E X P E R I M E N T 21

Liquids and Solids

The Vapor Pressure and Enthalpy

of Vaporization of Water

The Enthalpy of Fusion of Water

Purpose Individual atoms in molecules are linked by

chemical bonds that are “springy,” constraining the
• Determine the vapor pressure of water as a atoms that are bonded together to move like masses
function of temperature. connected by springs. As the molecules are heated,
the energies and amplitudes of their vibrations
• Use the vapor pressure data to make a
increase.
Clausius–Clapeyron plot [Ln(P) versus 1/T ].
To summarize, the energy we put into a molecule
• Determine the enthalpy of vaporization of water is stored as translational, rotational, and vibrational
from the slope of the Ln(P ) versus 1/T plot. motions of the molecules.
When we cool a substance, we remove energy
• Measure the enthalpy of fusion of ice using a
from it, and molecular motions slow down. We reach
Styrofoam-cup calorimeter.
the lowest temperature possible, called absolute
zero, when we have removed as much energy as pos-
sible from the substance. At this temperature, molec-
Introduction ular motion nearly ceases.
As we remove energy from gaseous molecules, at
Heat and molecular motion
some temperature they will condense into a liquid
Our accumulated knowledge about the effect of heat and eventually into a solid, because there are attrac-
provides a rather detailed picture of what happens tive forces between molecules caused by dipole–
when you heat (or transfer energy to) a substance. dipole (or induced-dipole) attraction. To separate the
On an atomic or molecular scale, heating increases molecules in a solid to the distances characteristic of
the motion of the atoms. If the atoms are linked by those in a gas, we must do work against the opposing
chemical bonds to form a molecule, we can focus our attractive forces. (Recall that work ⫽ force ⫻ dis-
attention not on individual atoms but on the mole- tance.) This work is the energy required to melt the
cule as a whole. solid and vaporize the liquid.
If we heat a molecule, it moves about faster. This Now imagine the following experiment. Suppose
motion of the molecule’s center of mass is called we begin adding energy to ice at a uniform rate while
translational motion (meaning “motion from place to measuring the temperature. For water, a plot of tem-
place”). Gaseous molecules have a substantial frac- perature versus energy (or time) would look like Fig-
tion of their total energy stored as kinetic energy of ure 21-1. As we warm the solid, the molecules begin
translation. They move about rapidly, bouncing off to move. On average, the molecules in the solid are
one another and off the walls of their container. not going anywhere. They simply begin to bounce
Molecules can also rotate about their centers of around in the cage formed by their surrounding
mass; as a gas is heated, the molecules rotate faster. neighbors. In effect, they are like gas molecules con-
Energy is stored in the rotating molecules, just as fined to a very small container not much larger than
energy is stored in a rotating flywheel. the molecule itself. At the same time, the amplitude

21-1
21-2 Liquids and Solids

140

120
H2O (g)
ΔHvap

100
H2O (liq) H2O (g)

80
t (°C)

60
H2O (liq)

40

20

ΔHfus
0
H2O (s) H2O (liq)
H2O (s)
–20
10 20 30 40 50
Energy (kJ)

FIGURE 21-1 The temperature versus energy heating curve for one mol of water.

