PHYSICAL CHEMISTRY MANUAL

Prof. Dr. Ferdane KARAMAN Assoc. Prof. Arzu HATİPOĞLU

Prof. Dr. Nergis ARSU Assoc. Prof. Dolunay ŞAKAR DAŞDAN
Prof. Dr. Özlem CANKURTARAN Assoc. Prof. Demet KARACA BALTA
Prof. Dr. Ayfer SARAÇ Assoc. Prof. Fatih ÇAKAR
Prof. Dr. Müzeyyen DOĞAN Assoc. Prof. Sevnur KESKİN DOĞRUYOL
Prof. Dr. Tarık EREN Res. Asst. Çağdaş BÜYÜKPINAR
Prof. Dr. Nevim SAN Res. Asst. Şeyda AYDOĞDU
Assoc. Prof. Meral AYDIN

İSTANBUL, 2017
 PHYSICAL CHEMISTRY MANUAL

Prof. Dr. Ferdane KARAMAN Assoc. Prof. Arzu HATİPOĞLU

Prof. Dr. Nergis ARSU Assoc. Prof. Dolunay ŞAKAR DAŞDAN
Prof. Dr. Özlem CANKURTARAN Assoc. Prof. Demet KARACA BALTA
Prof. Dr. Ayfer SARAÇ Assoc. Prof. Fatih ÇAKAR
Prof. Dr. Müzeyyen DOĞAN Assoc. Prof. Sevnur KESKİN DOĞRUYOL
Prof. Dr. Tarık EREN Res. Asst. Çağdaş BÜYÜKPINAR
Prof. Dr. Nevim SAN Res. Asst. Şeyda AYDOĞDU
Assoc. Prof. Meral AYDIN

İSTANBUL, 2017
Our former Faculty Member and Assistant Staffs who contributed in preparing of this
booklet:

Prof. Dr. Zekiye ÇINAR

Assoc. Prof Hale BERBER
Assoc. Prof Akif KAYA
Dr. Nazlı TÜRKTEN
Dr. Dila KAYA
Dr. Yasemin TAMER
Dr. Feyza KARASU
Dr. Murat KILIÇ
 PHYSICAL CHEMISTRY LABORATORY
STUDENT INFO

Name-Surname Student Number

PHOTO

e-mail GSM Number

Laboratory Assistant Term

No. Experiment Date Results Signature

9
 PHYSICAL CHEMISTRY LABORATORY
STUDENT INFO

Name-Surname Student Number

PHOTO

e-mail GSM Number

Laboratory Assistant Term

No. Experiment Date Results Signature

9
 DECLARATION

NAME-SURNAME:

STUDENT NUMBER:

I have been informed about the safety rules in the Physical Chemistry Laboratory by
instructors. I also have been warned about the possible dangers which I meet in laboratory in
case I do not obey the safety rules. I understand the importance of personal safety and know
that I should wear safety glasses, laboratory coat and gloves for the protection at all times in
the Physical Chemistry Laboratory. I accept the full responsibilities of any possible lab
accidents in case of violation of safety rules.
If I do not abide by the safety rules, I will not hold instructors of Physical Chemistry
Laboratory liable for any injuries which result.

Date:

Place: Physical Chemistry Laboratory

Signature:
 DECLARATION

NAME-SURNAME:

STUDENT NUMBER:

I have been informed about the safety rules in the Physical Chemistry Laboratory by
instructors. I also have been warned about the possible dangers which I meet in laboratory in
case I do not obey the safety rules. I understand the importance of personal safety and know
that I should wear safety glasses, laboratory coat and gloves for the protection at all times in
the Physical Chemistry Laboratory. I accept the full responsibilities of any possible lab
accidents in case of violation of safety rules.
If I do not abide by the safety rules, I will not hold instructors of Physical Chemistry
Laboratory liable for any injuries which result.

Date:

Place: Physical Chemistry Laboratory

Signature:
 CONTENTS

GENERAL INSTRUCTIONS IN THE LABORATORY ii

SAFETY RULES IN THE LABORATORY iii
Experiments
1. Determination of Heat of Solution with Solubility Method 1
2. Determining Surface Tension of Liquids Using The Ring (Du Nouy) Method 3
and Capillary Rise
3. Velocity of Molecules and The Maxwell Boltzmann Distribution Function 9
4. Determination of Heat of Vaporization of Liquids 15
5. Determination of Linear Expansion Coefficients of Metals by Dilatometric 19
Method
6. Viscosity 23
7. Refractive Index of Liquids and Molecular Refraction 28
8. Optical Rotation and Determination of Concentration by Polarimetric Method 33
9. Determination of The Heat of Combustion Using a Bomb Calorimeter 37
10. Solubility Diagram of Two Partially Miscible Liquids 42
11. Determination of The Kinetics of a Second Order Reaction Saponification of 46
Ethyl Acetate
12. Steam Distillation 50
13. Cryoscopy 54
14. Effect of Temperature on Reaction Rate and Determination of the Activation 60
Energy of a Chemical Reaction
15. Kinetics of the Decomposition Reaction of α,α'-Azobisisobutyronitrile 63
16. Refraction First Order Reactions Polarimetric Method 67
17. Ebullioscopy 71
18. Molecular Weight Determination by the Victor Meyer Method 75

REFERENCES 79

PERIODIC TABLE 80

i
GENERAL INSTRUCTIONS IN THE LABORATORY

1. Wear safety glasses, laboratory coat and gloves at all times in the laboratory.

2. Avoid loose clothing and loose long hair. Due to the fact that long hair is subject to fire
easily, it should be constrained by a hair band.
3. Read the experiment carefully, study the complete details of the experiment and do the pre-
lab assignments on time.
4. Know the safety rules which are specific for that day’s experiment before the laboratory
session starts. If you are in doubt about any procedure, ask your instructor before
commencing any preparation in the laboratory.
5. The results of all experiments must be recorded in the laboratory notebook. At the end of
experiment, the yield should be calculated. A short summary of the results including melting
points, boiling points, physical appearance of product, yield, etc. should be noted and
submitted to the instructor. If the work is approved by your instructor, you can proceed with
the next experiment in the laboratory.
6. Always be in the laboratory promptly. Never talk loudly, run and joke with your friends in
the laboratory. Wait your instructor silently.
7. Never eat, drink beverages chew gum and smoking in the laboratory.
8. Use mobile phone during experiment is not permitted in the laboratory with the exception
of emergency case.
9. Never bring your personal items (coat, backpack, handback, etc.), food and bevereage to
the laboratory. Use the cabinets in the out of the lab to store your personal items during lab
session.
10. Waste chemicals should be disposed as described by your instructor. There are special
containers in the organic laboratuary for this purpose. Do not spill any liquid chemicals and
put paper, broken glassware, or solid chemicals into the sink. A container is also provided to
store broken glassware.
11. Take only the amount of materials that you actually need for an experiment. Do not carry
any reagent bottles to your bench. Return all bottles and equipments to their shelf. Always
keep the balances clean and never dislodge them.
12. Clean and dry your laboratory bench at the end of the laboratory experiment.
13. Turned off the gas and water taps, remove the plug of your equipments before you leave
your working area.
14. Remove the gloves and wash your hands definitely at the end of the lab.

ii
SAFETY RULES IN THE LABORATORY

1. Do not leave experiments, which are heating or reacting.

2. Report all chemical spills immediately to your instructor. If any chemical is spilled or
splashed on your skin, wash the affected body area with copious amounts of water
immediately.
3. If you spill any acid or alkaline (base) on your skin or clothing, wash the affected body
area with water and then neutralize any acid with dilute ammonia-water solution or a solution
of sodium bicarbonate. Neutralise any spilled base with dilute acetic acid. Then wash with
dilute sodium bicarbonate. If you are not sure how to neutralize the spills, let your instructor
know immediately.
4. Always read the labels of chemicals used in the experiment carefully. Never use reagents
from unmarked bottle. If you are in doubt about reagent, ask your instructor for verifying.
5. Never pick up broken glassware with bare hands. Pick up with a brush and dust pan and
then place all broken glassware in the broken glassware container. Never put broken glass in a
garbage can.
6. Always be aware of what your neighbors are doing. Students who standing next to the
place where the accident occured are often injured in the laboratory. If an injury occur
regardless of how minor, report it immediately to the instructors.
7. Never work alone in the laboratory. When you need help in case of emergency, being alone
can be life threatening.
8. Do not inhale any fumes directly. Fume hoods should be used where poisonous or
irritating fumes are evolved. If anybody lose consciousness during a lab session due to
chemical fumes, report this situation to the instructors immediately.
9. Never taste or smell directly any chemicals in the laboratory. Keep in the mind that all
chemical materials are poisonous.
10. For diluting acids, always pour the acid into water while stirring. Never pour water into a
concentrated acid.
11. If any thermometer is broken, report it immediately to your instructor. Any spills of
mercury should be cleaned up immediately due to the fact that mercury pose a serious threat
for human body. The vapors accumulate in the room and raise dangerous concentrations in
the air. The exposure to heavy metal poisoning lead to serious health problems.
12. When inserting glass tubing into a rubber stopper, always use a cloth towel to protect
your hands. The glass should be moisturised with grease.

