University of Namibia

Department of Chemistry and Biochemistry

Physical Chemistry I
(CHM 3631)

Laboratory Manual

First Semester 2020

 Table of Contents

INTRODUCTORY NOTES...................................................................................................2

INDEMNITY….....................................................................................................................5

EXPERIMENT 1: CALIBRATION OF VOLUMETRIC GLASSWARE............................6

EXPERIMENT 2: DETERMINATION OF VAPOUR PRESSURE AND ENTHALPY OF

VAPORIZATION....................................................................................9

EXPERIMENT 3: PARTIAL MOLAR VOLUME.............................................................14

EXPERIMENT 4: DETERMINATION OF THE MOLAR VOLUME AND PARTIAL

MOLAR VOLUME OF ETHANOL IN DILUTE AQUEOUS
SOLUTION............................................................................................17

EXPERIMENT 5: EXCESS MOLAR VOLUMES OF LIQUID MIXTURES...................21

EXPERIMENT 6: LIQUID-SOLID PHASE DIAGRAMS.................................................24

EXPERIMENT 7: THE STANDARD FREE ENERGY OF FORMATION FOR THE

COMPLEX BETWEEN SALICYLIC ACID AND FERRIC
IONS.......................................................................................................29

EXPERIMENT 8: ENTHALPY OF MIXING OF ACETONE AND WATER..................34

EXPERIMENT 9: THE PARTITION COEFFICIENT – THE EQUILIBRIUM:

𝐼− + 𝐼2 ⇌ 𝐼−3..........................................................................................39

EXPERIMENT 10: PHASE EQUILIBRIA: A THREE-COMPONENT SYSTEM..........42

1
 INTRODUCTORY NOTES

A. PRESENTATION OF A FORMAL REPORT

Introduction

Whenever an experiment is carried out, a formal report needs to be written which is a way
of reporting the results of an experiment that was done. The main purpose of writing a
formal report is to let other people know the significance of the experiment. Therefore, it is
important that the report be written comprehensively. Many experiments in Physical
Chemistry require formal reports and these must be written individually, even when the
experiment is carried out with a partner or in a group. Given the experimental results, the
discussion can bear personality, or in extreme cases different conclusions can be drawn.
Much time is saved if graphs are plotted as the experiment progresses, since this permits a
rapid assessment of the quality and acceptability of the measurements. Reports should be
as short as possible yet contain everything necessary for any other Chemist to be able to
understand them without reference to the instruction sheets. In addition, skill in writing is a
worthwhile achievement and a valuable aid in the industry, medicine, commerce and
academic life.
Main features to concentrate on in report writing are:
1. A clear statement of the objective(s) of the experiment
2. A brief description of the method and apparatus
3. Working out the results
4. Presenting the essential conclusions of the theory, the results and calculations in a
clear and systematic manner
The format of the report given below is just a guide and attempts to improve the general
presentation bearing in mind the four features stated above can be made. Under no
circumstances is it claimed to be a perfect model.

General Format

1. Number and title of experiment

2. Writer’s Name(s) and Name(s) of partner(s)
3. Introduction
The purpose of experiment (i.e. aim), principles of the measurement, the theoretical
background, etc., in your own words! Do not copy word for word from the manual or from
reference books. A clear statement of the aim of the experiment may be included here but
can also be written separately.
4. Experimental Procedure
In this part, a brief description of the method and apparatus should be given. Any
additional information not written in the procedure of the manual or any corrections to it
should be noted in this section.
5. Results
Numerical results where possible should be presented in tabular form, supplemented where
necessary, by a summary of other data necessary for calculations. This is especially
important where long calculations are involved. The columns of the table should be
adequately labelled with sign, units and factors. Record everything relevant (e.g. data,
observations, notes and comments) directly into this section as you make measurements.
Label clearly what the value is and give units. Any account which concludes with, for
example, the statement “E = 35” where E has not been defined is meaningless. As for
graphs, make sure to label the axes and give units.
6. Discussion
This will usually be treatment of data such as calculations, error analysis, significance of
results, comparison with existing literature value(s), etc. It is important to make a point of
argument clear and logic consistent. Remember that no results can be absolutely correct.
Therefore, every measurement has a certain error and the error should be estimated for
every result given.
7. Conclusion(s)
Recite briefly the important conclusions of the theory, the results and calculations in a
clear and systematic manner. The precise form is at the student’s discretion, but it might
refer to the following:
(a) What was the most serious source of inaccuracy?
(b) How could the experiment be improved in general and with respect to accuracy?
(c) Did it succeed in demonstrating any particular principles?
Sometimes it is better to combine discussion and conclusions.
8. Answer all questions (if any)

B. SAFETY

The Chemistry that makes man healthy, happy, beautiful and proud in times of peace is
first made in the laboratory. Explosions can destroy and should not be allowed to be part of
our chemistry.
Laboratory safety is an essential and important aspect in the training of chemists. Every
student without corrective spectacles must wear safety glasses at all times in the laboratory.
Even if the operation you are performing appears to be safe there is still a hazard from
neighbouring experiments.
It is foolhardy to allow any laboratory chemical to enter the mouth. Never taste chemicals
or pipette liquids by using mouth suction (pipette fillers are available and must be used).
Do not place any piece of laboratory ware (e.g. the end of a rubber tube or teat) in the
mouth.
All accidents occurring in the laboratory must be reported to the Lecturer, Technologist
or Demonstrator in charge. If you are in any doubt regarding the safety of a particular
operation, seek advice from the Lecturer, Technologist or Demonstrator in charge.
Ensure that all glassware are very clean.
Clean your bench before you leave the lab or you’ll lose some of your lab marks.
 DEPARTMENT OF CHEMISTRY AND BIOCHEMISTRY
INDEMNITY

I, the undersigned, (Full Name and Surname of student)…………………………………

Student No....................................................................presently a student at the University
of Namibia, do hereby agree to participate in the practical sessions of the Department of
Chemistry and Biochemistry subject to the following conditions:

1. I undertake to comply with all laboratory rules and regulations pertaining to safety as
well as any reasonable instruction by a Lecturer/Technologist/Demonstrator in charge to
the foregoing.

2. I hereby indemnify and hold harmless the Department of Chemistry and Biochemistry
and any of its partner institutions offering training and practical sessions against any loss in
respect of any and all claims, proceedings, damages, costs and expenses that may arise in
the course of practical sessions as a result of my negligence or otherwise.

3. I hereby acknowledge and accept that there are certain risks including bodily injury
inherent in scientific laboratories and working with chemicals, laboratory equipment and
apparatus.