of vibration of the atoms bonded together increases, Because liquid molecules have a greater average
and the molecules may begin to rotate in their small energy than molecules in the solid, a greater number
cages. A few molecules at the surface of the ice may of them can escape into the gas phase, so the vapor
acquire enough kinetic energy to break free from the pressure of the liquid is greater than that of the
solid to become gas molecules. The number of gas solid. As we continue to heat the liquid, a greater
molecules may be large enough to produce a measur- number of molecules acquire sufficient energy to
able pressure. This pressure is called the vapor pres- escape from the liquid, so the vapor pressure
sure of the solid. increases as the temperature of the liquid increases.
At the temperature we call the melting point, the At the temperature we call the normal boiling point,
amplitude of the motions increases to the point where the vapor pressure is equal to 1 atm, all of the
where the forces between neighboring molecules are energy added goes into a second phase change,
no longer sufficient to hold them in fixed positions. called vaporization. If the container is not closed, the
The regular structure of the solid breaks down, form- vapor pressure cannot exceed 1 atm, so the liquid
ing “holes” (or vacancies) in the solid. The molecules begins to boil, forming bubbles of vapor that escape
can move more freely, jumping from hole to hole. from the liquid. If we keep adding energy, we eventu-
This produces a phase change—the solid becomes a ally convert all of the liquid to the gas phase.
liquid. The liquid has a dramatically lower viscosity The data showing the gas, liquid, and solid equi-
than the solid, so the material adopts the shape of libria can be displayed in a diagram called a phase
the container. diagram. The variables plotted are the pressure and
On average, the molecules of the liquid have temperature. The phase diagram for water between
more energy than those of the solid. The energy ⫺20 and ⫹20 ⬚C is shown in Figure 21-2. The lines
required to change the solid into a liquid is called the on the phase diagram represent the temperatures
heat of fusion or the enthalpy of fusion. and pressures at which two phases can coexist in
 Liquids and Solids 21-3

Vapor pressure
and the Clausius–Clapeyron equation
Look again at Figure 21-2. Note that the vapor pres-
sure 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 shown in Fig-
ure 21-2 for the solid–gas and liquid–gas equilibria is
the Clausius–Clapeyron equation:

P ⫽ A ⫻ e⫺⌬H>RT (1)

where ⌬H is the enthalpy of sublimation (J/mol) for

the solid–gas equilibrium or the enthalpy of vapor-
ization for the liquid–gas equilibrium; R is the gas
constant (8.314 J • mol⫺1 • K⫺1); T is the Kelvin tem-
perature (K); and A is a constant with the units of
pressure.
By taking the natural logarithm of both sides of
Equation (1), we can convert the equation to a linear
form:

⌬H 1
Ln(P ) ⫽ Ln(A) ⫺ a b (2)
R T

A plot of Ln(P) versus 1/T gives a straight line whose

slope is equal to ⫺⌬H/R (see Figure 21-3). Note that
FIGURE 21-2 The pressure versus temperature
the slope for the ice vapor pressure line is steeper
phase diagram for water in the range 20 C to
20 C. The lines show where two phases can than that for the water vapor pressure line. This is
coexist in equilibrium. At the triple point, all because the enthalpy of sublimation of the solid is
three phases coexist in equilibrium. greater than the enthalpy of vaporization of the liq-
uid by an amount of energy equal to the enthalpy of
fusion:
equilibrium. The unique point where all three
⌬Hsublimation ⫽ ⌬Hfusion ⫹ ⌬Hvaporization (3)
phases (gas, liquid, solid) can coexist is called the
triple point. If we have vapor pressure data for the liquid, we
Now recall the experiment where we imagined can determine the enthalpy of vaporization of the liq-
that we began to heat a solid initially at a low tem- uid. If we have vapor pressure data for the solid, we
perature. Figure 21-1 shows how the temperature can determine the enthalpy of sublimation of the
changes as we add energy to the substance, while solid. The difference between them gives the enthalpy
Figure 21-2 shows how the vapor pressure of ice and of fusion of the solid, as shown by Equation (3).
liquid water changes with temperature.
The enthalpy of fusion of water
Latent heat
There is another way to determine the enthalpy of
When you heat a substance, will a thermometer fusion of solid water (ice): making use of the temper-
immersed in the substance always indicate a temper- ature change of a known amount of liquid water
ature increase? Not necessarily. Figure 21-1 shows when ice is added to it. This method requires a
that while the solid is melting or the liquid is vapor- knowledge of the heat capacity of water. The experi-
izing, the temperature remains constant. Heat that ment can be carried out by using a simple calorime-
produces a phase change such as the melting of ice ter made of Styrofoam coffee cups and a thermome-
(or the boiling of water) without producing a temper- ter to measure the temperature changes.
ature change is called latent heat. A thermometer, It takes energy to melt ice which is initially at 0 ⬚C
therefore, can be used to measure temperature and to warm the water from the melted ice to the
changes but cannot always be used to measure final temperature of the water in the calorimeter.
energy changes. That energy comes from the warm water initially
21-4 Liquids and Solids

