Experiment

The Enthalpy of Vaporization and Enthalpy of Fusion of Water

INTRODUCTION

Heat and Molecular Motion

When a gas molecule is heated it moves faster. This motion of the center of mass
of the molecule is called translational motion (from one place to another place). Gaseous
molecules have a substantial fraction of their total energy as kinetic energy of translation.
That, they move about rapidly, bouncing off one another and the walls of their container.
Individual atoms in molecules are linked by chemical bonds that are “springy”,
constraining the atoms that are bonded together to move like masses connected by
springs. As the molecules are heated the energies and amplitudes of their vibrations
increase. The energy we put into a molecule is stored as translational, rotational, and
vibrational motions of the molecules.
When we cool a substance the energy from it is removed and molecular motion
slows down. The lowest temperature it can reach is called the absolute zero. At this
temperature molecular motion nearly ceases. As the energy is removed from the gaseous
molecules they will at some temperature condense into a liquid and eventually into a solid
because of the attractive forces between molecules caused by dipole-dipole attraction.
To separate the molecules in a solid to the distance characteristic of those in a gas, we
must do work against the opposing attractive forces (w = F x d). This work is the energy
required to melt the solid and vaporize the liquid.
In this experiment, we begin adding energy to ice at a uniform rate while measuring
the temperature. For water, a plot of temperature versus energy is usually displayed. As
the solid is warmed, the molecules begin to move. The molecules begin to bounce around
the cage formed by their surrounding neighbors. In effect, they are like gas molecules
confined to a very small container not much larger than the molecule itself. At the same
time the amplitude of vibration of the atoms bonded together increases and the molecules
may begin to rotate in their small cages. A few molecules at the surface of the ice may
acquire enough kinetic energy to break free from the solid to become gas molecules. The
number of a gas molecule may be large enough to produce a measurable pressure. This
pressure is called the vapor pressure of the solid.
At the melting point, the amplitude of the motion increases to the point where the
forces between neighboring molecules are no longer sufficient to hold them in a fixed
positions. The regular structure of the solid breaks down forming “holes” in the solid. The
molecules can move more freely, jumping from hole to hole. This produces a phase
change – the solid becomes a liquid. The liquid has a dramatically lower viscosity than
the solid, so that it adopts the shape of the container.
On average the molecules of the liquids have more energy than those of the solid.
The energy required to change the solid into a liquid is called the heat of fusion or the
enthalpy of fusion. Since liquid molecules have a greater average energy than
molecules in the solid, a greater number of them can escape into the gas phase, so that
the vapor pressure of the liquid is greater than the solid. As we continue to heat the liquid
a greater number of molecules acquire sufficient energy to escape from the liquid, so that
the vapor pressure increases as the temperature of the liquid increases. At this
temperature, the normal boiling point is achieved, where the vapor pressure is equal to 1
atm, all of the energy added goes into second phase change called vaporization.
The data showing the gas, liquid and solid equilibria is displayed in a diagram
called a phase diagram. The variables plotted are the pressure and temperature. The
lines on the phase diagram represent the temperatures and pressures at which two
phases can coexist in equilibrium, The unique point where all three phases (gas, liquid,
solid) can coexist is called the triple point.

Latent Heat

When you heat a substance, will a thermometer immersed in the substance always
indicate a temperature increase? Not necessarily, when the solid is melting or the liquid
is vaporizing, the temperature remains constant. Heat that produces a phase change
such as melting of ice (or boiling of water) without producing a temperature change is
called latent heat.

Vapor Pressure and the Clausius – Clapeyron Equation

The vapor pressure of the ice and liquid water does not increase in a linear fashion
with temperature. It increases in a more rapid, or exponential fashion. An equation that
fits quite well the vapor pressure data for the solid – gas and liquid – gas equilibria is the
Clapeyron - Clausius equation.

P = A x 10-ΔH/2.303 RT

where ΔH is the enthalpy of sublimation (J/mol) for the solid – gas equilibrium or the
enthalpy of vaporization for the liquid – gas equilibrium, R is the gas constant (8.3145
J/mol K), T is the temperature (K), and A is a constant with the units of pressure. By taking
the logarithm of both sides, we can convert the equation to a linear form

log P = log A – (ΔH/ 2.303 R) (1/T)

Note that the slope for the ice vapor pressure line is steeper than that for the water
vapor pressure line. This is because the enthalpy of sublimation of the solid is greater
than the enthalpy of vaporization of the liquid by an amount of energy equal to the
enthalpy of fusion.