4. I do hereby release, waive, discharge, and covenant not to institute civil action against
the Department of Chemistry and Biochemistry or the University of Namibia in the event
of a personal bodily injury whether it be minor, major or catastrophic acquired during
practical sessions.

5. I accept full responsibility for any damages to property deliberately caused by my

conduct for the duration of the practical sessions and I also accept any consequences and
penalties that might be as a result of this.

By signing this indemnity form, I confirm my understanding and acceptance of the above
conditions.

Signed at ……………………….. on this ……… day of ………………………. 20……

Signature of Student
As Witnesses:
1. …………………………. Name and Surname in full: ...……………………………....
2. …………………………. Name and Surname in full: ...……………………………....
Signatures of Witnesses
EXPERIMENT 1

CALIBRATION OF VOLUMETRIC GLASSWARE

Introduction

The first prerequisite of correct measurement and making up of solutions is satisfactory

glassware. To ensure that a volumetric apparatus is satisfactory, it should be tested for
accuracy before use to establish that the errors of graduation of the apparatus do not exceed
the permissible errors of a determination. Such testing or calibration is generally done by
weighing the amount of pure water held or delivered by the apparatus at a given
temperature and calculating the volume by using the relationship:

Density()  Mass(m)
Volume(V )
It is important to realize the following:
 The density of the water varies with temperature
 The volume of the glass vessel varies with temperature and
 The water filling the vessel is weighed in air

Owing to air buoyancy, which at a given temperature depends on the atmospheric

pressure, a vessel of large volume will weigh less than if it were weighed in vacuum. For
our purpose in this experiment, effect of air buoyancy will be neglected. The aim of this
experiment is to calibrate a pipette by measuring the mass of water and calculating this
volume using the density of water at the temperature of the experiment. The pipette must
be scrupulously cleaned before calibration is carried out. Great care must be taken in
both the measurement of volumes and in weighing.

Procedures

1. Weigh a clean dry 100 ml empty beaker on the analytical balance and record its
weight to four decimal places.
2. Pour distilled water into another clean beaker. From the water in the second beaker,
fill the 25 ml pipette to be calibrated up to graduation mark.
3. Allow the water to flow out slowly while holding the end of the pipette against the
wall of the container until the meniscus is brought into exact coincidence with the
mark.
4. Bring the tip of the pipette into contact with the wall of the empty clean dry beaker of
step 1, already weighed and allow the pipette to deliver freely while still held in contact
with the wall of the beaker for about 15 seconds after free outflow has ceased and then
remove. Do not blow out the water remaining in the tip of the pipette.
5. Weigh the beaker and the contents and determine the weight of the water only.
Obtain the temperature of the water and record this temperature to the nearest 0.5 °C
6. Consult the calibration table and read off the density of water at the temperature of
your measurement. Calculate the volume from this density and mass of water
obtained in step 5.
7. Obtain ten values of the mass of water and therefore ten values of the volume.

Results

Assuming that there is no substantial change in temperature during the experiment, obtain
a mean value of the volume of the pipette. Estimate the error in your measurement and
give your answer in the form:
Volume of pipette = ……….……………………±….........................cm3

Calibration Table

Temperature Density of water Temperature Density of water

(°C) (g·cm-3) (°C) (g·cm-3)
18.0 0.99862 25.5 0.99694
18.5 0.99853 26.0 0.99681
19.0 0.99843 26.5 0.99668
19.5 0.99833 27.0 0.99654
20.0 0.99823 27.5 0.99640
20.5 0.99813 28.0 0.99626
21.0 0.99802 28.5 0.99612
21.5 0.99791 29.0 0.99597
22.0 0.99780 29.5 0.99583
22.5 0.99768 30.0 0.99567
23.0 0.99757 30.5 0.99537
23.5 0.99745 31.0 0.99506
24.0 0.99732 31.5 0.99473
24.5 0.99720 32.0 0.99440
25.0 0.99707
0.999

0.998
Density /gcm-3
0.997

0.996

0.995

0.994

0.993 Temperature / oC

0.992
18 20.5 23 25.5 28 30.5

Figure: Variation of density of water with temperature

EXPERIMENT 2

DETERMINATION OF VAPOUR PRESSURE AND ENTHALPY OF VAPORIZATION

Introduction

The Clausius-Clapeyron equation in Physical Chemistry courses is introduced as a means

of describing the variation of the vapour pressure with temperature and for determining the
enthalpy of vaporization.
d ln P Hova
dT  RT 2
If ΔHvap is independent of temperature then
Ho
ln P  
vap
 constant
RT
This experiment demonstrates how one can determine the vapour pressure of water in the
range of 50 °C to 80 °C using the simplest of laboratory equipment i.e. a tall beaker, a
graduated cylinder and a thermometer as shown below:

Water Bath
Measuring Cylinder

Trapped Air Thermomete

Stirrer

Hotplate

Method

A sample of air is trapped in an inverted 10 ml graduated cylinder immersed in a beaker of

water. The water is heated to about 80 °C, and the trapped gas becomes saturated with
water vapour rapidly at this temperature. The temperature of the water bath and the volume
of the gas are recorded. The bath is then cooled and the readings of temperature and gas
volume are taken at intervals of 5 °C or less. The number of moles of water in the gas
phase changes with temperature but the amount of air is constant. With knowledge of the
moles of air in the gas sample, the partial pressure of air can be calculated at each
temperature, and the vapour pressure of the water can be obtained by determining the
difference from the barometric pressure. The number of moles of air in the mixture can be
found from the measurements of volume, temperature and pressure at the temperature near
0 °C, where water content of the gas is less than 1 % and is neglected. The enthalpy of
vaporization is calculated through the Clausius-Clapeyron equation from a plot of the
algorithm of the vapour pressure versus 1/T. There is a small systematic error resulting
from the use of inverted graduated cylinders because the meniscus at the water interface is
reversed (see the figure). It has been estimated, by introducing known volumes of air into a
completely filled inverted cylinder, that the error involved with the use of 10 ml graduated
cylinders is 0.2 ml. Then, this value is subtracted as a correction to each volume reading.