Ln(P) vs. 1/T(K) where m is the mass of the added ice; Cp is the heat
capacity of the melted ice water (as before); and ⌬T
3.0
is the temperature change of the melted ice water,
Tfinal ⫺ 0 ⬚C.
y = –5373.5x + 21.2 Thus, we can calculate each of the first three
2.5 r 2 = 1.0
terms in Equation (4), which enables us to determine
the remaining unknown term, ⌬Hfusion.
2.0 Water

Experimental Procedure
1.5 Triple point
Ln (P/torr)

Special Supplies: If available, an electric stirrer/hot

1.0 plate and magnetic stirring bar (egg shaped, 40-mm
length); 7 ⫻ 300 mm stirring rods, if hand stirring is to

Ice be used; 1 ⫻ 0.01 mL disposable borosilicate glass sero-

0.5
y = –6136.0x + 24.0 logical pipets (Corning 7079-1N or Kimble 72120-
r 2 = 1.0 11100); 1/8-in. ID ⫻ 1/32-in. wall thickness silicone rubber
0.0 tubing; rubber septa (size 4 natural rubber septa avail-
able from the Aldrich Chemical Co. as catalog number
Z10,073-0); 5-mL disposable plastic Luer-tip syringes to
–0.5
0.0033 0.0035 0.0037 0.0039 0.0041 use as filling devices; 1-L tall-form Berzelius beakers
1/T(K) (Corning 1060-1L or Kimble 14030-1000); 3/4-in. width
water-resistant labeling tape (TimeMed tape or equiva-
FIGURE 21-3 A Ln(P) versus 1/T lent, or electrician’s tape); crushed ice; 6-oz Styrofoam
(Clausius–Clapeyron) plot for water in the range
cups; 0–110 ⬚C thermometer (or, if available, a digital
20 C to 20 C. The slope for the water line
segment is 5373 K. The slope for the ice line thermometer reading to 0.1 ⬚C, such as the Hanna
segment is 6136 K. The value of r 2  1.0 Instruments Inc. CheckTemp 1 HI 98509); string or 22-
indicates a good fit to a straight line. The
gauge copper wire.
enthalpy of vaporization can be calculated from
the slope of the water line segment and the
enthalpy of sublimation from the slope of the ice
line segment: H  R  slope, where R is the gas SAFETY PRECAUTIONS:
constant in units of J/mol · K. ! Determining the enthalpy of
vaporization of water involves heating
one liter of water in a beaker. If the
placed in the calorimeter. Using the conservation of beaker is supported on an iron ring over
energy principle, we can write a burner, make sure that a second ring or
⌬Hcalorimeter ⫹ ⌬Hwarm water ⫹ ⌬Hice water ⫹ ⌬Hfusion ⫽ 0 beaker clamp is used to secure the beaker
(4) so that it cannot tip over.

We want to calculate the enthalpy of fusion of the

ice. Assume that the enthalpy change of the
calorimeter (Styrofoam cups plus thermometer) is NOTES TO INSTRUCTOR
negligible (zero), and that the enthalpy change of the
Only students working very efficiently can complete
warm water in the calorimeter is given by
all three parts of the experiment and the report in a
⌬Hwarm water ⫽ m Cp ⌬T (5) 3-hour lab period. We suggest three possible options:
allow two lab periods to complete the whole experi-
where m is the mass of the warm water put in the
ment; assign students parts 1 and 2 only; or have
calorimeter; Cp is the heat capacity of water at con-
students omit part 1 (the gathering of vapor pressure
stant pressure (4.18 J • g⫺1 • K⫺1); and ⌬T is the tem-
data for water) and do parts 2 and 3, using vapor
perature change of the warm water, Tfinal ⫺ Tinitial.
pressure data for water in the 50 to 75 ⬚C range from
The enthalpy change of the melted ice water is
Table 3 of the Appendix.
given by a similar expression,
A stirrer/hot plate and digital thermometer are
⌬Hice water ⫽ m Cp ⌬T (6) conveniences. If a stirrer/hot plate is not available,
 Liquids and Solids 21-5