iii
13. Do not put same dropper into all reagent bottles when you take liquid chemicals.
14. Before starting the lab experiment, check the glassware whether it is cracked or not. If you
have a defective glassware such as cracked or broken, never use it on heating.
15. After heating process, allow to cool glassware (beaker, flask, etc.) before handling them.
16. Never use an open flame near a volatile or flammable liquid (e.g. diethyl ether). If a fire
occur in a beaker or other containers, cover it with a towel, fire blanket or flame-retardant
item. Never use water to extinguish a chemical fire due to the fact that some chemicals react
with water and cause an explosion. If your clothes catch the fire, scream to get attention of
instructors and use a fire blanket or safety shower immediately. You should know the location
of fire extinguishers and other emergency equipment in the laboratory. In case of the large
fire, the lab instructors decide the evacuation of the laboratory. Please, obey all instructions in
any emergency.

iv
1.EXPERIMENT

DETERMINATION OF HEAT OF SOLUTION WITH SOLUBILITY

METHOD

1.1. Object

To determine the heat of solution by using the solubilities of a dissolved substance in a

solvent at different temperatures.

1.2. Theory

The homogenous dispersion of one substance in another is called dissolution. Solubility is

the amount of dissolved substance (solute) in 100 mL of solvent. The solubility of a solid in a
liquid depends on the type of solid, type of solvent and temperature. If the solution process is
endothermic, solubility increases with temperature. If the process is exothermic, solubility
decreases with the increasing temperature. The correlation between temperature and the
solubility of a substance can be stated by Van't Hoff equation:

𝑑 ln 𝑆 ∆𝐻𝑆
= (1.1)
𝑑𝑇 𝑅𝑇 2
Equation 1.1 can be integrated between limits Si and S2 which are the solubilities at Ti and T2
temperatures by assuming that heat of solution AHs does not change in this temperature
range:

𝑆2 ∆𝐻𝑆 1 1
ln = (𝑇 − 𝑇 ) (1.2)
𝑆1 𝑅𝑇 2 1 2

AHs can be determined from the slope of the line obtained by plotting lnS versus 1/T. On the
other hand, if the solubilities of the solid at two different temperatures are known, then AH s

can be calculated by using equation (1.2).

1.3. Apparatus And Chemicals

A 50°C thermometer with 0.1 intervals, 2 weighing dishes, 2 5 mL pipettes, 3 250 mL erlen
meyer flasks, a 500 mL erlen meyer flask, a burette, oxalic acid, 0.6 N sodium hydroxide
solution, phenolphthalein indicator.

1
1.4. Method of Procedure

1. Prepare the saturated solution of oxalic acid at 50oC and cool to room temperature.

2. Place the saturated oxalic acid solution in a water bath and set the temperature of the bath
to 25oC.

3. Stir the saturated solution with a glass rod and constantly check the temperature of the
solution. When the temperature is 25oC take a 5 mL sample from the solution by a mildly
heated pipette, add it in a 250 mL erlen meyer flask and add 3 drops of phenolphthalein
indicator. Titrate the sample with 0.6 N NaOH and write down the volume of required
NaOH (S0) to neutralize the solution. Repeat the same procedure for 30, 35 and 40oC and
record the required NaOH volumes.

1.5. Results and Calculations

1. Use the equation below and determine the amount of oxalic acid dissolved in 100 mL
solution (solubility) at every temperature.

𝐸×𝑁×𝑆0 100
𝑆= × (1.3)
1000 𝑉

For equation (1.3);

S: Solubility, g/100 mL
S0 : Volume of 0.6N NaOH, mL
V: Volume of the titrated oxalic acid solution, mL
E: Gram-equivalent of oxalic acid
M(H2C2O4.2H2O) = 126 g/mol

2. Use the solubilities at two different temperatures and calculate the molar heat of solution
(AHs) of oxalic acid by using equation (1.2).

3. Plot InS versus 1/T. Calculate the molar heat of solution (AHs) from the slope of the
obtained line.

4. Compare the AHs values you have obtained by using analytical and graphical methods in
steps (2) and (3) and comment on both methods' accuracies.

2
2. EXPERIMENT

DETERMINING SURFACE TENSION OF LIQUIDS USING THE RING

(DU NOUY) METHOD AND CAPILLARY RISE

2.1. Object

To determine the surface tension of a liquid by Du Nouy ring and capillary rise methods and
to investigate the temperature effect.

2.2. Theory

The cohesive forces among liquid molecules are responsible for the phenomenon of surface
tension. In the bulk of the liquid, each molecule is pulled equally in every direction by
neighboring liquid molecules, resulting in a net force of zero. The molecules at the surface do
not have other molecules on all sides of them and therefore are pulled inwards. This creates
some internal pressure and forces liquid surfaces to contract to the minimal area. Figure 2.1
shows a liquid system in contact with its vapor.

Figure 2.1 Liquid-vapor interface

For the liquid to minimize its energy state, the number of higher energy boundary molecules
must be minimized. In order to enlarge the surface of a liquid by an area AA, a certain amount
of work AE must be performed;

∆𝐸
𝜀= (2.1)
∆𝐴

3
ε is the specific surface energy. It is identical with the surface tension;

𝐹
𝛾= (2.2)
𝑙

where force F acts along the edge of length l tangential to the surface to maintain the liquid
film. Surface tension has the dimension of force per unit length, or of energy per unit area.
When a ring of radius r is used, the length of the edge is;

𝑙 = 2.2𝜋𝑅 (2.3)
Surface tension is therefore measured in forces per unit length. In SI unit system, the unit for
surface tension is newton per meter but in the the cgs unit system dyne per cm is also used.
One dyn/cm corresponds to 0.001 N/m.

Influence of Temperature on Surface Tension

When a liquid is heated, kinetic energy of molecules increases. This results in a weakening of
the cohesive forces. The surface tension decreases linearly and, for all liquids, reaches the
value zero at the critical temperature Tk.

𝛾𝑚 = 𝑘𝛾(𝑇𝑘′ − 𝑇) (2.4)

Where; Tk' is the critical temperature and k is a constant for almost all substances (2.1 x 10-7 J
K-1 mol-2/3).

2.3. Methods of Measurement

Because surface tension manifests itself in various effects, it offers a number of methods to its
measurement. Which method is optimal depends upon the nature of the liquid being
measured, the conditions under which its tension is to be measured, and the stability of its
surface when it is deformed. These methods are; Capillary rise method, Stalagmometric
method, Du Nouy ring method, Wilhelmy plate method, Bubble pressure method.

2.3.1. Capillary Rise Method

Capillary rise is due to adhesive forces between the walls of the capillary tube and the liquid.
Adhesive forces pull the edges of the liquid upwards. The surface tension in the liquid
constantly pulls molecules from the surface inward (due to higher molecular energy levels at

4
the surface), but also holds the molecules at the surface together (cohesive forces). This
causes all of the liquid to rise rather than just the at the edges. The surface tension is
competing with the adhesive forces as well as the forces due to the weight of the liquid
column being lifted.

Figure 2.2 Wetting and non-wetting liquids in the capillary tube

Wetting liquids like water rise, non-wetting liquids like mercury descend in the capillary tube.
If the contact angle with the walls of the capillary tube is smaller than 90o, the liquid wets the
tube and a concave meniscus is formed on the surface of the liquid. Conversely, when the
contact angle is greater than 90o, the liquid does not wet the tube and a convex meniscus is
formed on the surface.