Equipments

Hotplate
5000 ml beaker
250 ml beaker
10 ml graduated cylinder
100 ml cylinder
Thermometer
Glass rod
Pot

Procedures

1. Fill 10 ml graduated cylinder about 9 ml with distilled water.

2. Cover the top with a finger and quickly invert and lower the cylinder into a tall beaker
that has been filled with water. An air sample of 4 to 5 ml should be trapped within the
cylinder.
3. Add more water if necessary to the beaker to ensure that the trapped air is surrounded
by water. Then, heat with a hotplate to approximately 80 °C. Stir the water bath
frequently to avoid thermal gradients.
4. Observe the volume of trapped air. When it expands beyond the scale on the
cylinder, remove the burner and allow the water to cool.
5. When the gas begins to contract and the volume can be read again, read and record the
gas volume to the closest 0.1 ml and the temperature of the water to the nearest 0.1 °C.
6. As the water cools, make additional measurements at approximately 5 °C intervals
down to 50 °C. Ice may be added to speed up the cooling.
7. After the temperature has reached 50 °C, cool the water rapidly to less than 5 °C
by adding ice. Record the gas volume and the water temperature.
8. Obtain a reading of the atmospheric pressure.
Treatment of Data

1. Correct all volume readings by subtracting 0.2 ml to compensate for the inverted
meniscus. Using the measured values for the volume and temperature from step 7 and
the atmospheric pressure, calculate the number of moles of the trapped air. Assume
that the vapour pressure of the water is negligible compared to atmospheric pressure
at the low temperature.
2. For each temperature, calculate the partial pressure of air in the gas mixture as follows:

Pair  nair RT
V
Where
Pair = pressure of air
nair = number of moles of air
V = volume (m3)
R = universal gas constant (Joule/mol·K)
T = temperature (K)
3. Calculate the vapour pressure of water at each temperature, i.e.
PH 2O
 Patm  Pair

where Patm is the atmospheric pressure. Ask the demonstrator for this value. (An
optional, small correction may be made by correcting for the effect of the difference
in water levels).
4. Plot 1
ln PH versus and draw the best straight line through the points. Determine
O
2 T
the slope and using the Clausius-Clapeyron equation, calculate ΔHvapour . Find the value
of vapour pressure at 65 °C using the graph.
EXPERIMENT 2

DETERMINATION OF VAPOUR PRESSURE AND ENTHALPY OF VAPORIZATION

Atmospheric pressure is 1 atm.

1 atm = 101.3 kiloPascal (kPa) = 760 mmHg = 760 torr. 1 bar = 100 kPa
R= L J
0.08214 = 8.314
atm mol  K
mol 
K

Temperature Volume
(°C) (mL)

t V nair Pair P𝐻 𝑂
2

Temperatur Volum Numbers of Moles of Partial Pressure Vapour Pressure

e (°C) e (ml) Air Trapped of Air of Water
(mole) (atm) (atm)

5
50
55
60
65
70
75
80
 1
ln PH2 O
T
EXPERIMENT 3

PARTIAL MOLAR VOLUME

Introduction

Knowledge of partial molal volumes is necessary for the study of primary ionic solvation,
the effect of pressure on chemical potentials or activity coefficients or the relation with
osmotic pressure, etc.

Theory

Any extensive property of X of a mixture is given by

  
X  n1 X 1  n2 X 2  ..........ni X i

where X¯ i is the partial molal quantity of a constituent i. This quantity is the contribution
per mole of the constituent i to X in the system and is given by:
  X 
X i  
 i T ,P,n ,n1 2 …………………………………………………………………(1)
n
The partial molal volume, (V¯ i), for instance, is the increase in volume of the system
resulting from the addition, at a constant temperature and pressure, of 1 mole of i to such a
large quantity of the system that there is no appreciable change in the concentration. The
value of V¯ i may, of course, vary with the concentration of i in the system. In an ideal
mixture, ¯Vi is equal to the molal volume Vi of the pure substance.
For determining partial molal volumes in binary mixtures the method of intercepts is
convenient. Consider, for example, a mixture containing a total of one mole of two
components, mole fractions x1 and x2, respectively. Hence

x1 + x2 = 1

and

dx1 + dx2 = 0

But

V =¯V1 x1 + V¯ 2 x2
or

dV =¯V1 dx1 + V¯ 2 dx2

so that

dV = (V¯ 2 - V¯ 1) dx2 ...............................................................................................................................(2)

If the volumes of the mixtures of different composition, but of total molality of unity are
plotted against mole fractions (see figure), then the intercepts BD and AC of the tangent to
the curve at mole fraction x1 are equal to V¯ 2 and V¯ 1 at composition x1. Let α be the
angle between the tangent and the line V = 0. The slope of the tangent is from eqn. (1).

dV
tan  V V1
dx2 2
V=1/ρ

C
X1
A Mole fraction X2 (or % wt w2) B

Figure: Method of intercepts for partial molal quantities determination

But

BD  V  x1 tan  V1 x1  V2 x2  x1 (V2 V1 )  V2 (x2  x1 )  V2

Similarly
AC  V  x2 tan V 1
Furthermore, the intercepts of the tangents to the curve of the reciprocal of specific gravity
against weight percent on the vertical axis gives the partial specific volume; the latter
multiplied by the respective molecular weight yields the partial molal volume.

Apparatus

Absolute alcohol, distilled water, 50 cm3 beakers; analytical balance (± 0.1 mg)

Procedures

Prepare a series of aqueous alcohol solutions at room temperature as follows:

%wt. alcohol 90 75 65 60 55 50 45 40 35 20 10 5
3
Valcohol/cm 5.6 4.5 4.0 3.7 3.4 3.1 2.8 2.5 2.2 1.3 0.6 0.3
3
VH2O/cm 0.5 1.2 1.7 2.0 2.2 2.5 2.7 3.0 3.3 4.0 4.3 4.6
Weigh a small beaker. Add 4 cm3 of water and weigh it again. Weigh the beaker
containing the same volume of each of your alcohol solution. The specific gravity of the
solution is then given by:

WID d (W I  W )
4  W 
to
o
W
where WI and W are the apparent masses of the solution and water, respectively. D is the
density of water at room temperature (at 298 K, D = 0.997 gcm-3) and d is the mean density
of air (0.001184 gcm-3 at 750 mmHg pressure and 298 K; 0.001199 gcm-3 at 770 mmHg
pressure and 298 K).

Treatment of results

Tabulate the results for percentage by weight of alcohol and specific gravity of the
solutions. Plot a graph of 1/ρ against % weight of alcohol.
Determine the intercept of the tangent at 50% weight of alcohol. Multiply this by the
molecular mass of ethanol to yield a value for the partial molal volume, ¯V2, at this
concentration.
EXPERIMENT 4

DETERMINATION OF THE MOLAR VOLUME AND PARTIAL MOLAR VOLUME

OF ETHANOL IN DILUTE AQUEOUS SOLUTION.