the solution can be heated on a simple hot plate or

over a Bunsen burner while stirring by hand with a
stirring rod. Likewise, a digital thermometer allows
more accurate and convenient temperature measure- 1-mL glass
disposable
ments, but an ordinary thermometer can be used,

1ml in 1/100
serological
estimating the temperature to the nearest 0.5 ⬚C. pipets
If the serological pipets are precut and lightly fire
Rubber
polished beforehand, students can move ahead more septum
quickly to the vapor pressure measurements. (Any
cotton plugs in the pipets should be removed. This is
most easily done by connecting them to a water tap

1ml in 1/100
0

and forcing them out by water pressure.) In our expe-

.1 .1
rience, polystyrene serological pipets are trouble- Tape
some when used with water, because water does not .2 .2

wet the polystyrene, making it very difficult to .3 .3 0

remove trapped air bubbles.

.4 .4
132 mm .2 .2

.5 .5
3 cm .3 .3

.4 .4
.6 .6
.5 .5
1. The Vapor Pressure of Water Assemble the .7 .7
.6 .6
microscale vapor pressure measuring device as
.7 .7
.8 .8
shown in Figure 21-4. You will need two 1-mL .8 .8

borosilicate glass serological pipets (with 0.01-mL Tape

graduations), a size 4 rubber septum (or stopple), a
6-cm length of silicone rubber tubing (1/8 in.-ID ⫻ A
1
/32-in. wall thickness), and two 10-cm lengths of tape Silicone
(TimeMed or electrician’s tape). rubber
Take one of the 1-mL serological pipets and, using tubing
STIR HEAT
a glass knife or glass tubing cutter or triangular file,
score it precisely at the 0 mark and the 0.85-mL
mark. In turn, moisten the score, and grasp the tub- B
ing with both thumbs opposite the score. Apply pres-
sure with your forefingers pushing against your
FIGURE 21-4 (A) Enlarged view of the
thumbs. The glass pipet will normally break cleanly construction of the microscale apparatus for
with only light pressure. Then lightly fire polish each measuring vapor pressure. (B) Overall view of
end where the pipet has been cut, just enough so that the apparatus.
the sharp edge is just slightly rounded so that it will
not cut the rubber tubing. (200-grit sandpaper can
also be used to take off the sharp edge of the glass.) Then fold over the ends of the tape, so that the adhe-
Take the second pipet and make a single score at the sive sides of the tape are sealed to each other to
0.85-mL mark. Snap off the bottom end of the pipet, make a semirigid connection at the bottom of the
and lightly fire polish the end of the pipet. pipets.
Next, cut a 6-cm length of silicone rubber tubing Next, turn the assembly upside down and insert
and push each end onto the lower ends of the pipets the untaped end of the shorter pipet into a beaker
to make a connecting loop. The ends of the rubber containing deionized water. Apply suction to draw
tubing should come up to about the 0.82-mL mark. the water up into the two pipets. (This can be done
When you face the assembly, make sure that you can with a 5-mL Luer-tip syringe and short length of sili-
easily read the graduation numbers on the pipets. cone rubber tubing connected to the end of the
Now cut a 10-cm length of TimeMed or electri- longer pipet.) When the assembly is turned upright,
cian’s tape and lay it on the bench top with the adhe- the water level should be somewhere between the
sive side up. Lay the connecting rubber loop in the 0.35- and 0.40-mL marks in both pipets. Add or
middle of the tape, with the two pipets parallel and remove water as necessary. Take care to eliminate all
spaced about 3 cm apart and with the top edge of the bubbles in the pipets and connecting rubber tubing
tape just even with the ends of the rubber tubing. loop before proceeding to the next step.
21-6 Liquids and Solids