Figure 2.3 A liquid rise in a capillary tube

In capillary rise method, the height of the liquid in the capillary tube up to the surface is
measured. If a liquid with density p rises h in the capillary tube, then the total weight of this
liquid column will be equal to surface tension force. By using force balance equations, surface
tension is obtained as;
ℎ×𝑟×𝜌×𝑔
𝛾= (2.5)
2 cos 𝜃

5
Where g is the gravitational acceleration and 9 is the contact angle. For wetting liquids
θ<90°and cosθ ~ 1, surface tension equation takes the form;

ℎ×𝑟×𝜌×𝑔
𝛾= (2.6)
2

2.3.2. Du Nouy Ring Method

The Du Nouy ring method involves slowly lifting a 2-3 cm diameter ring, often made of
platinum or platinum/iridium alloy from the surface of a liquid. In surface tension
measurements, the ring is dipped into the liquid horizontally and then it is raised towards the
liquid-air interface. The maximum force acting on the ring at the moment the liquid film tears
is measured (Figure 2.4). Since metals have high energies, the adhesion of the liquid on to
metal surface is more than the cohesion in the liquid.

Figure 2.4. Liquid film surface during tear from the ring

Besides, the contact angle between the ring and the liquid is generally equal to zero due to the
complete wetting of the surface. Therefore, at the moment the liquid film tears from the ring
the force to be overcome is cohesive force instead of adhesive force. The force required to
raise the ring from the liquid's surface is measured and related to the liquid's surface tension.
This technique was proposed by the French physicist Pierre Lecomte du Nouy (1883-1947) in
a paper published in 1925.
The surface tension can be calculated from the diameter of the ring and the tear-off force;

F  2(2rort ) (2.7)

2.4. Apparatus and Chemicals

Torsion dynamometer, surface tension measuring ring, magnetic heating stirrer, silk thread,
graduated cylinder, universal clamp, water jet pump, electronic temperature control, rubber
tubing, distilled water, ethyl alcohol, soapy water.

6
 Figure 2.5 Experimental set-up

2.5. Method of Procedure

1. Set up the experiment as shown in Figure 2.5.

2. Degrease the measuring ring with alcohol, rinse it with distilled water and dry it. Use a silk
thread to attach the ring to the left arm of the torsion dynamometer.

3. Set the indicator to '0' and compensate the weight of the ring with the rear adjusting knob
so that the lever arm is in the white area between the marks.

4. Pour the liquid to be investigated into a 1000 mL crystallizing dish and also fill the
immersion tube and the rubber hose by briefly applying suction with the water jet pump.
The ring must be completely submerged.

5. Open the stopcock that is connected to the immersion tube via the rubber hose and let the
liquid slowly run out of the crystallizing dish into the smaller one. Continuously readjust
the torsion dynamometer while the liquid runs out to keep the lever arm in the white area
between the two marks.

6. Stop the measurement at the moment when the liquid film tears from the ring, and read off
the last value set on the torsion dynamometer.

7. Pour the liquid collected in the small crystallizing dish back into the dish on the magnetic
stirrer and repeat the above procedure at temperatures 30°C, 45°C, 60°C and 75°C.

7
8. Repeat the above procedures for soapy water and ethyl alcohol at room temperature.

9. For the capillary method, pour water, ethyl alcohol and soapy water into different beakers
at room temperature and immerse cappilary tubes with known radiuses into these liquids

10. Liquids in beakers will rise in the capillary tubes. Measure the rise h (cm) using a ruler.
11. Calculate the surface tensions of each liquids by using p, r, obtained h values and equation
2.6.

2.6. Results and Calculations

1. The diameter of the ring used in the experiment is 2.r = 19.65 mm.
2. Literature values are, ywater = 72.8 dyn/cm, yethanol = 21.97 dyn/cm at 25°C
3. List all the values you obtained in the following table.
4. Plot surface tension (y) versus temperature (K).

Table 2.1 Surface tension values

Surface Tension Surface Tension Temperature Surface Tension
Liquid/ Solution
(Du Nouy) (Cappilary Rise) (oC) (Du Nouy)
(mN/m) (dyn/cm) 30 (mN/m)
Water 45
Ethyl Alcohol 60
Soapy Water 75

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3. EXPERIMENT

VELOCITY OF MOLECULES AND THE MAXWELL BOLTZMANN

DISTRIBUTION FUNCTION

3.1. Object

To apply the Kinetic Theory of Gases, to determine the velocity distribution of the gases and
to compare to the theoretical Maxwell-Boltzmann velocity distribution.

3.2. Theory

Even in a small amount of a gas, there are a large number of molecules. These particles have a
range of different velocities, and the velocity of any single particle constantly changes due to
collisions with other particles. However, the fraction of a large number of particles within a
particular velocity range is nearly constant. The Maxwell distribution of velocities specifies
this fraction, for any velocity range, as a function of the temperature of the system. According
to kinetic theory of gases, gas molecules are traveling in various directions with different
velocities (see Figure 3.1).

Figure 3.1 The distribution of gas molecules in a three-dimensional environment

In Figure 3.1, the distance of each point from the origin is proportional to the size of
molecular velocity and since the distribution of molecular velocities is the same and they
exhibit isotropic behavior.

An ideal gas molecule has the below kinetic energy;

𝑚𝑐̅ 2
𝐸̅𝑘 = (3.1)
2

9
where;
Ek: Average kinetic energy
m: Mass of the molecule
c: Average velocity of the molecule
From kinetic theory, the pressure of an ideal gas can be described by:

1
𝑃 = 3 × 𝜌 × ̅̅̅
𝑐2 (3.2)

where;

P: Pressure
ρ: Density
Equations (3.1) and (3.2) are combined to obtain the following equation for 1 mol ideal gas:

𝑃 × 𝑉̅ = 𝑅 × 𝑇 (3.3)

By the substitution of equation (3.2) into equation (3.3), the average velocity of a gas
molecule (c) is found as:

3𝑘𝑇 1⁄2
𝑐̅ = ( ) (3.4)
𝑚

k: Boltzmann constant
R: Ideal gas constant
T: Absolute temperature
M: Molecular weight
m: Mass of a molecule
The above equations indicate that the average kinetic energy of an ideal gas is directly
proportional to the absolute temperature of the gas. The direct determination of the velocity of
a gas molecule is impossible because its velocity changes continuously due to collisions with
other molecules. For a great number of molecules, the distribution function for molecular
velocities can only be derived by means of statistical methods. This has been done by
Maxwell and Boltzmann with the following result:

10
 𝑚𝑐2
𝑑𝑁 2 𝑚 3⁄2 −( )
=√ ( ) 𝑐 2 𝑒 2𝑘𝑇 𝑑𝑐 (3.5)
𝑁 𝜋 𝑘𝑇

This equation describes the probability that the velocity of a molecule is within the interval
{c,c+dc}. The corresponding distribution function for oxygen at 273 K is shown in Figure 3.2
as an example.

Figure 3.2 Maxwell-Boltzmann velocity distribution curve for oxygen molecule at 273 K

The velocity corresponding to the maximum point of the curve is known as the velocity with
highest probability and described by the following relation:
2𝑘𝑇 1⁄2
𝑐𝑤 = ( ) (3.6)
𝑚
Substituting equation (3.6) into equation (3.5) leads to:
3⁄2 𝑐2
𝑑𝑁 2 1 2 −(𝑐2𝑤)
= √ ( 2) 𝑐 𝑒 𝑑𝑐 (3.7)
𝑁 𝜋 𝑐 𝑤

According to equation (3.7);

 2 8
cw : c : c  2 : : 3  1 : 1.13 : 1.22


In the model experiment with glass balls, the velocity of the balls is proportional to the
distance thrown s:

11
 𝑔 1⁄2
𝑐 = 𝑠 (2ℎ) = 𝐾𝑠 (3.8)

g: Acceleration at the earth surface (= 9.81 m/s2)

h: Height difference between outlet and receiver

The experimental results (number of balls per distance thrown interval) can be displayed
graphically in the form

1 𝑁𝑖
.
∑ 𝑁𝑖 ∆𝑐
= 𝑓(𝑐) (3.9)

Ni: Number of balls in the interval i, i = 1...23

Δc : Velocity interval corresponding to Δs = 1 cm (0.078 ms)

In this equation, Ni, indicates the number of balls with velocity difference Ac

Figure 3.3 Experimental and theoretical velocity distribution in the model experiment

Figure 3.3 shows the theoretical and experimental Maxwell-Boltzmann velocity distribution
curve. At 1500 K, the fraction of molecules with velocities in the range 1500 m/s ile 1501 m/s
is 5.10-6. The fraction of molecules in this range is very small. At 273 K this fraction is
approximately equal to zero. It means that there is no molecule moving with this velocity or
the number of such molecules is very low. At low temperatures, the distribution of velocities
is narrow. However, an increase in temperature broadens the velocity distribution towards
high velocities. At high temperatures, there are more molecules having high velocities and
thus high energies.