Introduction

Extensive properties of solutions (e.g. volume, energy, free energy, etc.) are not truly
additive when pure components are mixed. If volume VA of a liquid is added to volume VB
of the same liquid at a given temperature and pressure, the intermolecular interactions and
hence the intermolecular spacing will be unchanged and the resulting volume will quite
simply be VA + VB (i.e. ΔVm = 0). However, if volume VA of a liquid is added to volume VB
of a different liquid (in which it is miscible) the intermolecular interaction and
consequently the intermolecular spacing will be specific to the particular mixture and the
volume of the liquid mixture will generally differ from VA + VB (i.e. ΔVm ≠ 0, except for
ideal mixture). The value of ΔVm for non-ideal mixture depends not only on the nature of
the components of the mixture but also on the relative proportions. It is convenient to
express this aspect in terms of partial molar volume, V¯ i, mathematically defined as:

 V 
V  for component A and;

n A T , P, nB
A

 V 
V  for component B,
 
n B T , P, nA
B

where nA and nB are the amounts (moles) of components A and B.

The total volume V, of the solution is equal to the volumes of all the components in the
solution; the volume of each component is equal to the product of the number of moles of
that component and its partial molar volume, thus

V = nA V¯ A + nB ¯VB

There are two methods of determining partial molar volumes. By measuring the volumes
of the mixtures containing variable amounts of one component mixed with the fixed
amount(s) of the other component(s). The alternative method involves measurement of
intercepts.

Method

Prepare about 50 cm3 mixtures of ethanol and water of accurately known composition by
mass into stoppered bottles, i.e. 0 – 100 % (wt/wt) ethanol (mixtures containing
approximately 0, 20, 40, 60, 80 and 100 % of ethanol would do). Determine the density of
each solution at 25 °C.

Equipments
Analytical balance
50 mL volumetric flask or pyknometer
Thermostat bath at 25 °C
100 ml beaker
Pipette
Glass rod
Absolute ethanol

Procedures

The procedures for different concentrations of ethanol are the same. The following is an
example of 60 % ethanol with water (wt/wt).
1. Weigh 50 mL empty volumetric flask on the analytical balance accurately and write
the reading down.
2. Accurately weigh about 40 g of water in 100 mL beaker, and then add about 60 g of
absolute ethanol with a pipette on the analytical balance.
3. Stir the mixture with a glass rod and pour it into the volumetric flask to the mark
carefully.
4. Weigh the volumetric flask with the mixture accurately and write the reading down.
5. Calculate the net mass of 60 % mixture in 50 ml as follows:

mnet = mtotal – mempty volumetric flask

Repeat the same procedure for other concentrations of ethanol.

Treatment of Experimental Data and Discussion

1. Calculate the molar volume of ethanol defined as:

Vm = RMM / ρ =[46.07 / ρ] (cm3/mol)

where RMM is the relative molar mass and ρ is the density of ethanol.
2. Calculate the specific volume (i.e. reciprocal density) of each solution and plot against
the percentage by weight of the ethanol. Draw a smooth curve through the points, and
draw tangents to the curve at 20, 40, 50, 70, and 80% by weight/weight
concentrations. The intercepts of these lines on the 0 % and 100 % ordinates give the
partial specific volumes of water and ethanol, respectively, at various concentrations.
Hence, calculate the partial molar volume, i.e. partial specific volume × RMM.
3.
4. Draw two curves on the same graph showing the variation of
(a) the partial molar volume of ethanol with mole fraction, and
(b) the partial molar volume of water with mole fraction.
5. Why do you think the method used here would not give very accurate partial molar
quantities? Give one reason only.
EXPERIMENT 4

DETERMINATION OF THE MOLAR VOLUME AND PARTIAL MOLAR VOLUME

OF ETHANOL IN DILUTE AQUEOUS SOLUTION

Temperature: 25 °C
Molar mass: EtOH = 46.07 g/mol. H2O = 18.01 g/mol
Measured volume: 50 ml
Mass of EtOH Mass of H2O Total mass Total mass in 50 ml EtOH: H2O
g g g g % wt/wt

EtOH: H2O nEtOH n𝐻 𝑂 XEtOH X𝐻 𝑂

2 2 ρ 1/ρ V¯ ¯V 𝐻 𝑂 V¯ m
2 V¯ m
% wt/wt mol mol g/cm3 3 3
cm /g EtOH cm /g EtOH 𝐻𝑂
2

3
cm /g cm /mol cm3/mol
3

EtOH = Ethanol
n = number of moles
X = mole fraction
wt/wt = weight by weight
ρ = density of mixture
Vm = molar volume
¯V = partial specific volume
¯Vm = partial molar volume
EXPERIMENT 5

EXCESS MOLAR VOLUMES OF LIQUID MIXTURES

Introduction

Excess volume, VE, is the difference between the change in volume observed when species
are mixed and the change of an ideal solution, i.e.

E
V  obs VA VB
V

or

E mA  mB mA mB
V 
    A B

where Vobs = volume of mixture observed

mA, mB = mass of liquid A and B, respectively
ρ = density of mixture
ρA, ρB = density of liquid A and B, respectively.
It is often convenient expressing VE, in units of volume per mole and hence the term excess
molar volume, VmE . Mathematically,

VmE VE
nA  nB
where nA, nB = moles of liquid A and B, respectively.
VmE can take both positive and negative values depending on several factors such as
temperature, segment-segment interactions, chain length, etc.

Procedures

You will be provided with hexane and any of the following organic solvents:
cyclohexanone, cyclohexanol, cyclohexane, propanol, ethanol or hexane.
Prepare the following mixtures by weight (weights must be made to 4 decimal places!):

H/g 19 18 17 16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1
S/g 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19
H = Hexane and S = any of the following: cyclohexanone, cyclohexanol, cyclohexane,
propanol, ethanol or hexane.
Measure the densities of the pure solvents and the mixtures using the density bottle(s).

Treatment of Experimental Data and Discussion

1. Do the measured densities of the pure solvents compare well with the literature values?
2. Make a table H / g, S / g, moles S, Mole fraction H, Mixture density / g·cm-3 and V mE
/cm3mol-1.
3. Plot VE versus mole fraction of H.
4. Comment on the interactions between hexane and the other organic solvent used.
EXPERIMENT 5
EXCESS MOLAR VOLUMES OF LIQUID MIXTURES
1. Calibration of the density bottle
Room temperature =
Density of water =

Run Wt. bottle Wt. bottle+water Wt. water Vol. bottle

1
2
3
4
5
6

2. Example of treatment of data

No. Wt. H nH Wt. S nS XH mH ρ VE

(g) (g) (g) / g·cm-3 / cm3·mol-1
EXPERIMENT 6

LIQUID-SOLID PHASE DIAGRAMS

Objective

To construct the liquid-solid phase diagram using cooling curves method.