Next, get a rubber septum and force the smaller water bath to cool too rapidly—about a degree per
diameter end (3.4-mm ID) of the septum onto the minute is satisfactory. Take readings about every
unsealed end of the shorter pipet. This makes a tight 5 ⬚C as the water bath cools to about 50 ⬚C, stirring
seal, trapping a small volume of air and water vapor. when you are not taking a reading. Cold water or
Make sure that the septum is forced on as far as it small amounts of ice may be added, followed by
will go, so that it seals off the end of the pipet. (The thorough stirring, to obtain temperatures below
small end of the septum will come down to about the 60 ⬚C more quickly. You can use a small beaker to dip
0.04-mL mark.) Then take another 10-cm piece of out water so that the 1-L beaker does not overflow.
tape, adhesive side up as before, and lay the pipets When the temperature reaches 50 ⬚C, record the
down on the tape with the two pipets parallel and the last readings of temperature and volume. Then wrap
top edge of the tape just below the rubber septum, as a towel around the beaker to protect your hands, and
shown in Figure 21-4(A). Fold over the ends of the carry it to a sink. Without disturbing the vapor pres-
tape to make a second connection. Now you can use sure apparatus, cautiously add cold tap water, allow-
the longer pipet end as a handle, and the whole ing the water in the beaker to overflow into the sink.
assembly will be semirigid. After a minute or so, carefully lift out the vapor pres-
Fill a tall-form 1-L beaker nearly to the brim with sure apparatus, taking care to keep it upright, and fill
water. If available, a stirrer/hot plate is convenient the 1-L beaker with a slurry of crushed ice and water.
for making measurements, along with a Teflon- Place the vapor pressure apparatus in the ice bath,
covered magnetic stirring bar. (We find that an egg- and stir until the temperature is below 3 ⬚C (prefer-
shaped bar gives good stirring and is less prone to ably less than 1 ⬚C). When the temperature is nearly
flopping around.) If you are going to heat the beaker constant, take readings of the temperature and the
over a gas burner and stir by hand, place an iron ring volume of trapped gas. Be careful to take this reading
or beaker clamp around the upper portion of the accurately because it corresponds to the volume of
beaker to reduce the risk of it tipping over. (Caution: air in the apparatus, a crucial quantity in subsequent
Hot water can produce very painful burns.) Use a calculations.
sturdy stirring rod, about 300 mm in length, to do Read and record the barometric pressure and
the stirring, and be careful not to strike the fragile temperature of the barometer.
bulb of the thermometer. Calculations: If we assume that the vapor pres-
Put the microscale vapor pressure assembly in sure of water at 3 ⬚C is negligible in comparison to
the beaker up against the side of the beaker so that it atmospheric pressure, we can calculate the number of
will be out of the way of the stirrer if you are using a moles of air trapped in the pipet, nair, by assuming
magnetic stirrer/hot plate. (A piece of tape can be that air behaves as an ideal gas:
used to hold it upright in place.) Thorough stirring is
PV3 °C
necessary to ensure constant temperature through- nair ⫽ (7)
RT
out the beaker before each volume and temperature
reading is made. Using string or copper wire, sus- where P is the atmospheric pressure (in torr); V3 ⬚C is
pend the thermometer so that the bulb is located the volume (in milliliters) measured at the lowest
approximately at the interface between the water and temperature (⬍3 ⬚C); R is the gas constant (6.237 ⫻
trapped air in the pipet, and so you can easily see the 104 mL • torr • mol⫺1 • K⫺1), and T is the Kelvin tem-
temperature graduations. (A digital thermometer is perature of the ice water.
even more convenient.) For each of the temperature–volume measure-
Stir the solution until the temperature reading is ments made between 75 ⬚C and 50 ⬚C, calculate the
constant; then record the initial volume of air and partial pressure (in torr) of air in the pipet from the
water vapor to the nearest 0.005 mL. (Read the vol- equation
ume at the bottom of the curved meniscus, as you do
RT
when reading the volume in a graduated cylinder or Pair ⫽ nair ⫻ (8)
V
buret.) Rapidly heat the water until the volume of
trapped gas is about 0.8 mL (this typically requires a For each temperature, we obtain the vapor pressure
temperature of about 80 ⬚C if the initial volume at of water from Dalton’s law of partial pressures:
room temperature is about 0.4 mL). Then turn down
Pwater ⫽ Ptotal ⫺ Pair (9)
the heat (or turn it off) and stir the solution nearly
continuously (if you are stirring by hand), pausing where Ptotal is equal to the barometric pressure,
only to take nearly simultaneous readings of the vol- ignoring the small pressure exerted on the column of
ume of trapped gas and temperature. Don’t allow the air by the weight of water corresponding to the dif-
 Liquids and Solids 21-7