12
3.3. Apparatus and Chemicals

Experimental setup is shown in Figure 3.4.

4 glass beakers (50 mL), a spoon, a digital stopwatch and glass balls will be used.

Figure 3.4 Experimental set-up for the kinetic theory of gases

3.4. Method of Procedure

1. In order to measure the velocities of the balls, it is necessary to determine the average
number of glass balls expelled from the apparatus during 1 minute.

2. To do this, fill the apparatus with 400 glass balls. Instead of counting 400 glass balls,
determine the average weight of one glass ball by weighing. (For example, if the weight
of one glass ball is 0.1 g, then the average weight of 400 glass balls will be 40 g. In this
case, it can be considered that there are 400 glass balls in 40 g.)

3. Set the height of the upper piston to 6 cm and the oscillator frequency to 50 s-1.
4. Now open the outlet for 1 minute and determine the number of balls expelled by
weighing them. Refill the apparatus with these balls and repeat the experiment twice and
determine the average number of balls expelled per minute.

5. Fill the average number of glass balls expelled per minute into each of four glass beakers.
6. Fill the apparatus with 400 glass balls and make the following apparatus settings:
- height of the upper piston: 6 cm
- height difference between outlet and receiver: 8 cm
- oscillator frequency: 50 s-1
7. When the frequency is stable, open the outlet for 5 minutes. After each minute, pour the

13
 balls from one of the beakers into the apparatus to maintain a constant 'particle density'.

8. After 5 minutes, close the outlet.

9. Determine the number of glass balls in each of the 24 compartments of the receiver by
weighing.

3.5. Results and Calculations

Number of Number of
f(c)(s/m) c(m/s) f(c)(s/m) c(m/s)
Balls Balls
1 13
2 14
3 15
4 16
5 17
6 18
7 19
8 20
9 21
10 22
11 23
12 24

1. Plot f(c) versus c.

2. Is the velocity distribution you obtained in agreement with the Maxwell-Boltzmann
equation? Compare.

14
4. EXPERIMENT

DETERMINATION OF HEAT OF VAPORIZATION OF LIQUIDS

4.1. Object

To determine the heat of vaporization of a liquid and apply the Trouton's rule.

4.2. Theory

Vaporization of a liquid occurs with the absorption of heat. To determine the heat of
vaporization, the known mass of a liquid whose heat of vaporization to be found is vaporized
in a special vaporization tank. The amount of absorbed heat can be calorimetrically
determined regarding the heat of vaporization.

When liquids are heated at constant temperature, the liquid reaches the temperature at which
it is transferred from liquid phase to vapor phase. The temperature of the vaporization point
remains constant until the liquid phase is entirely vaporized. If one mole of liquid is
vaporized, the molar enthalpy of liquid, H, increases with the effect of absorbed heat, Qv. This
difference in enthalpies, AHv, is the enthalpy of vaporization. Heat of vaporization is the heat
needed to vaporize the liquid substance at its normal boiling point, in other words to break the
bonds between liquid molecules. If the amount of liquid substance is one unit of mass (1
gram), it is called specific heat of vaporization; if the amount is one mole, it is called molar
heat of vaporization (AHv, J.mol-1).

The entropy of vaporization which is the ratio of molar heat of vaporization of a liquid (AHv)
and normal boiling temperature (Tv, K), is around 80-90 J.mol-1.K-1 for majority of liquids.
This rule is known as the Trouton's rule. Substances with hydrogen bonds (such as water,
alcohols, amines etc.) and liquids whose boiling points are below 150 K do not obey this rule.
In conclusion, the entropy change which accompanies vaporization, ASv, can be expressed as
below using the second law of thermodynamics. The entropy of vaporization for Trouton's
rule can be calculated by using the equation below:

∆𝐻𝑉
∆𝑆𝑉 = ≅ 80 − 90 𝐽/𝑚𝑜𝑙. 𝐾 (4.1)
𝑇𝑉

15
 Figure 4.1 Experimental set-up

4.3. Apparatus and Chemicals

The experimental set-up can be seen in the figure above. Acetone and methanol will be used
in the experiments.

4.4. Method of Procedure

1. Pour 900 g of distilled water in calorimeter tank. Also place a stirring bar, temperature
probes and electric probes in the tank.

2. Weigh the empty spiral vaporization container. (m1)

3. Add 15 mL acetone in the spiral vaporization container and weigh it again. (m2)
4. Place the spiral vaporization container in the calorimeter tank. Attach the air control valve
and the vacuum connection tube to a safety bottle and assemble the system.

5. Turn on the tempereture gauge and wait for approximately 5 minutes for it to reach the
thermal equilibrium. Write down the thermal equilibrium temperature. (T1= oC)

6. Open the air control valve and vacuum. Wait until the system's temperature is constant, in
other words until the temperature drops about 1oC. In order to prevent the liquid from
spilling out of the vaporization container's spiral, maintain the equilibrium by opening and
closing the air control valve. Write down the constant temperature. (T2= oC)

7. Remove the vacuum from the system and tightly close the air control valve.
8. To determine the total heat capacity of the calorimeter, perform electrical calibration.
Attach the work-force meter (constanter) probe to the 8V AC for electrical heating.
Constantly heat the system and write down the applied energy at various temperatures

16
 (Ws) in the heating range. When the system's temperature rises about 1oC and work-force
meter shows about 4000 Ws, remove the work-force meter probe and switch off the
heating by pushing the stop button on the energy gauge. Write down the applied electrical
energy (Wel = Ws) and the final temperature of the system (T3= oC)

9. When the experiment is over, dry the spiral vaporization container and weigh it. (m3)

10. Repeat the same steps for methanol.

4.5. Results and Calculations

1. Calculate the amount of liquid in the spiral vaporization container (m4), by subtracting the
mass of the empty container (m1) from the mass of the container with liquid (m2).

𝑚4 = 𝑚2 − 𝑚1 (4.2)

2. Calculate the amount of liquid in the spiral vaporization container after the experiment

m5 = m3 -m1 (4.3)

3. Calculate the mass of liquid vaporized. (mvapor).

𝑚𝑣𝑎𝑝𝑜𝑟 = 𝑚4 − 𝑚5 (4.4)

4. Calculate the enthalpy change (ΔHv) which occurs during the condensation of m grams of
vapor at the boiling point. This value is proportional to the heat capacity of the calorimeter,
Ck .

∆Hv = -Ck ∆Tv (4.5)

In equation (4.5), ΔTv is the difference in temperature during the vaporization of m grams
of liquid;

∆Tv = T2 -T1 (4.6)

5. Vaporization of m grams of liquid causes a 1°C drop in system's temperature. The energy
lost during this temperature decrease is equal to the electrical energy given to the system to
increase the temperature 1°C and it is proportional to the heat capacity of the system.

17
 Wel = Ck ∆Tel (4.7)

In equation (4.7), ΔTel is the difference in temperature of the system;

∆Tel = T3 -T2 (4.8)

Equation (4.5) can be rearrenged so that the molar heat of vaporization can be written as
below:

∆𝑇 𝑀
∆𝐻𝑣 = −𝑊𝑒𝑙 ∆𝑇 𝑣 (4.9)
𝑒𝑙 𝑚

Calculate the molar heat of vaporization (ΔHv, J/mol) using equation (4.9).

