Clausius-Clapeyron Equation

INTRODUCTION This is the Clausius-Clapeyron equation, which gives us

The relationship between the vapor pressure of a liquid and a way of finding the heat of vaporization, the energy that
the temperature is shown graphically as: must be supplied to vaporize a mole of molecules in the
liquid state.

A plot of ln P vs. 1/T has the form of a straight line. Com-

pare equation (1) to
Vapor Pressure

y = mx + b (2)
which is the equation for a straight line. In equation (1),
ln P is y, 1/T is x, and -∆Hvap/R is m.

In today’s experiment, you will measure the vapor pressure

of water over a range of temperatures, plot the data, measure
the slope of the line, and then calculate ∆Hvap for water.

The method you will use to measure the vapor pressure will
require careful readings of the volume of air and water vapor
Temperature
in an inverted graduated cylinder immersed in a beaker of
The same data, if “massaged”, that is, expressed in a different water. You will half fill the graduated cylinder with water,
manner, can be shown graphically as a straight line: and then immerse it upside down in enough water to cover
the cylinder. Then you will warm the water in the beaker. As
the temperature increases, the air in the graduated cylinder
expands, and the vapor pressure of the water increases. Once
the water in the beaker reaches a high enough temperature,
the assembly is allowed to cool. A series of volume and
temperature readings are taken, and then the water in the
beaker is iced. At ice temperatures, the vapor pressure of
water is negligible. The volume at that point is due to the air
alone, within the limits of the measurements. This volume is
recorded. Using the gas law equation, the number of moles
of air in the cylinder is calculated:
PVcold
n
RT cold (3)
Then, for each of the other temperatures and volumes
This linear relationship can be expressed mathematically measured, the pressure from this number of moles of air
as is calculated. The total pressure in the graduated cylinder
H vap 1 is atmospheric pressure. The difference, then, between the
ln P C (1)
R T pressure caused by the air and the atmospheric pressure must
be due to the vapor pressure of water. This is an application
of Dalton’s law of partial pressure:
where ln P is the natural logarithm of the vapor pressure,
Ptotal = P1 + P2 + … (4)
∆Hvap is the heat of vaporization, R is the universal gas
constant (8.31 J·K-1mol-1), T the absolute temperature, and
C a constant (not related to heat capacity).

1
 EQUIPMENT the water in the beaker, and record the temperature (to the
Work in pairs nearest degree) and the volume of gas in the cylinder (to
Special supplies: the nearest 0.01 ml).
• 1-1000 ml beaker with components
From your drawer: Remember that the cylinder is inverted. In this diagram:
• 1 thermometer
• 1 stirring rod
5.0
From the large drawer: gas
• 1 Bunsen burner
• Ring stand and hardware
EXPERIMENT
Assemble the components from the beaker on the thermom-
eter as shown in the diagram. water
6.0
Cork
the volume of gas is about 5.63 ml. The meniscus is exag-
gerated in the drawing.

Record temperatures and volumes every 5°C or so until

Rubber loop you have 5 or 6 readings. You can hasten the cooling by
Copper wire
adding small amounts of water or ice to the beaker, but the
temperature in the beaker must be uniform when you make
the measurements. This requires good stirring. After the 5th
or 6th reading, it will be time to lower the temperature of
Vinyl loop the water in the beaker to below 5°C. Use a small beaker
to remove about half of the water in the beaker, taking care
that you do not disturb the water in the inverted cylinder.
1000 ml Fill the beaker with ice, and stir. If all of the ice melts, and
beakeeer the temperature is still above 5°C, remove more water, and
add more ice. Stir the water in the beaker for a few min-
utes to allow the temperature of the water in the cylinder
to equilibrate with the temperature in the beaker, and then
make the cold temperature and volume reading

Take great care with this last measurement, because all of

your data will become tainted if this reading is off.

View the assembled apparatus at the instructor’s desk as

needed. Before placing the graduated cylinder/
thermometer assembly into the beaker, fill the cylinder DATA
with deionized water. There are two types of tubes, if Barometric Pressure: 23.76
Torr
you have the cone tube, fill to 10 mL, if you have the flat
tube, fill to 7 mL. The beaker should have around 800 Volume Temperature
ml of deionized water in it. Now place the tip of your 3.9 75
ml °C (highest T)
finger over the mouth of the cylinder, and invert the
3.5 70
assembly and lower it into the beaker. Once the mouth of ml °C
the cylinder is submerged into the water in the beaker, 65
3.2
you can release your finger. Clamp the cork at the top of ml °C
the thermometer so that the assembly is firmly in place. 3.0 ml 60 °C
The inverted cylinder should be just above the bottom of
2.8 ml °C
the beaker, and the water in the beaker should just cover 55
the top of the cylinder. Heat the beaker with a Bunsen 2.7 50
ml °C
burner turned on to its maximum heat output until the
water reaches 72 to 75°C. Turn off the burner. The Cold: 1.9 ml °C (to be < 5 °C)
volume of entrapped gas in the cylinder should nearly 2
fill the cylinder. If gas bubbles out of the cylinder at
the top temperature, do not be concerned. Stir
 CALCULATIONS (Solving for the Heat of Vaporization of Water)