ference in the water heights in the two arms of the

apparatus as the gas expands. (If desired, a correc-
tion for this effect can be easily made, since it is a
linear function of the volume reading of the gas.)

2. The Enthalpy of Vaporization of Water Using

the vapor pressure data obtained in part 1, calculate
the natural logarithm of the pressure, Ln(P) (torr),
and 1/T (K) for each data point, retaining four signif-
icant figures. Plot Ln(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. (A spreadsheet program, such as Microsoft
Excel or another graphing program, also may be used
to make the plot and to determine the best-fit
straight line and slope, if you have access to the pro-
gram and know how to use it. Figure 21-3 is an exam-
ple of a plot produced using Excel.)

Ln(P ) 2 ⫺ Ln(P ) 1
slope ⫽ (10)
(1>T ) 2 ⫺ (1>T ) 1

(Note that the slope is a negative number, with units

of Kelvins.) Calculate the enthalpy of vaporization
from the relation

⌬Hvap (J>mol) ⫽ ⫺R ⫻ slope (K) (11)

taking R ⫽ 8.314 J • mol⫺1 • K⫺1.

3. The Enthalpy of Fusion of Ice Weigh to the near-

est 0.1 g and record the mass of a pair of nested 6-oz
Styrofoam cups to be used as a calorimeter. Place
100 mL of water in a 250-mL beaker and warm it to
about 10 ⬚C above room temperature. Carefully pour
all of the warm water into the Styrofoam-cup
calorimeter. Reweigh and record the mass to the
nearest 0.1 g. Put a digital thermometer in the
calorimeter or suspend a 0 to 100 ⬚C thermometer in
the calorimeter by means of a string or copper wire
from an iron ring on a ring stand to reduce the risk of
breaking the thermometer (see Figure 21-5). Stir the
FIGURE 21-5 A Styrofoam-cup calorimeter. The
warm water with the thermometer until the reading beaker provides extra stability so that the nested
is constant. Record the temperature to the nearest cups won’t tip over.
0.2 ⬚C.
Blot about 25 g of crushed ice in a triple layer of
absorbent paper towels to remove as much of the
adhering water as possible. Using a stirring rod,
brush the ice into the calorimeter. Stir until all of the
ice has melted, noting the approximate temperature.
If needed, add more (blotted) ice until the tempera-
ture is about 10 ⬚C below room temperature. Care- Calculations: Calculate the enthalpy of fusion of
fully note the lowest temperature attained, and ice (in joules per gram) from your data, using Equa-
record it to the nearest 0.2 ⬚C. To get the mass of ice tions (4) to (6). Also calculate the enthalpy of fusion
added, reweigh the calorimeter and record the mass in units of joules per mole and compare your results
to the nearest 0.1 g. with the accepted experimental value.
21-8 Liquids and Solids