Introduction

One way to determine a liquid-solid phase diagram experimentally is by thermal analysis.

Here, one allows a liquid solution (melt) of the two components to cool at a fixed rate and
measures the system’s temperature as a function of time. This is repeated for several
different liquid compositions to give a set of cooling curves. The usual method of
constructing liquid-solid phase diagrams is from cooling curves.
The figure below shows a cooling process on a solid-liquid phase diagram and the cooling
curve associated with it.
Temperature
Temperature

Stage 1

Stage 2

Stage 3

Stage 4

Time 0 XB 1
A B

Figure: A typical cooling curve and phase diagram for freezing of an A-B solution

Liquid is cooled during stage 1. During stage 2, the solid component B is freezing from
solution. Since the freezing process releases energy, the temperature falls off less rapidly in
stage 2. The liquid is at its eutectic during stage 3. The temperature does not change during
this eutectic halt because liquid is not stable below the eutectic temperature, which means
that all the liquid must freeze before the temperature can resume downward. Stage 4
represents the cooling of the two solid phases.
Note that the time variable is approximately proportional to the amount of heat q lost from
𝑑𝑇
the system, so that
𝑑𝑡 of the cooling curve is approximately proportional to the
reciprocal of the system’s heat capacity

dq p
C p  dT

In this experiment, the naphthalene-biphenyl system will be studied.

Equipments

Analytical balance
Hotplate
Stop watch
Test tube
250 ml beaker
50 ml beaker
Stand
Clamp
Boss head
Thermometer
Pot
Naphthalene
Biphenyl
Ice

Procedures

1. Place 5.0 g of naphthalene (note the exact weight) in the test tube and melt it by
immersing the tube in a boiling water bath.
Avoid overheating!
2. Remove the tube from the bath, position it in the tube holder.
3. Put the thermometer into the test tube and start taking readings every 30 seconds until
the content of the tube is solid.
Use the thermometer with reasonable scale.
If cooling is too slow, you can use ice + water bath to speed up although this
may affect your results- why?
4. Repeat step 1- step 3 by adding 0.7, 0.8, 1.0, 1.5 and 2.0 g of biphenyl consecutively.
Remember to write down actual amounts weighed.
5. Perform step 1- step 3 starting from pure biphenyl in a clean tube. Additions of the
naphthalene should be 0.5, 0.6, 0.7 and 1.1 g.
Note: In an ideal situation, the mixtures are supposed to be made in separate test tubes
to obtain more accurate results.

Treatment of Data

1. Plot the cooling curves (you can put 5- 6 on one graph). Identify the
temperatures for the solidification (the arrest points of the temperature, take into
account supercooling and that you can deal with eutectic or a compound
formation in the particular mixture).
2. Construct the phase diagram using the temperatures identified above. Express the
composition of the mixture in terms of mole fractions.
3. Using the phase rule, determine the number of degrees of freedom at the
eutectic point.
What factors decide whether a solution will behave ideally or not? What conclusions can
be drawn about the naphthalene-biphenyl system?
EXPERIMENT 6

LIQUID-SOLID PHASE DIAGRAMS

Room Temperature: °C
Cooling of Naphthalene-Biphenyl System
Time Temperature
Sec. °C
Naphthalene + Biphenyl + Biphenyl + Biphenyl + Biphenyl + Biphenyl
5.0000 g 0.7000 g 0.8000 g 1.0000 g 1.5000 g 2.0000g
0
30
60
90
120
150
180
210
240
270
300
330
360
390
420
450
480
510
540
570
600
630
660
690
720
750
780
810
840
 Cooling of Biphenyl-Naphthalene System
Time Temperature
Sec. °C
Biphenyl + Naphthalene + Naphthalene + Naphthalene + Naphthalene
5.0000 g 0.5000 g 0.6000 g 0.7000 g 1.1000 g
0
30
60
90
120
150
180
210
240
270
300
330
360
390
420
450
480
510
540
570
600
630
660
690
720
750
780
810
840
870
900
930
960
990
1020
EXPERIMENT 7

THE STANDARD FREE ENERGY OF FORMATION FOR THE COMPLEX

BETWEEN SALICYLIC ACID AND FERRIC IONS

Introduction

Ferric ions in aqueous solutions at pH 2.6 – 2.8 form a strongly coloured complex with
salicylic acid (orthohydroxybenzoic acid):

Fe3+ + x(sal) →← Fe(sal)x3+

where sal stands for salicylic acid.

By measuring the intensity of the colour produced on mixing different proportions of the
reactants, the stoichiometry of the complex can be found. In addition, if the extinction
coefficient of the complex is known, its concentration in a particular mixture can be found
and hence the apparent equilibrium can be deduced from:

Kc=[complex] / [Fe3+] [sal] x

However, the state of equilibrium is governed rigorously by the thermodynamic

equilibrium constant defined by:

 complex
KTh 
 xsal  Fe 3

where the α are the equilibrium thermodynamic activities. The two expressions are related
by:

  complex 
KTh   Kx c

  Fe 3 sal 

where the γ terms, called activity coefficients, have the property that they approach unity
as the concentrations approach zero. In the present experiment the concentrations used are
such that γsal ≈1. Although the activity coefficients of the charged species cannot be taken
to be approximately unity, we may assume that γsal ≈Kc so that they almost cancel out in
the above expression leaving:

KTh ≈ Kc
In general, the change in Gibbs free energy for a reaction

A+B→C+D

where A, B, C and D are present with activities αA, αB, αC and αD is given by the equation:

ΔG =ΔG°+ RT ln (αC×αD / αA×αB)

If all the substances are present in their standard states (i.e. all activities are unity) then ΔG
=ΔG°, which is the standard free energy change of the reaction. For solutes in solution, the
standard state is a hypothetical one in which it is present at a concentration of 1 mol·dm-3
and a pressure of 1 atm but behaves ideally, i.e. obeys Henry’s law.
The standard free energy change is related to the thermodynamic equilibrium constant by
the van’t Hoff isotherm:

ΔG° = - RT ln KTh

Like heats of reaction, the standard free energy change is an additive property and
therefore ΔG° (and hence KTh) can be determined for the reactions which may be difficult,
if not impossible to study directly, from other reactions of known ΔG°.

