1: From the data you have it should be possible to estimate the molar entropy change upon crystallization.
Explain how this could be done, and outline how you would calculate the overall entropy change (system +
surroundings) for the crystallization from a supersaturated solution. What sign should this overall entropy change
have? Why?
Question 2: In step 4.4, do you have to assume adiabatic conditions, isothermal conditions, both or neither? Explain.
Question 3: Provide a rough estimate of the error that is introduced in the calculation above by ignoring the heat
transferred to the solid. The heat capacity of the crystals is 229 J mol
1
K
1
at 298K and 246 J mol
1
K
1
at 320K

APPENDIX A SAFETY
Sodium acetate trihydrate is an innocuous compound which presents little risk in normal use. However, you should
keep it off your skin and ensure you do not inadvertently inhale any powder.
Exercise normal care in your use of hot plates and liquids, and laboratory glassware.
10. Solution thermodynamics Page 7


APPENDIX B PROBLEMS AND SOLUTIONS

Problem... Indicates... Solution
In step 4.4 no precipitation
occurs even when a crystal
of SAT is added
Solution was not
supersaturated at the
temperature you are using
a) If there was solid present before the crystal was added,
the solution could not have been supersaturated; prepare
another solution.
b) If there was there no solid present and adding a crystal
did not induce precipitation, the solution never contained
enough solid to be saturated; prepare another solution.



August 5, 2010.