CONSIDER THIS Bibliography

You can use the microscale vapor pressure apparatus De Muro, J. C.; Margarian, H.; Mikhikian, A.; No, K. H.;
to determine the vapor pressure of other pure Peterson, A. R. “An Inexpensive Microscale Method
volatile liquids, such as alcohols (methanol, ethanol, for Measuring Vapor Pressure, Associated
2-propanol, etc.), or of solutions, where the effect on Thermodynamic Variables, and Molecular Weights,”
the vapor pressure of adding a nonvolatile solute to J. Chem. Educ. 1999, 76, 1113–1116.
a volatile solvent can be observed. Levinson, G. S. “A Simple Experiment for Determining
Water has a considerably higher boiling point and Vapor Pressure and Enthalpy of Vaporization of
lower vapor pressure than other molecules of similar Water,” J. Chem. Educ. 1982, 59, 337.
or larger molar mass. For example, dinitrogen
(N2), methane (CH4), methanol (CH3OH), acetone
[O£C(CH3)2], and dimethyl ether (CH3OCH3) all have
lower boiling points and higher vapor pressures than
water at the same temperature. How might this be
explained?
If the intermolecular forces between molecules of
a substance were very small, what effect would you
expect this to have on the boiling point and vapor
pressure of the substance? Give one or two specific
examples of molecules where you might expect the
intermolecular forces to be very small. What would
you look for? Should the atoms of the molecules be
large or small? Why might this matter? Should the
electronegativity difference of the atoms bonded to
one another be large or small? Why might this matter?
Use the information presented in Figure 21-3 to
calculate a value for the enthalpy of fusion of water.
Compare it to the literature value of 6009 J/mol.
REPORT 21
Liquids and Solids Name __________________________________________________

The Vapor Pressure and Enthalpy Date ______________________ Section ____________________

of Vaporization of Water
Locker ___________________ Instructor__________________
The Enthalpy of Fusion of Water

Data and Calculations

1. The vapor pressure of water

Data

V(mL) t(°C) Barometric pressure (torr)

(t ⬍ 3 °C)

Calculations

Calculate the moles of air in the graduated cylinder, using the temperature–volume data at the lowest temper-
ature (t ⬍ 3 °C).

PV
nair ⫽
RT

where P is the barometric pressure (in torr), V is the volume (in milliliters) at ice-water temperature,
R ⫽ 6.237 ⫻ 104 mL • torr • mol⫺1 • K⫺1, and T is the Kelvin temperature of the ice water.

nair: mol

Calculate each entry in the following table, using your volume–temperature data and the equations

T(K) ⫽ t (°C) ⫹ 273.2

nairRT
Pair ⫽
V

21-9
(Calculate Pair in units of torr, using the value of nair from the previous step.) Then calculate Pwater using
Dalton’s law,

Pwater ⫽ Ptotal ⫺ Pair

where Ptotal is the barometric pressure. (Calculate Pwater in units of torr.)

V(mL) T(K) Pair(torr) Pwater(torr)

2. The enthalpy of vaporization of water

Data

Use your data from part 1. (If you did not do part 1, your instructor will direct you to a source of vapor
pressure–temperature data.)

Calculations

Write the values of the vapor pressure of water and the temperature from the table in part 1 (or another
source, if your instructor so directs) in the following table, and calculate for each pair of pressure–
temperature values the log of the pressure and the reciprocal of the temperature, retaining four significant
figures.

P(torr) T(K) Ln(P) 1/T, (K1)

Plot Ln P(torr) versus 1/T(K) 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. Or better, if you have access to a computer with a spreadsheet program such as Excel,
use the graphing capabilities of the spreadsheet to make a plot of your data points and add a best-fit linear
trendline.

