25.

ENTHALPY OF VAPORISATION OF METHANOL FROM

VAPOUR PRESSURE MEASUREMENTS
Experiment Station: 1

PRE-LABORATORY WORK
In your laboratory notebook write down the following (see Introduction, What You
Should Record):

• the experiment title and the date the experiment will be carried out

• a brief statement of the experiment to be performed

• a brief plan of the experimental procedure

Please submit the answers to the following questions as a Word document using the
‘upload’ facility on the web marks and absences site at:
https://mole2.chm.bris.ac.uk/lab2005-6/index.jsp before midnight on the day before
96
you are due to carry out this practical .

1. To calibrate the pressure transducer you need to take a series of readings, each
of which involves three measurements: the heights of the columns of mercury in
the left and right sides of the manometer (hL and hR), and the barometric
pressure (patm).

p p ⎛ hL hR ⎞
= atm − ⎜⎜ − ⎟ 25.1
mmHg mmHg ⎝ mmHg mmHg ⎟⎠

Using the following values, calculate p and its error. Show working.

hL = 821.0±0.5 mmHg, hR = 381.0±0.5 mmHg, patm = 738.80±0.07 mmHg

2. Calculate the entropy of vaporisation of water ∆Svap, from the following data:
∆Hvap = +40.7 kJ mol–1; Tb = 100.0 ºC. What is the relevance of the plus sign in
the enthalpy value. Show working.

The data obtained in this experiment MUST be processed using spreadsheets, make
sure you read Appendix D before you carry out this experiment. If you are still
unsure, consult a Demonstrator.

SAFETY DATA
Methanol HIGHLY FLAMMABLE, TOXIC Keep away from flames
Mercury TOXIC Report any spillage
immediately to a
member of laboratory
staff
Glassware under reduced RISK OF IMPLOSION Apply safe laboratory
pressure practice

96 See Introduction, Instructions for Submitting Files via the Web System.

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INTRODUCTION
In this experiment you will measure the vapour pressure of methanol over the
temperature range 5-60°C. The enthalpy and entropy of vaporisation are calculated
from the measurements.

At any temperature between the triple-point temperature and the critical temperature,
a pure liquid and its vapour can coexist in equilibrium. The corresponding vapour
concentration, expressed as the vapour pressure, p, is a function only of
temperature. The temperature at which p equals 1 atmosphere is the boiling point,
Tb. This experiment involves the measurement of the vapour pressure of methanol
over a range of temperatures via a pressure transducer. The aim of the experiment is
to determine the enthalpy of vaporisation, ∆Hvap and the entropy of vaporisation,
∆Svap of methanol.

In this experiment you will encounter the following practical techniques:

• A vacuum frame

• High vacuum distillation.

• Vapour pressure

• Enthalpy

• Entropy

EXPERIMENTAL
The experiment is in two parts: calibration of the pressure transducer and
measurement of the vapour pressure of methanol.

Take time to study the apparatus and Fig 25.1 overleaf before you start.
ONLY LIGHT FINGER PRESSURE IS NEEDED TO SEAL S1, S2, S3. TAKE CARE NOT TO
OVERTIGHTEN THEM.

With all stopcocks closed, start the rotary pump.

GENTLY open S4 to the system. When the manometer indicates a steady pressure
difference of ~760 mmHg, open S2 and S3.

Switch on the transducer control unit. Do not touch the two pre-set control knobs.
The meter should read somewhere near 000 mV (within 100 mV).

After pumping for a few minutes, close S3; the meter reading should remain steady.
If not, the cause is probably volatile material contaminating bulb B3: re-open S3 for
some minutes and repeat the test. (The removal of volatile material from B3 can be
accelerated by warming it with hot water whilst pumping). With S3 closed, the meter
reading should not increase by more than 003 mV per 5 minutes.

Transducer Calibration
The transducer is calibrated by measuring its output as a function of pressure in the
range 0-400 mmHg. The pressure in the system is equal to atmospheric pressure
(read on the Fortin barometer) MINUS the height difference indicated on the

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manometer. Work throughout in mmHg and attempt to read heights on the
manometer to ±0.5 mmHg.

Close S4 and S2, and open S3. VERY GENTLY, open S5 until a few mmHg of air has
leaked into the system. Record hL and hR for the two arms of the manometer and the
corresponding meter reading. Repeat and continue until the meter goes off-range.
PLOT RESULTS AS YOU GO, TO DETECT ERRONEOUS READINGS AS THEY OCCUR.
The calibration should be reasonably linear.