ΔHsublimation = ΔHfusion + ΔHvaporization

The Enthalpy of Fusion of water

There is another way to determine the enthalpy of fusion of solid water (ice): by
making use of the temperature change of a known amount of liquid water when ice is
added to it. This method requires knowledge of the heat capacity of water. The experiment
can be carried out using a simple calorimeter made of Styrofoam coffee cups and a
thermometer to measure the temperature changes.
The energy required to melt ice, initially at 0oC, and warm the water from the melted
ice to the final temperature of the water in the calorimeter comes from the warm water
initially placed in the calorimeter. Using the conservation of energy principle we can write

ΔHcalorimeter + Δwarm water + ΔH ice water + ΔHfusion = 0

To calculate the enthalpy of fusion of the ice, we may assume that the enthalpy
change of the calorimeter is negligible (zero), and that the enthalpy change of the warm
water in the calorimeter is given by

ΔHwarm water = mCpΔT

where m is the mass of the warm water put in the calorimeter, Cp is the heat capacity of
water at constant pressure (4.184 J/g.K) and ΔT is the temperature change of the warm
water , Tfinal – T initial.

The enthalpy change of the ice water is given by a similar expression

ΔHice water = mCpΔT

where m is the mass of the added ice, Cp is the heat capacity of the melted ice, and ΔT
is the temperature change of the ice water , Tfinal - 0oC. Thus we can calculate each of
the first three terms in the above equation, which enables us to determine the remaining
unknown term, ΔHfusion.

OBJECTIVE

The objectives of this experiment are to determine the vapor pressure of water as
a function of temperature, to evaluate the enthalpy of vaporization of water from the slope
of the log P versus 1/T plot (Clausius Clapeyron expression) and to measure the enthalpy
of fusion of ice.

PROCEDURE

The Vapor Pressure of Water

1. Fill a 2-L beaker with tap water.

2. Fill a 10-ml graduated cylinder about 2/3 full of water, stopper it with your thumb,
and place it upside down in the beaker. The volume of trapped air should be
between 4.5 and 5.5 ml. If necessary, remove the graduated cylinder and adjust
the volume of trapped air by adding or removing water.
3. A length of copper wire wrapped around the base of the graduated cylinder can be
used to support the inverted graduated cylinder in a near vertical position.
4. Make sure that the graduated cylinder is at least 1 to 2 cm from the side of the
beaker.
5. Suspend a thermometer (0 to 100oC) so that the bulb of the thermometer is near
the volume of trapped air in the inverted graduated cylinder.
6. Using a hot plate, heat the water rapidly to about 75oC. Turn off the hot plate.
Note: Thorough stirring is necessary to ensure constant temperature throughout
the beaker before each reading is made.
7. After stirring, observe the meniscus in the inverted cylinder. Read and record the
volume you read on the scale at the bottom of the curved meniscus. The initial
volume should be about 10 ml. As the water cools, the volume of trapped gas will
decrease. Stir the water, and carefully read and record the temperature (nearest
0.05 mL) and corresponding volume (nearest 0.05 mL). (If the volume is greater
than 10 mL, you will have to wait until the volume decreases to 10 mL before you
make the first reading)
8. Continue reading and recording the volume and temperature at about 5oC intervals
until the water has cooled to about 50oC. Ice or cold water may be added, followed
by thorough stirring, to obtain temperatures below 60oC more quickly. You can use
a small beaker to dip out water so that the 2–L beaker does not overflow. Use a
glass stirring rod to do the stirring, being careful not to strike the fragile bulb of the
thermometer.
9. When the temperature reaches 50oC, record the last readings of temperature and
volume.
10. Then, wrap a towel around the beaker to protect your hands, and carry it to a sink.
Without disturbing the trapped volume of gas in the inverted graduated cylinder,
cautiously add cold tap water, allowing the water in the beaker to overflow into the
sink.
11. After 2 or 3 min. carefully pour off about 20 % of the water. (Don’t let any air escape
from the graduated cylinder). Add crushed ice and stir until the water temperature
is lowered to less than 5oC.
12. Read and record the volume and temperature with the same precision as before.
Later, in the calculations for your report, you will correct all volume readings by
subtracting 0.2 ml to compensate for the inverted meniscus. Record the
barometric pressure.
13. If we assume that the vapor pressure of water at 5oC is negligible in comparison
to atmospheric pressure, we can calculate the number of moles of air trapped in
the graduate, nair, by assuming that air behaves as an ideal gas

nair = PV5oC / RT
where P is the atmospheric pressure , V5oC is the volume measured at the lowest
temperature (< 5oC), R is the gas constant) and T is the temperature of the ice
water in kelvins.

14. For each of the temperature - volume measurements made between 75 and 50oC,
calculate the partial pressure (in torr) of air in the graduated cylinder

Pair = nair x RT/V

 15. For each temperature, we obtian the vapor pressure of water from Dalton’s law of
partial pressures:

Pwatet = Ptotal - Pair

where Ptotal is equal to the barometric pressure, ignoring the small pressure exerted
on the column of air by the weight of water above it in the beaker.