6. Calculate the entropy of vaporization (ΔSv, J/mol) using the obtained ΔHv value and
equation (4.1).

7. Compare the ΔSv you have calculated to Trouton's rule and explain if this rule applies to
acetone and methanol and also explain if the ΔSv you found is correct by using the
molecular properties of these liquids.

Mmetanol : 32.04 g.mol ΔHv,acetone : 29.1 kJ.mol Tv,methanol : 64.7 °C

Macetone : 58.09 g.mol ΔSv,methanol : 100.0 J.mol Tv,acetone : 56.5 °C

ΔHv,methanol : 33.8 kJ.mol ΔSv, acetone : 88.3 J.mol

18
5. EXPERIMENT

DETERMINATION OF LINEAR EXPANSION COEFFICIENTS OF

METALS BY DILATOMETRIC METHOD

5.1. Object

To measure the linear expansion of brass, steel, copper, aluminium and Duran glass using a
dilatometer, to calculate the linear expansion coefficients and to determine the volume
expansion coefficient of water.

5.2. Theory

The linear expansion of solid bodies and the volume expansion of water are functions of
temperature. In order to investigate expansion, tubes made of brass, steel, copper, aluminium
and glass are clamped tight at one end, and water from a temperature controlled bath is
circulated through them. The change in length at various temperatures is measured using a
dilatometer. The measurement of the volume change of water is achieved using a flat-
bottomed flask with an upright graduated tube, which is located in a temperature controlled
bath (pycnometer).
An increase in the temperature of a solid body intensifies oscillation of the atoms in the
lattice. This causes the average distance between the atoms to be increased, and with this, an
increase in the volume V at constant pressure p.
1 𝜕𝑉
α= ( ) (5.1)
V 𝜕𝑇 𝑃
f is the thermal expansion coefficient. If only one dimension is considered (e.g. length), one
obtains the thermal linear expansion coefficient α;

1 𝜕𝑙
γ= ( ) (5.2)
V 𝜕𝑇 𝑃

where l is total length of the body.

In a liquid, a temperature increase intensifies the thermal movement of the particles and hence
increases the volume. An exception is the anomalous behaviour of water between 0°C and
4°C. By measuring the increase in volume or length, thermal expansion coefficients can be

19
calculated through the equation;
∆𝑉
𝛼= (5.3)
𝑉0 ∆𝑇
∆𝑙
𝛾= (5.4)
𝑙0 ∆𝑇

where;
V0 : Initial volume prior to temperature change
l0 : Corresponding initial length
To evaluate the experiment, prepare plots of the changes in the length of the tubes and the
volume change of water versus the temperature. Calculate the coefficients of expansion from
the slopes using equations (5.3) and (5.4). In the case of materials with temperature-
dependent coefficients of expansion, the plot does not give a straight line; the coefficient of
expansion can only be calculated for temperature intervals or expressed as approximate
polynomials.

5.3. Apparatus and Chemicals

Dilatometer with clock gauge, brass tube, iron tube, glass tube, copper tube, aluminium tube,
flat bottomed flask, immersion thermostat, 100°C, water bath

Figure 5.1 Experimental set-up

5.4. Method of Procedure

5.4.1. Measurement of Linear Expansion

1. Clamp the first tube over its whole length (600 mm) in the dilatometer.
2. Connect it to the circulating pump of the thermostat via rubber tubing. Keep the tubing as
far as possible away from the dilatometer in order not to heat up the frame of the
dilatometer.

20
3. For the same reason, avoid long periods of readjustment of the temperature controlled bath
and set the temperature only with the accuracy of the thermostatic control. After the initial
temperature (approximately 20°C) has been reached, set the meter to '0', and then raise the
temperature in four steps, each of 10°C to 15°C.

4. Record the respective changes in length and the corresponding temperatures.

5. Repeat this measurement series with each of the remaining four materials.

Figure 5.2 Experimental set-up

5.4.2. Measurement of Volume Expansion

1. First calibrate the pycnometer. To do this, determine the empty mass of the flat- bottomed
flask with graduated tube.
2. Fill the pycnometer with water and refit the graduated tube.
3. Use a syringe with a cannula to fill the graduated tube up to approximately the '100' mark.
4. Warm the filled pycnometer to 80°C in the temperature controlled bath to remove any
dissolved gases. After this, subject it to temperature equilibriation at 25°C, and
meticulously remove all gas bubbles (Caution: knocking on the graduated tube can easily
cause it to break!).
5. Read off the fluid level in the graduated tube, carefully dry its outer surface, and again
accurately weigh the pycnometer.
6. Use the injection syringe to add 1 ml water to the upright graduated tube and temperature
equilibrate the new volume at the same temperature. Again read off the level and weigh
the apparatus.
7. Repeat this process for five fill levels. From these values and the density of water (0.997
g/cm3 at 25°C) calculate the volume corresponding to one graduation. This value should
be about 0.01 ml. With the empty mass of the pycnometer, the absolute value can be
derived.

21
5.5. Results and Calculations

1. Plot linear expansion of tubes versus absolute temperature (K).

2. By using Equation (5.4) and slope of graphs, calculate linear expansion coefficients (y)
and record in Table 5.1.
3. By using tare of pycnometer calculate the weight of water.

4. By using obtained volume values and density of water (0.997g/cm3 at 25oC) calculate the
volume expansions of water.
5. Plot volume expansions of water versus absolute temperature (K). By using Equation (5.3)
and slope of graph, calculate thermal expansion coefficient of water (a) and record in Table
5.1.
6. Compare your values with reference values in Table 5.1 and make comments.

Table 5.1 Linear expansion coefficients

Reference Experimental
Brass 1.8 x 10-5 K-1
Copper 1.5 x 10-5 K-1
Aluminium 2.3 x 10-5 K-1
Iron 1.2 x 10-5 K-1
Glass 3.6 x 10-5 K-1
Water 2.75 x 10-4 K-1 *
(*) in the range of 20-30 oC.

22
6. EXPERIMENT

VISCOSITY

6.1. Object

To determine the viscosity of liquids and to investigate the variation of viscosity with
temperature.

6.2. Theory

The property that characterizes a fluid's resistance to flow is its viscosity. The kinetic theory
of gases describes viscosity as a transport of momentum from a mobile plane to another.
Viscosity of gases is too low, but viscosity of solids is too high. However, the viscosity of
liquids is variable in a broad range which is influenced by the characteristics of the liquid and
the temperature. The viscosity of a liquid is a measure of internal resistance to flow. The rate
of flow of a liquid through a tube mostly depends on the forces that tend to slow down its
flow. However, the planes of the fluid in the tube flow at different speeds.

The planes near the walls of the tube flow more slowly than the ones at the center of the tube.
Therefore, we can consider the whole liquid as a set of tubes one in the other having the same
center. If a plane in a liquid with surface area S (cm2) moves with a velocity v (cm.sec-1) with
respect to another parallel plane separated by a distance l (cm) then this plane exerts a
frictional force f (dyne) on the other which is directly proportional to the velocity of flow and
the surface area of the layers but inversely proportional to the distance at which the planes of
the liquid are separated from each other.

S
f  .(V . ) (6.1)
l

The proportionality constant ^ is known as the coefficient of viscosity that depends on the
characteristics of the liquid and the temperature. The unit for the coefficient of viscosity is
poise (dyn.sec.cm-2). The reciprocal of viscosity is defined fluidity Φ as shown in Equation
(6.2).

Φ = 1/η (6.2)

23
The viscosity coefficient of a liquid can be determined by measuring the flow rate of a liquid
through a capillary tube. Poiseuille has found out that flow rate (v) of a liquid, amount of
liquid flowing per second is directly proportional to the pressure difference (p) across the tube
and to the fourth power of the radius (r) of the tube and inversely proportional to the viscosity
coefficient (η) of the liquid. The volume of liquid (V) flowing at time t is:

v (r 4 P)
 (6.3)
t 8l

where;
l: length of the capillary tube (cm)
r: radius of the capillary tube (cm)
P: pressure difference across the tube
Then equation (6.3) is rearranged to give;

r 4 PT
 (6.4)
8Vl

Measurement of all the quantities in this equation separately is defined as absolute

measurement. Because of the difficulty to calculate the radius of the tube, relative
viscosity measurement is preferred. The principle of this method is to measure the
viscosity of the liquid sample relative to the reference sample. When both sides of
these two equations are divided by each other, we get the below expression.