Theory

Job’s method of continuous variations employs equimolar solutions of two reactants mixed
in various proportions. This method suggests that the maximum amount of equilibrium
product is formed when the proportions of the reactants correspond to the empirical
formula of the product. For example, if the reaction can be represented by:

aA + bB = AaBb

then the greatest amount of product is present when a parts A are mixed with b parts of an
equimolar solution B.
In the present experiment, the concentration of the ferric complex is monitored by its
absorbance of light. The Beer-Lambert Law states that the fractional reduction in the
intensity of a beam of light as it passes through an absorbing medium is proportional to the
number of absorbing molecules in the light path. This can be expressed mathematically in
the following way:

Absorbance (or optical intensity) = log10 ( Io / I ) = εcl

where
Io is the initial intensity
I is the transmitted intensity
ε is the molar absorptivity (or molar extinction coefficient) of the solute being measured
c is the concentration (mol/dm3)
l is the path length (cm).

Apparatus and Materials

Spectrophotometer
Cuvette (1 cm)
Burette
Retort stand
Burette clamp
Small funnel
Small beaker
Thermometer
50 cm3 beaker
250 cm3 volumetric flask
100 cm3 volumetric flasks
Spatula
Wash bottle
Filter paper
0.0020 M HCℓ stock solution
0.0010 M Salicylic Acid
Ferric Nitrate

Procedures

1. The optimum pH for the complex is about 2.6 - 2.8, which can be obtained sufficiently
nearly by working throughout with solutions of the substances of approximately
0.0020 M HCℓ.
2. Prepare 0.0010 M solution of Ferric Nitrate by dissolving 0.1010 g in 250 cm3 of
0.0020 M HCℓ solution.
(N.B. This solution hydrolyses on standing and must be used immediately
after preparation).
3. By means of two burettes, prepare 10 cm3 mixtures of 0.0010 M Ferric Nitrate and
0.0010 M Salicylic Acid in HCℓ in the ratios 1:9, 2:8, 3:7, …7:3, 8:2, 9:1. Record the
temperature of the mixtures.
4. Determine the absorbance of each solution using the spectrophotometer provided at
wavelength = 527 nm. Use deionized water as blank.
5. Prepare a series of ferric solutions having strengths of 0.00010, 0.00020, 0.00040, and
0.00050 M in 100 cm3 volumetric flasks and make up to the mark with deionized
water respectively.
6. Pour about 10 cm3 of each of these solutions into small beakers respectively.
7. Add excess solid Salicylic Acid (half a spatula) to small beakers respectively in order
to convert the ferric salt wholly into the complex form.
8. Filter off undissolved solid.
9. Determine the absorbance of the four resulting solutions using the corresponding
ferric solution without adding Salicylic Acid to the blank at the same wavelength.

Treatment of results

1. Plot a graph of absorbance against mole fraction of ferric for the mixtures made from
the equimolar solutions. The maximum in the curve gives the empirical formula of the
complex.
2. Plot the absorbance values for the second part of the experiment against concentration
of ferric ions. If the Beer-Lambert Law holds, the graph should be a straight line
through the origin. Draw the best straight line through the points and from the slope
of the graph calculate the molar extinction coefficient of the complex.
3. Use the value of the molar extinction coefficient to find the concentration of the
complex in the 5:5 reaction mixture. Since the formula of the complex has been
found, it is now possible to calculate by difference the concentration of uncombined
Salicylic Acid and Fe3+ present in the mixture and hence Kc for the reaction.
4. Using the Kc value, calculate the standard free energy of formation of the complex
from the expression:

ΔG° ≈ - RT lnKc = -2.203 RT log10Kc

(R = 8.314 J·K-1·mol-1)
5. What extra information would be needed to predict the effect of altering the
temperature on Kc?
EXPERIMENT 7

THE STANDARD FREE ENERGY OF FORMATION FOR THE COMPLEX

BETWEEN SALICYLIC ACID AND FERRIC IONS

Temperature: °C
Wavelength: 527 nm
Absorbance of Complexes* (Part A)
Ferric Nitrate Salicylic Acid Abs.
ml ml

*
Use deionised water as the blank

Absorbance of Complexes (Part B)

Ferric Nitrate Blank Abs.
×10-3 mol/L
EXPERIMENT 8

ENTHALPY OF MIXING OF ACETONE AND WATER

Introduction

The molar enthalpy of mixing, ΔHmxg / (nA + nB) of two liquids A and B to form a liquid
mixture, can be defined as the enthalpy change accompanying the formation of 1 mole of
the liquid mixture from the requisite amounts of the pure liquid components at the same
temperature and pressure as the mixture. In this experiment, the molar enthalpies of mixing
of various mixtures of acetone and water will be determined.

Requirements

Beckman thermometer
Magnetic stirrer
Tallform beaker
Stop watch
Burette
Retort stand
Clamp
Boss head
Test tube
Forceps
Acetone

Procedures

The procedure may be divided into two parts:

(a) Determination of the heat of mixing, for each mixture
(b) Determination of the heat capacity of the calorimeter plus the mixture, for
each mixture.
Before proceeding further, ensure that the Beckman thermometer supplied (HANDLE
WITH CARE!) is set to read about 2.0 when placed in water at room temperature. If not,
readjust (consult demonstrator).
Now support the large boiling tube (the calorimeter vessel) on the magnetic stirrer. Place a
magnetic stir bar in the tube, add 200.00 cm3 of acetone, and then assemble the stopper
with the Beckman thermometer and a small test tube passing through the two holes. Ensure
that the thermometer bulb is covered by the mixture. Place 4.20 cm3 of water in the test
tube and ensure that the portion of the test tube containing the water is below the level of
acetone. Switch on the magnetic stirrer.
(a) Determination of the enthalpy change on mixture

Read and record the temperature (the Beckman thermometer can be read to three
decimal places) at the end of each minute for 5 minutes. At the end of this period,
smash the bottom of the test tube by means of a sharp tap with the iron rod supplied.
Ensure that thorough mixing takes place by raising and lowering the broken test tube a
few times. The temperature will either rise or fall, depending upon whether the mixing
process is exothermic or endothermic, respectively. Continue reading and recording the
temperature at the end of each minute for a further 5 minutes. On graph paper, plot the
temperature as ordinate against time in minutes as abscissa. Join the plotted points. The
figure obtained may look more or less as follows. For an exothermic process:

Trail Period
× × × ×
Temperature

× × × ×
ΔTm

Lead Period

Time

The rise in temperature ΔTm corresponding to mixture formation may be estimated by

extrapolating the lead and trail periods and drawing a vertical line through a point
mid-way up. Note that the mixing process takes place relatively rapidly after the test
tube is broken.