The Enthalpy of Vaporization of Water

1. Using the vapor pressure data obtained, calculate log P (torr) and 1/T(K) for data
point, retaining four significant figures. Plot log of P versus 1/T. Draw the best
straight line through the points. Calculate the slope of the plot, using two points on
the line that are far apart.

ΔHvap (J/mol) = -2.302 R x slope

Taking R = 8.314 J/mol K

The Heat of Fusion of Water

1. Weigh to the nearest 0.1 g and record the mass of a pair of nested 6-oz Styrofoam
cups to be used as a calorimeter.
2. Place 100 mL of water in 250–ml beaker and warm it to about 10oC above room
temperature.
3. Carefully pour all of the warm water into the Styrofoam cup calorimeter.
4. Reweigh and record the mass to the nearest 0.1 g.
5. Suspend a 0 to 100oC thermometer in the calorimeter by means of a wire from an
iron ring on a ring stand to reduce the risk of breaking the thermometer. Stir the
warm water with thermometer until the reading is constant. Record the temperature
to the nearest 0.2 oC.
6. Blot about 25 g crushed ice in a triple layer of absorbent paper towel.
7. Using a stirring rod, brush the ice into the calorimeter.
8. Stir until all of the ice has melted, noting the approximate temperature.
9. If needed, add more (blotted) ice until the temperature is about 10oC below room
temperature. Carefully note the lowest temperature attained and record it to the
nearest 0.2 oC.
10. Reweigh the calorimeter and record the mass to the nearest 0.1 g.
11. Calculate the enthalpy of fusion of ice (in joules per gram) from your data. Also
calculate the enthalpy of fusion in units of joules per mole and compare your results
with the accepted experimental value.
 Section: ______________________
Group No: ______________________
Members: Laboratory Schedule: ____________
_____________________________________
_____________________________________ Date Performed: _________________
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_____________________________________ Date Submitted: _________________
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Experiment
The Enthalpy of Vaporization and Enthalpy of Fusion of Water

REPORT SHEET

1. The Vapor Pressure of Water

Data

V (ml) T (K) Barometric Pressure

(atm)

Calculations

nair = PV / RT ______________ moles

Vcorrected = V-0.2 mL ______________ mL

Pair = nairRT/Vcorrected ______________ atm

Pwater = Ptotal – Pair ______________ atm

Vcorr (mL) T (K) Pair (atm) Pvapor (atm)

 2. The Enthalpy of Vaporization of Water

P (atm) T (K) Log P 1/T

Plot log P versus 1/T and draw the best straight line through the points; that is, draw the
line so that as many points as possible lie near the line and so that there are about as
many positive as negative deviations for individual points.

Calculate the enthalpy of vaporization from the slope of the Clapeyron – Clausius plot.

ΔHvap =-2.303 R x slope ____________ J/mol

The accepted value of ΔHvap is 42.6 kJ/mol

3. The Enthalpy of Fusion of Water

Mass of empty Styrofoam cups ________ g

Mass of empty Styrofoam cups + 100 mL warm water ________ g
Initial Temperature of warm water ________ oC
Mass of cups + warm water + ice ________ g
Final Temperature of water + melted ice ________ oC
Calculated heat of fusion of ice, ΔHfus ____________ J/g
Calculated the heat of fusion of ice
Calculated molar heat of fusion of ice, ΔHfus _______ J/mol
The accepted value of ΔHfus = 6.01 KJ/mol

Post-Laboratory Questions

1.) Would the method used for determining the vapor pressure of water be applicable
in the determination of the vapor of a volatile liquid such as ethanol? If so, explain
what change/s you would make in the experiment
2.) Why could contact with steam at 100oC produce a more severe burn on the skin
than contact with liquid water at the same temperature?

3.) Orange growers often spray water on their tress to protect the fruit in freezing
weather. Explain how the energy of the water – ice phase transition could provide
protection from freezing weather.

4.) What is the purpose of blotting the ice to remove excess water before adding the
ice to the calorimeter?

5.) Why is the 100 mL of water heated to about 10oC above room temperature before
the ice is added?

6.) When water is supercooled, it freezes at a temperature below 0.0oC. If 10.9 kJ of

heat is released when 2.00 mol of supercooled water at -15.0oC freezes, calculate
the molar enthalpy of fusion for ice at 0.0oC and 1 atm. Assume the molar heat
capacities for H2O (s) and H2O (l) are 37.5 J/K mol and 75.3 J/Kmol, respectively,
and are assumed temperature independent.
7.) The heat of vaporization of water at the normal boiling point, 373.2 K is 40.66
kJ/mol. The specific heart capacity of liquid water id 4.184 J/K g. and of gaseous
water is 2.02 J/Kg. Assume that these values are independent of temperature.
What is the heat of vaporization of water at 340.2 K.