1 P1t1
 (6.5)
 2 P2 t 2

Since pressures P 1 and P 2 are directly proportional to the densities d 1 and d 2 , the ratio
of coefficients of viscosity is;

1 p1t1 d1t1
  (6.6)
 2 P2 t 2 d 2 t 2

Viscosity constant k is defined by equation (6.7)

24
 2
k (6.7)
d 2t 2

Viscosity constant k is a temperature dependent value. It does not depend on the type
of the characteristics of the liquid. Viscosity coefficient can be expressed in terms of
k as;

  kdt (6.8)

For compounds belonging to the same chemical class, viscosity increases with increasing
molecular weight. For example, in straight-chain hydrocarbons, viscosity increases as the
length of the chain increases. Hydrogen bond increases the viscosity of the compounds having
hydroxy groups. The reason for the high viscosity of glycerine molecule is that it has three
hydroxy groups. The viscosity of gases increases, but the viscosity of liquids decreases with
increasing temperature. The relation between the viscosity coefficient of a liquid and
temperature is given by;
𝜂 = 𝐴𝑒 𝐸⁄𝑅𝑇 (6.9)
or
𝑙𝑛 𝜂 = 𝑙𝑛 𝐴 + 𝐸 ⁄𝑅𝑇
(6.10)
where;
A: a constant
E: the activation energy for viscous flow
E depends upon the characteristics of the liquid. A plot of ln η vs 1/T is a straight line with a
slope equal to E/R.

6.3. Apparatus and Chemicals

The Ostwald Viscometer shown in Figure 6.1 is used as a viscometer in the experiment.
Generally, viscometers are used to measure the time required for a fixed volume of liquid to
flow through the capillary tube. A fixed volume of liquid fills the wide arm. In the right side
of the viscometer, there is a capillary tube. The time for the liquid to flow from level a to level
b is measured. The viscometer is placed in a water bath to keep the temperature constant
throughout the experiment and the temperature is continuously checked with ±1°C sensitivity.
In this experiment, distilled water and 50% glycerine solution will be used.

25
 Figure 6.1 Ostwald viscometer

6.4. Method of Procedure

1. Using a pipette, add a fixed volume of distilled water to the wide arm of the viscometer
and heat the water bath to reach 30°C. Allow the temperature of the distilled water to
reach equilibrium with the temperature of the water bath. Attach a pipette pump to the thin
arm of the viscometer. By applying a pressure, the water is forced up above the level and
then remove the pump. It is allowed to fall back through the capillary under a pressure due
to its own weight and measure the time for the liquid to fall from level a to level b. Repeat
this procedure three times. (Note that it is important to maintain the temperature constant
throughout the experiment.)

2. Repeat the same procedure for the distilled water at 40°C and 50°C temperatures and
measure the flow time of distilled water at these temperatures.

3. Empty the water from the viscometer and fill in with 50% glycerine solution. Repeat the
same procedure, substituting 50% glycerine for the distilled water and measure the flow
time at these temperatures.
4. Measure the density of 50% glycerine at these temperatures by using a picnometer. Write
all values in Table 6.1 and Table 6.2.

26
 Table 6.1 Measured values of water

T°C dwater (g/cm) ηwater (poise) t (sec) k

30 0.99568 0.008004
40 0.99224 0.006536
50 0.98807 0.005492

Table 6.2 Measured values of the sample (50% glycerine)

T°C T 1/T d (g/cm) t (sec) k η (poise) In η

30 303 0.00330 1.0355
40 313 0.00319 1.0272
50 323 0.00309 1.0219

6.5. Results and Calculations

1. Calculate the viscosity constant k for each temperature using equation 6.8 with the given
values of ηwater and dwater in Table 6.1 and measured twater values throughout the
experiment.

2. After the viscosity constant k for each temperature is found out, calculate the viscosity
constant k for each temperature of the sample with using the same equation.

3. Plot the ln η vs 1/T graph as described by equation (6.10). The graph should be linear and
has a slope equal to E/R. Calculate the activation energy for viscous flow of the liquid (E)
from the slope of the graph.

4. Comment your results at the end of the experiment.

27
7. EXPERIMENT

REFRACTIVE INDEX OF LIQUIDS AND MOLECULAR

REFRACTION

7.1. Object

To determine the index of refraction and the density of a given liquid, to calculate the specific
and molecular refraction and to determine the concentration of a given solution by
refractometry.

7.2. Theory

Refraction is the change in direction of a monochromatic ray of light passing from one
transparent and homogeneous medium into another. The basic reason is the density difference
of the two media and the fact that light moves with different velocities in different media
(examples: formation of rainbow, mirage).

Snell's law (also known as the Snell-Descartes law and the law of refraction) is a formula
used to describe the relationship between the angles of incidence and refraction, when
referring to light or other waves passing through a boundary between two different media,
such as water and glass. Although named after astronomer Willebrord Snellius (1580-1626),
the law was first accurately described by scientist Ibn Sahl. For this law;

1. Incident ray, refracted ray and normal are on the same plane (Figure 7.1).

Figure 7.1 Refraction of light

28
 2. When a ray of light passes from a low density medium into a high density medium, it
refracts approaching to the normal and its velocity decreases.

3. The ratio of the sines of the angles of incidence and refraction is constant and equal to
the ratio of the velocities of the light in the two media. This is known as "Snell's
Law";

sin 𝜃1 𝑣1
𝜂= = (7.1)
sin 𝜃2 𝑣2

Where each θ is the angle measured from the normal of the boundary, v is the velocity of light
in the respective medium (SI units are meters per second, or m/s) and n is the index of
refraction (which is unitless) of the respective medium. In order to make n a definite,
characteristic constant, v1 is referred to the velocity of light in vacuo. Since this velocity is a
maximum value independent of the wavelength, n is always greater than unity. Ordinarily air
is chosen as the reference medium. In that case the refractive index must be multiplied by the
ratio vvacuum/vair = 1.00029 in order to get the true refractive index.

Measurement of the angle of refraction depends upon the concept of projecting light rays
travelling in all directions on to a prism in contact with the liquid sample and detecting the
border of the light and dark regions. Critical angle is the angle of incidence for which the
angle of refraction is 90o. Since the ray of light cannot travel in the medium with any greater
angle than the critical angle, the region corresponding to greater angles will be dark and those
corresponding to smaller angles will be light. The boundary of these two regions gives the
critical angle.

The apparatus used to measure the index of refraction is called Abbe Refractometer. In the
Abbe Refractometer the liquid sample is sandwiched into a thin layer between an illuminating
prism and a refracting prism. The dark region generated by the rays with greater angles of
incidence than the critical angle and the light region formed by the rays with smaller angles
can be detected.

Refractive index is related to wavelength of light and density of the medium (temperature,
pressure, concentration). Specific and molecular refraction that are not related to temperature
and pressure are calculated during the experiment (Equations 7.2 and 7.3).

29
For Lorenz and Lorentz, specific refraction (R) is;

R= (1 / ρ) x [(n2 - 1) / (n2 + 2)] (7.2)

and molecular refraction is;

R= (M / ρ) x [(n2 - 1) / (n2 + 2)] (7.3)

Here; ρ is density of the sample, M is molecular weight, n is refractive index.

7.3. Apparatus and Chemicals

The apparatus to be used is "Abbe refractometer" whose working principle is based on critical
angle. It consists of two prisms of flint glass with a refractive index of 1.75 which can be
separated so as to allow the introduction of a few drops of liquid. The prisms can be rotated
by a movable arm which carries the reading glass.

The position of the border line of total reflection is observed through the fixed telescope and
by turning the movable arm it is made to coincide with the intersection of the cross hairs in
the telescope as seen in Fig. 7.2. The arc is graduated so as to read directly refractive indices.
The compansator is used to produce a dispersion equal but opposite to that of the liquid. It
permits the border linet o be changed from a colored band to a sharp colorless band. In order
to carry out measurements at constant temperature, the apparatus is connected to a waterbath
and thus water at a given temperature is circulated through the casing of the prisms.

Figure 7.2 Abbe Refractometer

30
 Figure 7.3 Abbe Refractometer

7.4. Method of Procedure

1. Open the instrument's prism case. By turning the latch, separate the lower prism.
2. Place three or four drops of liquid on the lower prism enough to coat the entire prism with
a thin film and then close the prism assembly.