(b) Determination of the heat capacity of the calorimeter plus the mixture

This determination is carried out immediately after the measurements described in part
(a) are carried out- and makes use of the reaction mixture prepared in (a). The
calorimeter is left as it was at the end of part (a), i.e. the broken test tube and glass
fragments, etc., remain part of the calorimeter.
Read and record the temperature at the end of each minute for 5 minutes. At the end of
this period switch on the power to the heating element in the tube, so that a potential
difference of exactly 2.50 V and a current of approximately 2 A are applied. Measure
the current by means of the digital multimeter provided. Simultaneously, switch on the
stop-clock/stopwatch provided. Read and record the potential difference and current on
the meters as accurately as possible. Continue reading and recording the temperature of
the calorimeter at the end of each minute. When the temperature has risen by
approximately 1 °C, switch off the heater, and also the stop-clock/stopwatch. Note the
time period over which the heater was activated. Continue reading and recording the
temperature against the time in minutes. On graph paper, plot the temperature as
ordinate against the time in minutes as abscissa. Join the plotted points. The figure
obtained may look more or less as follows:

× × ×
×
Temperature

ΔTh

× × × ×

Time

Note that in contrast to the situation encountered in the heat of mixing experiment
described in part (a), the electrical heating extends over an appreciable time interval.
The rise in temperature ΔTh resulting from the electrical heating may be estimated by
extrapolation as described in part (a) and as shown in the figure above.
More sophisticated and accurate methods exist for correcting calorimetric data for heat
exchange with the surroundings. However, the extrapolation method described above is
sufficiently accurate for the purposes of this experiment.
Repeat the above procedures for the following mixtures:
i. Starting with 200.00 cm3 of acetone – 4.20 cm3 water mixture, add
successively 7.90 cm3, 7.00 cm3, and 15.80 cm3 of water.
ii. Starting with 200.00 cm3 of water, add successively 15.00 cm3 volumes of
acetone until a total of 45.00 cm3 is reached.
Note that particularly after a heat of mixing determination in which the mixture formation
is markedly exothermic, it may be necessary to cool the calorimeter vessel before the heat
capacity is determined. This may be done by wrapping tissue paper around the vessel and
moistening the paper with acetone. Evaporation of the acetone will result in the required
cooling effect.

Calculations

(a) Calculations of heat capacity

If the potential difference applied to the heater is denoted “V”, the current “i” and
the time for which the heater was activated is denoted “t”, then the heat capacity
“Cp” of the calorimeter plus contents is given by

Cp = Vit/ ΔTh

(b) Calculations of enthalpies of mixing

The enthalpy of mixing “ΔHi” for any particular mixing experiment is given by

ΔHi = - Cp ΔTm

(The negative sign is introduced for reasons of sign convention)

(c) Calculations of molar enthalpies of mixing
The mixtures produced in this experiment are not all produced by mixing the pure
components together. Some of the mixtures are prepared by adding more of one of the
pure components to an existing mixture from a previous determination. It is therefore
necessary to accumulate enthalpies of mixing ΔHi as calculated in part (b) above in
order
EXPERIMENT 8

ENTHALPY OF MIXING OF ACETONE AND WATER

Room Temperature: °C
Cp: 200 J/K
Volume of Acetone: 200.00 ml
Volume of Water: 4.20 ml

Readings of Temperatures from Beckman Thermometer (Part A)

Lead Period Main Period Trail Period
EXPERIMENT 9

I + I2 →← I3
¯ ¯
THE PARTITION COEFFICIENT-THE EQUILIBRIUM:

Introduction

THE DISTRIBUTION OR PARTITION LAW:

It was originally supposed that a substance which was soluble in two immiscible liquids
would distribute itself in such a way that the ratio of the concentrations in the two
layers would be constant at a given temperature. Thus:

Concentrat ion of A in liquid I AI

  const.
Concentration of A in liquid II AII

This simple law, however, breaks down under certain conditions, namely when A does not
exist in the same form in the two liquids. An example is benzoic acid (C6H5COOH)
distributed between water and benzene. Benzoic acid exists mainly as a dimer in benzene
solution and the partition law found to apply in this case is

C H COOH 2 water
6 5  const.
C6 H5COOH benzene

Nernst, therefore, modified the partition law to state that when a solute distributes itself
between two immiscible solvents, there exists, for each molecular species, at a given
temperature, a constant ratio of partition between the two solvents, and this ratio is
independent of any other molecular species which may be present. It can be shown (see
any physical chemistry textbook) that this statement of the partition law leads to the above
equation in the case of the benzoic acid partition.
This experiment involves the partition of iodine between reagent grade hexane and an
aqueous solution of potassium iodide. In the hexane layer the iodine exists as I2 molecules,
¯
as it does in pure water. In a KI solution, however, the iodine combines with I to form the
¯
I3 complex, the following equilibrium being set up:

I + I2 →← I3
¯ ¯

The KI and KI3 are insoluble in hexane. The purpose of the experiment is to determine the
¯
equilibrium constant of the above reaction. To do this, we require the concentration of I2, I
¯
and I3 in the aqueous layer. The principle of the determination is as follows.
The partition coefficient of I2 between hexane and pure water is obtained. Then, iodine is
shaken up with hexane and KI solution. The ratio of the concentration of free iodine in the
aqueous layer to the concentration of iodine in the hexane layer will be the same as in the
case of pure water (by Nernst’s partition law above), i.e. it is unaffected by the KI and the
¯
fact that some iodine has formed a complex with I . So if we determine the concentration
of iodine in the hexane layer by titration we can calculate the concentration of free iodine
in the KI solution. A titration of the aqueous layer will yield the total amount of iodine
¯ ¯
present in this layer, both free and combined in the form of I3 . The concentration of I3 can
¯
thus be obtained by difference. If the amount of I originally present in the aqueous layer is
¯
known, we can find, again by difference, the amount of I which has not combined to form
¯
I3 . Thus, we can use the fact that the partition law refers to iodine in the same form (i.e. of
the same molecular species) in the two layers, and not to the total amount of iodine
present. We now have sufficient information to calculate the equilibrium constant.