21-10
REPORT 21 SHEET 2

Name __________________________________________________ Date ______________________

Ln (P/torr) for water versus 1/T (in reciprocal kelvins, K⫺1) in the range 50–75 °C

5.8

5.6

5.4

5.2
Ln (P/torr)

5.0

4.8

4.6

4.4

4.2
0.00285 0.00290 0.00295 0.00300 0.00305 0.00310

1/T(K–1)

21-11
Calculate the enthalpy of vaporization from the slope of the Clausius–Clapeyron plot. Choose two points that
lie on the straight line you have drawn through your data points on the Ln(P) versus 1/T plot, preferably points
that are near each end of the line. Calculate the slope of the line from the equation

Ln(P ) 2 ⫺ Ln(P ) 1
slope ⫽
(1>T ) 2 ⫺ (1>T ) 1

Calculate the enthalpy of vaporization from the equation

⌬Hvap ⫽ ⫺R ⫻ slope

J/mol

The accepted value for ⌬Hvap is 42.6 kJ/mol. (The value given in most textbooks of 40.7 kJ/mol is the enthalpy
of vaporization at 100 °C. The value given here is the average value for the temperature range 50–75 °C.)

your value ⫺ accepted value

percentage difference ⫽ ⫻ 100% ⫽ %
accepted value

3. The enthalpy of fusion of water

Calculations

Mass of empty Styrofoam cups: g

Mass of Styrofoam cups ⫹ 100 mL warm water: g

Initial temperature of warm water: °C

Mass of cups ⫹ warm water ⫹ ice: g

Final temperature of water ⫹ melted ice: °C

Data

From your data, calculate the enthalpy of fusion of ice using Equations (4) to (6).

⌬Hcalorimeter ⫹ ⌬Hwarm water ⫹ ⌬Hice water ⫹ ⌬Hfusion ⫽ 0

0 ⫹ mww CP ⌬Tww ⫹ miw CP ⌬Tiw ⫹ ⌬Hfusion ⫽ 0

where mww is the mass of the warm water, ⌬Tww the temperature change of the warm water [see Equation (5)],
miw the mass of the ice water (mass of ice added), and ⌬Tiw the temperature change of the ice water [see
Equation (6)]. Show your calculation.

Calculated heat of fusion of ice in joules per gram of water, ⌬Hfusion: J/g

Calculate the heat of fusion of ice in joules per mole of water (i.e., for 18.0 g of water).

Calculated molar heat of fusion of ice, ⌬Hfusion: J/mol

The accepted value of ⌬Hfusion ⫽ 6.01 kJ/mol.

Calculate the percentage difference between your value and the accepted value.

your value ⫺ accepted value

percentage difference ⫽ ⫻ 100% ⫽ %
accepted value

21-12
REPORT 21 SHEET 3

Name __________________________________________________ Date ______________________

CONSIDER THIS

1. Water has a considerably higher boiling point and lower vapor pressure than other molecules of similar or
larger molar mass. For example, dinitrogen (N2), methane (CH4), methanol (CH3OH), acetone [O£C(CH3)2], and
dimethyl ether (CH3OCH3) all have lower boiling points and higher vapor pressures than water at the same
temperature. How might this be explained?

2. If the intermolecular forces between molecules of a substance were very small, what effect would you
expect this to have on the boiling point and vapor pressure of the substance? What properties would you look
for in a molecule in order to have a low boiling point and high vapor pressure? Should the atoms of the
molecules be large or small? Why might this matter? Should the electronegativity difference of the atoms
bonded to one another be large or small? Why might this matter? Give two or three examples of molecules
where you might expect the intermolecular forces to be very small.

Questions
3. Use the information presented in Figure 21-3 to calculate a value for the enthalpy of fusion of water.
Compare it to the literature value of 6009 J/mol.

4. Why would contact with steam at 100 °C produce a more severe burn than contact with liquid water at the
same temperature?

5. Orange growers often spray water on their trees to protect the fruit in freezing weather. Explain how the
energy of the water B ice phase transition could provide protection from freezing weather.

21-13