3. Look through the instrument's eyepiece and turn the prism adjustment knob until a distinct
light/dark border becomes visible.

4. Adjust the compensator dial to remove as much color as possible from both the light and
dark areas.

5. Adjust the eyepiece to bring the light/dark border into a sharp focus, and then readjust the
prism knob to place this border in the center of the crosshairs. Read the refractive index
from the scale visible through the eyepiece. The value can be read directly to the third
decimal place. The fourth decimal is estimated. Therefore, repeat each measurement three
times and take the average.

6. Clean the prisms with alcohol solution for each measurement.

7. Indicate the densities of the samples (glycerin and water) by a pycnometer at the ambient
temperature (Equation 7.4).

Pt°c = [(w1 x D) / w] - [0.0012 (w1 - w) / w] (7.4)

Here w1 is gravity of the sample at t temperature, w is gravity of pure water at t

temperature, D is density of water at t temperature and t is the experiment temperature.

31
7.5. Results and Calculations

1. Determine the refractive index of the sample at the ambient temperature by using the
average values.

2. Calculate the density of the sample at the ambient temperature by using equation (7.4).
3. Calculate the specific and molecular refractions of the sample by using equations (7.2).
4. Compare the results with the literature values and find the error ratio.

5. Measure the refractive indices of pure water, 25%, 50%, 70% and 100% glycerin
solutions. Plot refractive index (ordinate) versus concentration (abscissa).

6. Determine concentration of the sample using the graph.

32
8. EXPERIMENT

OPTICAL ROTATION AND DETERMINATION OF

CONCENTRATION BY POLARIMETRIC METHOD

8.1. Object

To measure the angles of rotation of solutions consisting of an optically active substance with
different concentrations, to determine the relation between the angle of rotation and
concentration and to determine concentration by means of polarimetric method.

8.2. Theory

Light is composed of a large number of electromagnetic waves vibrating at right angles to the
direction of propagation with all directions being equally probable. An electromagnetic wave
consists of an electric field and a magnetic field. These two components vibrate on two
mutually perpendicular planes perpendicular to the direction of propagation as well. Normal
light can spread along every direction on the plane but when this light is passed through
certain materials it can be collected on one plane. This type of light is called plane polarized
light or shortly polarized light vibrating in one direction. This kind of light can be obtained by
Nicol Prism that is made of CaCO3.

On the other hand, circularly polarized light represents a wave whose electric field vector
forms a spiral in clockwise or counterclockwise direction.

Substances that can rotate plane-polarized light to left or right are called optically active
substances. The rotation of plane-polarized light by an optically active substance is shown in
Figure 8.1.

Figure 8.1 Rotating polarized light plane by optically active substance

33
In order to be optically active, the substance should not have a symmetry plane or a centre of
symmetry. Moreover, it should be non-superimposable with its mirror image. Optically active
substances have an asymmetric carbon atom. If the four groups bonded to the central carbon
atom are different from each other, the central carbon atom is called asymmetric carbon atom
or chiral carbon atom (Figure 8.2). Substances that rotate the plane-polarized light clockwise
are called "dextro-rotatory compounds" whereas the ones that rotate counterclockwise are
termed "levo-rotatory compounds".

Figure 8.2 Chiral carbon atom

The parameters that affect the angle of rotation are;

• Temperature
• Wavelength of the light
• Distance light travels
• Structure of the compound
• Concentration of the compound
At a certain temperature, for a certain wavelength, the specific rotation;

𝛼
[𝛼]𝑡𝜆 = (8.1)
𝑙𝑐

where;
α: Angle of rotation
l: Length of the polarimeter tube (dm)
c: Sample concentration (g/mL)
Polarimeters are used in the determination of molecular dimensions and concentration and
also in the control of foodstuffs.

34
8.3. Apparatus and Chemicals

3%, 6%, 9% and an unknown concentration of glucose solutions and a polarimeter (Figure
8.3)

Figure 8.3 Polarimeter

A polarimeter is a device used for the measurement of optical rotation and its scheme is
depicted in Figure 8.3.
Polarimeter consists of a monochromatic light and two Nicol prisms which the optically
active substance is placed between them. A Nicol prism is constructed by cutting CaCO3
prism in half along a suitable diagonal plane and cementing the sections together with Canada
balsam. When the unpolarized light comes to this prism, it branches two polarized light which
their vibration planes are perpendicular to each other. At CaCO3-Canada balsam interface,
one component is totally reflected to the side, where it is absorbed by a black coating applied
to the prism. Other polarized light transmits through the prism. When the second Nicol prism
is placed at an angle of 90 degrees with the first prism, if the substance which is in the sample
tube is not optically active, no light radiates from the second prism. If the substance is
optically active, a light radiates from the second prism. The polarimeter analyser must be so
adjusted that both semicircles visible in the ocular have the same level of brightness. The
angle of rotation (a) can then be directly read from the scale. If the analyser is turned towards
right the optically active substance is dextro, if it should be turned towards left then the
substance is levo.
Light source of polarimeter is sodium vapour lamp or mercury vapour lamp. Wavelengths of
sodium lamp are 589-589.6 nm. Wavelengths of mercury lamp are 435.8; 491.6; 546.1; 577.0;
579.1 nm.

8.4. Method of Procedure

1. Polarimeter tube is filled with water. Turn-on the polarimeter and wait for 5 min to warm

35
 the lamp. Empty water in the polarimeter tube. Wash the polarimeter sample tube with a
small amount of the solution to be measured and fill the sample tube with the solution.
Close and wipe the sample tube and check that the solution contains no bubbles. Place the
polarimeter tube in the polarimeter.

2. Measure the angles of rotation of the solutions, 3%, 6% and 9% glucose solutions. For
each of the solutions, find the transition point of the following circular shapes shown in
Figure 8.4 and read the angle of rotation (α) from the polarimeter scale.

Figure 8.4 Different fields of vision observed during a measurement

3. Measure the angle of rotation for the unknown concentration of glucose solution. Pour out
the solution from polarimeter tube and clean it, fill it with distilled water then place into
polarimeter. Turn-off the polarimeter.

8.5. Results and Calculations

1. Calculate the specific rotation of glucose [𝛼]𝑡𝜆 by using the angles of rotation for each of
the solutions and equation (8.1).

2. Take the average of the specific angles of rotation. This value is the average value of the
specific angle of rotation of glucose at 20oC. Calculate the weight percentage composition
of the unknown solution by using the average value of the specific angle of rotation and
equation (8.1).

3. Plot the angle of rotation (a) versus solution concentration (c, g/100 mL).

Read the concentration of the unknown solution from the graph.

36
9. EXPERIMENT

DETERMINATION OF THE HEAT OF COMBUSTION USING A BOMB

CALORIMETER

9.1. Object

To determine the heat of combustion and to calculate the heat of formation of naphthalene
using a bomb calorimeter.

9.2. Theory

In a chemical reaction, the structure of the reactants changes and new substances which are
called "products" are formed. During a reaction, some chemical bonds are broken and some
new chemical bonds form. All these changes cause a change in the energy of the system.
While some chemical reactions (exothermic reaction) occur, heat is evolved to the
surroundings. In some others (endothermic reaction), heat is absorbed from the surroundings.
All these energy changes are shown as the "heat of reaction".

The heat of reaction is the heat that is absorbed or evolved to form products from reactants at
constant temperature and pressure. The absorbed or evolved heat at constant pressure, is equal
to the enthalpy change (ΔH) in the system. Therefore; the heat of reaction is called the change
in the enthalpy of the system in a chemical reaction and designated by ΔHr.

The heat of reaction can be calculated by using the enthalpy of formation (ΔHf) of the
compounds. The heat of formation of a chemical compound is the heat of reaction of its
formation reaction in which 1 mole of the compound is formed from its elements at 1 atm
pressure and 25°C temperature. Actually, ΔHf can be described as molar enthalpy of a
chemical compound. The heat of formation of every element in its stable and pure state is
assigned the value zero.

The heat of reaction can be calculated by using the heats of formation of substances as
described in the below expression.