Requirements

Burette
Retort stand
Burette clamp
Small funnel
200 ml measuring cylinder
300 ml Iodine flask
500 ml beaker
50 ml bulb pipette
25 ml bulb pipette
10 ml graduated pipette
Pipette filler
Wash bottle
Iodine saturated in Hexane
Hexane
0.1200 M KI
0.02000 M Sodium Thiosulphate
Starch indicator

Procedures

1. Take six stoppered bottles, add about 200 cm3 of water to the first three, and add about
100 cm3 of 0.1200 M KI solution to the second three by measuring cylinder
respectively.
2. Prepare the mixtures using two burettes as follows:
 Volume of iodine solution Volume of pure hexane
(cm3) (cm3)
Bottle 1 25 0
Bottle 2 20 5
Bottle 3 15 10
Bottle 4 25 0
Bottle 5 20 5
Bottle 6 15 10

3. Shake all the bottles well but avoid heating the solutions with your hands. Allow the
layers to separate.
4. Titrate the aqueous layer of each mixture against 0.02000 M sodium thiosulphate
solution, using starch as indicator. Use 50.00 cm3 of aqueous layer for the first three
mixtures and 25.00 cm3 for the second three mixtures.
5. Titrate 5.00 cm3 of the hexane layer in each case against the sodium thiosulphate
solution.
NOTE:
The starch indicator solution should only be added towards the end of the
titration. Use the pipette filler provided when pipetting the hexane solutions, since
hexane vapour may be harmful.
The tip of the pipette must pass through the hexane layer to reach the aqueous layer.
To prevent hexane solution from entering the pipette warm the bulb by hand, then
keep a finger firmly pressed on the back of the pipette.
It may be necessary to clean the pipette after each filling with hexane solution.
Make a note of the precise concentrations of the Na2S2O3 and KI provided. This
information will be written on the reagent bottles.

Calculating the partition coefficient

Calculate the partition coefficient, D, using the formula

D = [I2]hexane / [I2]water

¯
from the data obtained in the absence of I , and find the mean value. Using this value,
¯
calculate the equilibrium constant for each of the three determinations involving I in the
aqueous phase, and quote a mean value to the appropriate number of significant figures.
EXPERIMENT 10

PHASE EQUILIBRIA: A THREE-COMPONENT SYSTEM

Introduction

The aim of this experiment is to study the miscibility characteristics of three familiar
liquids: diesel, methanol and tetrahydrofuran (THF) and to summarize the results in the
form of a three-component phase diagram. Diesel itself is a rather complex mixture of
hydrocarbons having 15-25 carbon atoms in their molecules. However, for the purposes of
this experiment, we can consider diesel to be a single component.
Background to the diesel problem1
This country, together with much of the rest of the world, has to cope with a shortage of
crude oil. Since diesel and petrol are both obtained from crude oil, this creates both a diesel
and an oil problem. Owing to South Africa and Namibia being predominantly mining and
agricultural countries, the requirement for diesel is proportionately greater than for many
other countries. Diesel requirements therefore determine the volume of crude oil that is
imported.
One possible short term solution to the diesel problem could be to mix diesel with a
suitable diluent, in much the same way as petrol can be mixed, for example, with ethanol.
Unfortunately, diesel will not mix with ethanol or methanol in all proportions at normal
temperatures. For economic reasons, ethanol and methanol are the only two diluents that
can be considered at present. A way around this difficulty might be to add a, hopefully,
small quantity of a third component, or CO-SOLVENT, which will keep the diesel and
diluent in a single phase.
In this experiment, the use of tetrahydrofuran (THF) as a co-solvent for diesel and
methanol will be investigated. THF can be readily produced in large quantities from
furfural, obtained by acid hydrolysis of bagasse or maize husks, both waste materials of
our agricultural industry. THF has combustion properties which allow it to be used in
diesel engines.
Phase diagrams for three-component systems
When dealing with three-component systems an equilateral triangle is used. The corners of
the triangles represent the pure components. Refer to Fig. 1 (a). Points on horizontal lines
represent mixtures containing 75%, 50% and 25% A. The other components can, of course,
be represented in the same way, as shown in (b) and (c). Fig. 1(a), (b) and (c) can then be
combined as shown in Fig. 2.
The point x will then represent a mixture containing 50% A, 25 % B and 25% C. The
percentages can be expressed as volume percentage, mass percentage, etc., as is most

1
T M Letcher, CHEMSA, 7(2), 35(1981)
convenient. If only B and C were present, the mixture could be represented by a point on
BC (Y say, Fig.3). If A is now added to the mixture the composition would move towards
A and the relative amounts of B and C would remain constant. In other words, any point on
AY represents a composition for which B:C = CY:BY.

A A A
25%

75% 50%
50%
25% 75%

C B C
B C 75% 50% 25% B

(a) (b) (c)

Fig. 1.

A A A

T1 T2
T3
T4

C B C
B C B
Y
Fig 2. Fig 3. Fig 4.

Procedures

Make up mixtures (of total mass of about 50 g) of diesel and methanol containing 5, 25,
55, 75 and 90 % by mass of diesel in the stoppered flasks provided. It is not necessary to
make up mixtures having compositions exactly 5 %, 20 %, etc., but the actual composition
must be known. All these mixtures will consist of two separate liquid phases. If the bottles
are shaken, the two-phase liquid mixture will appear turbid and caramel-coloured.
Titrate the 90 % diesel mixture with THF and swirl the contents of the bottle after each
addition to assist equilibration. A point will be reached when one drop of THF changes the
turbid two-phase liquid mixture into a clear transparent one-phase liquid. The bottle is then
carefully wiped with a tissue paper and weighed. Calculate the composition of the solution
in terms of mass percentages and mark the point on the triangular graph paper supplied.
Measure the temperature of the solution. Repeat the procedure for the remaining solutions.
Join the points to form a smooth curve. This curve separates the region in which the three
components are completely miscible from the region in which two phases appear.
Effect of temperature

Increasing the temperature usually increases the region in which complete miscibility is
obtained. The effect of temperature can be represented by a three-dimensional diagram in
which the additional axis is the temperature axis. A more convenient representation is
effectively a projection of the lines obtained at different temperatures onto one plane (see
Fig. 4).

Questions

1. What is the minimum amount of THF that must be added in order that diesel and
methanol be mutually soluble in all proportions, at room temperature?
2. Can you foresee any difficulties that would be encountered when trying to use this fuel
blend (containing minimum amount of co-solvent as reported in question 1 above) on a
cold morning? Suggest some experiments that would have to be carried out in order to
avoid these difficulties.
3. Give the molecular structure of tetrahydrofuran and explain why this substance
is effective as a co-solvent for this system.
4. Would you expect H2O to be an effective co-solvent? Explain.
5. If some water were present in the methanol used to make up the fuel blend , would you
expect this to increase or decrease the extent of the two-phase region on the phase
diagram?
Reference: James and Princhard, Practical Physical Chemistry, 3rd Ed., p.83
Atkins, Physical Chemistry, 4th Ed., pp. 199-202