Use the cold temperature data and equation (3) to find the number of moles of air in the cylinder.
Use R = 62.4 L·torr·K-1mol-1. Convert the temperature to Kelvins, and the volume to liters.
2.602E-6
Show the mathematical setup here: moles of air __________
n=23.76*1.9E-3/62.4*278
n=PV/RT.

he table below:

For ( ) an (2), rewrite the volume and temperature data in the table below, converting the units to liters and
(3) For each of the higher temperature sets of volume and temperature, use the value for n just calculated, along
with the V and the T, to calculate the pressure of the air using the gas law.
(4) After the pressure of air at each tempera-ture is calculated, subtract the value from the atmospheric pressure
recorded from the barometer. This will be the vapor pressure of water at that temperature.
( ) sin (4), ress the ln button on our calculator an recor ln alue in the table.
( ) Calculate an recor the alue of for each te erature. ou shoul roun our calculate alues to 3
si ni cant i its. nRT/V=p

2 3 P air / torr 4 P vapor / torr 1 1

Volume / L T /K ln P /K
T
0.0039 348 14.48 9.27 5.23 2.87E-3

0.0035 343 15.91 7.84 5.06 2.92E-3

0.0032 338 17.15 6.6 4.89 2.96E-3

0.0030 18.02 5.73 4.75

333 3.00E-3
0.0028 328 4.74 4.56 3.04E-3
19.01

0.0027 323 19.423 4.327 3.10E-3

4.46
cold: 0.0019 278 23.75

ou will lot the last two colu ns of the ate fro this table on the ne t a e. fter the oints are lace on the ri ,
use a trans arent ruler to raw the best strai ht line throu h the oints. his esti ate best fit line shoul e ten the full
wi th an hei ht of the ri . t is li el that none of the oints will actuall touch the line ou raw. f ou loo at the
line b hol in the a er u so that ou are si htin alon the line fro one of its en s, then the oints shoul a ear
e enl scattere about the line. fter the line is ro erl lace , a e two ar s on the line, one near the extreme left,
one near the extreme right side of the line. If possible, make the marks where the line crosses the intersection
of two grid lines. Make marks different from the marks used to show the actual data points. The coordinates of the left
mark will be x1 and y1, the coordinates of the right mark will be x2 and y2. Write x1y1 by the left mark and x2y2 by
the right mark.
5.4 4.2 2.85 3.125 y y1 -4.363
From the line: y2 = _____, y1 = _____, x2 = _____, x1 = _____ Calculate the slope: 2 __________
x 2 x1
Be careful to use the exponents on the x terms. The graph begins with the number 2.80. Notice that the label on the x-
axis applies the exponent 10-3 to the numbers. The slope will be a large, negative, number. Enter your data points into the
Clausius-Clapeyron Excel template on one of the computers, and obtain a computer-generated graph and slope
calculation printout. Use this to see how well you placed the line by hand. Include this printout with your experiment.
H vap 36.3
From equation (1), page 1, the slope . Calculate ∆Hvap: _________
(Use R = 8.314 J·K-1·mol-1) R

The book value for ∆Hvap at the temperatures of the experiment is 42.6 kJ·mol-1. Calculate the % error in your measured
Hexp H book -14.8%
value: X 100 %error % error = _________
H book

The % error tends to be high. One major problem is that the vapor pressure does not reach its equilibrium value. This makes
the value of the heat of vaporization higher than it should be. A solution to this problem is to do the measurements in an
evacuated container. Equilibrium vapor pressures are attained more rapidly in the absence of air.
 Name_________________________________________ Grade___________ Date ___________

Graph: Natural Log of the Vapor Pressure versus Inverse Temperature

6.0

5.9

5.8

5.7

5.6

5.5
(2.85,5.4)
5.4

5.3
x
5.2

5.1
x
5.0
ln P

4.9 x

4.8
x
4.7

4.6
x
4.5

4.4
x
4.3

4.2
(3.125,4.2)

4.1

4.0
2.80 2.85 2.90 2.95 3.00 3.05 3.10 3.15 3.20
1 ( x 10-3K-1)
T

QUESTION

P2 H vap 1 1
1. The two point version of the Clausius-Clapeyron equation is ln . Use this equation and the
P1 R T2 T1

following data to calculate ∆Hvap of water: At 20 °C, the VP of water is 17.5 Torr. At 60°C, the VP of water is 149.4 Torr
(Use R = 8.314 J·K-1·mol-1).
In(149.4/17.5)=(-H/8.314)*(1/333. -1/293).

H=43433