S
5

Transducer
S
6
S S S
1 2 3

B B
1 2

B
3 Manometer

S
4
To rotary
pump

Figure 25.1 Apparatus used in this experiment

Vacuum Distillation
If necessary, open S5 to let the system up to atmospheric pressure then remove S1
and half fill B1 with methanol. Close S1 and S5. A pure sample must now be
obtained by vacuum distillation.

Evacuate the system with S2 and S3 open. Close S3; open S1, to flush out the
system with MeOH vapour. After ~20 seconds close S4.

Distil about 3 ml of MeOH from B1 to B2 by immersing B1 in warm water and B2 in

ice water.

Close S1, remove the two water-baths, open S4 and pump away about a third of your
purified sample from B2.

Close S2, open S3 and re-evacuate B3.

Close S4, open S2 and distil about 1 ml of MeOH from B2 into B3.

Close S3.

Measurement of the Vapour Pressure, p

Stand a large beaker on the hot-plate/stirrer and raise it using the lab-jack so that it
surrounds B3. Fill it with ice/water up to the bottom edge of the plastic cap on S3.
Switch on the stirrer. Measure the temperature (to 0.1°C) and the corresponding
transducer output.

195
Turn on the heater and raise the temperature in intervals of 5-10°C, allowing it to
stabilise briefly at each new value before recording the meter reading. Make several
measurements at each temperature so that you are sure that the contents of B3 have
reached thermal equilibrium with the water bath. AGAIN PLOT YOUR RESULTS IN
ROUGH AS YOU CARRY OUT THE EXPERIMENT.

If you have time, take a few more measurements with the temperature descending –
cool by adding crushed ice. If any hysteresis is present, this probably indicates that
your apparatus has failed to reach thermal equilibrium.

Close-Down
When measurements are complete, open S2, S3 and S4 and pump for at least
30 minutes to remove all MeOH from B2 and B3. Finally, close S2 and S3 and open
S4 to atmosphere; switch off the rotary pump.

DATA ANALYSIS
The Clausius-Clapeyron equation relates the vapour pressure of a liquid to the
temperature.

∆H vap
ln p = − +c 25.2
RT

This equation has the form y = mx + c and so a plot of ln p against 1/T is linear with a
slope of –∆Hvap/R and an intercept of c.

The normal boiling point can be found by extrapolation to find the temperature at
which p = 760 mmHg.

Since ∆Gvap is zero when a liquid and a vapour are in equilibrium (i.e. they coexist)
and

∆G = ∆H – T∆S 25.3

It follows that the entropy of vaporisation, ∆Svap, at the boiling point can be found
from

∆H vap
∆Svap = 25.4
Tb

This equation only holds true for a phase change

Use Least to plot ln(p/kPa) against K/T to determine a value (and uncertainty) for the
enthalpy of vaporisation, ∆Hvap. Either by extrapolation or by algebraic solution,
determine Tb and thence ∆Svap and estimate the errors in these quantities.

REPORT
97
Short report format , include the following:

97 See Introduction p.11 and Appendix F. Please submit as a Word document using the
‘upload’ facility on the web marks and absences site.

196
1. Trouton's rule says that ∆Svap is close to +88 J K-1 mol-1 for normal liquids. Do
your results support this and why should this rule hold?

2. What does your value of ∆Svap tell you about the structure of liquid methanol?

3. Compare your values to literature values – quote your source(s) in the

References section of your report.

Also upload a copy of the Excel spreadsheet you used to process your data.

SOURCES OF INFORMATION
http://www.bris.ac.uk/is/selfhelp/faqs/librarycollections/findjournalarticle.html

P. W. Atkins and J. de Paula, Atkins’ Physical Chemistry, 7th ed., Oxford University
Press, Oxford (2002) pp.144-147.

P.W.Atkins, Elements of Physical Chemistry, 3rd ed., pp.101-102, Oxford University

Press, Oxford (2000).

Handbook of Chemistry and Physics, CRC Press (2003-2004),

http://www.hbcpnetbase.com/.

197
198
SAFETY INFORMATION SHEET
METHANOL VAPOUR PRESSURE
This information must be read before the experiment is attempted. You are required
to sign the declaration at the bottom of the page and have this countersigned by a
demonstrator before commencing the practical. Do not sign this form until you are
satisfied that you appreciate the risks associated with all aspects of the experiment.

Methanol HIGHLY FLAMMABLE, TOXIC Keep away from flames

Mercury TOXIC Report any spillage
immediately to a
member of laboratory
staff
Glassware under reduced RISK OF IMPLOSION Apply safe laboratory
pressure practice

I have read the risk assessment and will comply with these procedures.

Name Group Date

(Please print)

Signature Demonstrator's
Signature

CAREFULLY TEAR THIS SHEET FROM YOUR LABORATORY MANUAL

AND HAND IT TO A DEMONSTRATOR

199