Δ𝐻𝑓 = ∑𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 𝑛𝑖 Δ𝐻𝑓,𝑖 − ∑𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠 𝑛𝑖 Δ𝐻𝑓,𝑖 (9.1)

A calorimeter is an apparatus used to measure the heats of reaction of the chemical reactions
experimentally. The principle of the calorimetry is to determine the temperature difference of

37
the reaction throughout experiment. By using this temperature difference and heat capacity of
the calorimeter, the evolved heat in the reaction can be calculated. For the determination of
the value of the heat of formation of a compound in a calorimetric reaction, the reaction must
take place as quickly as possible without forming any side reactions.

In order to measure heats of formation in a calorimeter the reactions must go to completion

and only one product is formed. The heats of formation of some compounds (compounds
consisting H, S, N etc.) can not be determined experimentally. In that case, the heat of
formation of a compound can be calculated from the measured value of the heat of
combustion of the compound. The combustion reaction is defined as the reaction in which one
mole of the substance is burned with excess oxygen which is necessary to burn the substance
completely.
Combustion reactions may take place in a constant volume bomb calorimeter at constant
temperature and in the presence of oxygen at 25 atm pressure. Bomb calorimeter is immersed
in a water bath and combustion reactions are carried out by using electrical energy. Since heat
is evolved in the reaction, at thermal equilibrium the temperature of the water is a bit higher
than the initial temperature. The quantity of evolved heat (Qcal) can be calculated by using the
heat capacity of the bomb calorimeter Ccal (7310 J/K) and the change in temperature (ΔT) in
the combustion reaction of the substance. The following formula is valid for the quantity of
evolved heat:
𝑄𝑐𝑎𝑙 = −𝐶𝑐𝑎𝑙 Δ𝑇 (9.2)
The enthalpy (H) is defined as,
H = E + PV (9.3)
Heat of reaction can be written from the definition of enthalpy in equation (9.3)
ΔHr = ΔE + [(PV)products -(PV)reactants ] (9.4)
When gas substances exist in the reaction medium, the equation can be written as below;
ΔHr = ΔE + [Pproducts -Preactants ]V (9.5)
In this equation, V is the constant volume of the bomb calorimeter. Gaseous substances
obey the ideal gas law at high temperatures, then we get equation (9.6).
ΔH = ΔE + ΔnRT (9.6)
In this equation, Δn is the change in the mole numbers of gas molecules in the reaction. When
all the reactants and products are solid and liquid in a reaction, the equation can be written as
equation (9.7).
ΔHr = ΔE (9.7)

38
In this experiment, the following reaction formula is valid for the combustion of naphthalene:

C10H8 + 12O2 → 10CO2 + 4H2O

The heat of combustion of naphthalene (AHc,Naft) is expressed as below.

ΔHc,Naft = 10(ΔHf )CO2 + 4(ΔH)H2O - (ΔHf)Naft (9.8)

The only unknown term is the heat of formation of naphthalene (ΔHf,Naft) in this equation.
The heat of combustion of naphthalene (ΔHc,Naft) can be calculated by using equation (9.9).
𝐶𝑐𝑎𝑙 Δ𝑇𝑀𝑁𝑎𝑓𝑡
Δ𝐻𝑐,𝑁𝑎𝑓𝑡 = (9.9)
𝑤𝑁𝑎𝑓𝑡

Ccal: Heat capacity of the calorimeter

WNaft: Mass of the naphthalene pellet (g)
MNaft : Molar mass of naphthalene (g/mole)
ΔHc,Naft: Molar heat of combustion of naphthalene
ΔT: Temperature difference during the combustion of naphthalene

9.3. Apparatus and Chemicals

Naphthalene, iron wire, bomb calorimeter, glass test vessel, magnetic heating stirrer, magnetic
stirrer bar, O2 tube, temperature meter digital, temperature probe, power supply, connecting
cord, pellet press for calorimeter

Figure 9.1 Experimental set-up

1. Cut an approximately 10 cm long length from the iron wire and weigh it.

2. Weigh approximately 400 mg naphthalene sample into a weighing dish.

39
3. Form a pellet of naphthalene sample with the two open ends of the iron wires in it by
using a pellet press. Prepare 3 pellet samples.

4. Weigh pellet sample consisting of naphthalene and iron wire.

5. Fit the pellet with the two ends of the wires in the contacts of the lid of the bomb
calorimeter. It should be located above the center of the sample vessel. Close the bomb
calorimeter.

6. Place bomb calorimeter into the glass test vessel.

7. After filling the bomb calorimeter with oxygen at a 10 bar maximum pressure, close the
control valve and disconnect it from the pressure tube.

8. Fill the combustion vessel with exactly 850 g of water and insert the sealed bomb
calorimeter and the temperature immersion probe in it. Set the temperature meter to
measure the temperature difference (ΔT) over time.

9. Place the magnetic stirrer bar in the calorimeter and switch on the magnetic stirrer.
10. Connect the contact sockets of the bomb calorimeter to 15 V voltage of the power supply
unit. Power on the power supply and begin recording the initial temperature.

11. Set the temperature meter to measure the temperature difference ΔT over time and record
the temperature twice per minute to an accuracy of 0.01 K.

12. After each measurement, shut off the power supply to release excess oxygen and the gases
evolved during the reaction before opening the bomb.
13. Perform the measurements three times for each substance. Take the average of the
measured values to minimize any random errors.

9.4. Results and Calculations

1. Plot the temperature-time graph as seen in Figure 9.2 by using the values of temperature
differences.

40
 Figure 9.2 Temperature-time difference graph

2. Figure 9.2 illustrates how to determine the corrected temperature difference (ΔT) in order
to calculate the heat of combustion. This correction is necessary due to the exchange of
heat between the calorimeter and its surroundings. The vertical straight line must be
placed so that the shaded areas around the point of inflection are of the same size.
3. Heat of combustion can be calculated by using the corrected temperature difference value
(ΔT) in equation 9.9.
4. The heat of combustion of naphthalene can be calculated by using equation 9.8 with the
values corresponding to the standard heats of formation of the oxides CO2 (-393.77 kJ/
mol) and H2O (-286.17 kJ / mol).
5. Find out the literature value of the heat of formation of naphthalene. Compare the
literature value with the measured experimental value. Calculate the experimental error
and comment on the reasons.

41
10. EXPERIMENT

SOLUBILITY DIAGRAM OF TWO PARTIALLY MISCIBLE LIQUIDS

10.1. Object

To construct the solubility diagram of two partially miscible liquids and to determine their
"Critical Solution Temperature".

10.2. Theory

For liquids, there are three types of states at any given temperature;

 Miscible

 Partially miscible

 Immiscible

Besides, solubility depends upon temperature, it may happen that two liquids which are
completely miscible at a specific temperature may become partially miscible at a different
temperature.

Phenol/water system is an excellent example of partially miscible liquids. When small

amounts of phenol is added to water at ambient temperature, phenol dissolves completely in
water and a single phase homogeneous mixture is obtained. If you continue adding phenol, at
a particular concentration, mixture becomes saturated and two phases occur. The upper layer
is a solution of water in phenol, and the lower layer is a solution of phenol in water. At a fixed
temperature, the composition of each solution is fixed and both of the solutions are in
equilibrium with each other.

As the temperature is raised, mutual solubility increases and the two liquids dissolve in each-
other. Two solutions of different compositions existing in equilibrium with one another are
known as conjugate solutions. They are saturated solutions of one component in the other.
The line connecting the coexisting liquids is designated as the tie line. Above a particular
temperature, such solutions are completely miscible in all proportions. Such a temperature is
known as the "Critical Solution Temperature" as shown in Figure 1.1. Above this
temperature, the liquid mixture is homogeneous. Below this temperature, the mixture

42
separates into two layers. Critical solution temperature is 65.85 0C for phenol/water system.
The left side of the curve shows solutions of phenol in water, and the right side solutions of
water in phenol.

In this experiment, a number of mixtures of known concentration of phenol and water are
prepared and heated until complete miscibility is achieved. As the mixtures cool, two-phase
systems form at certain temperatures which are recognisable by the appearance of turbidity.
Plotting separation temperatures against concentrations of the mixtures gives the solution
diagram of the system and critical solution temperature can be determined.

Solubility curves of partially miscible liquids generally include a maximum critical solution
temperature like phenol/water system. However, systems like triethylamine/water and
nicotine/water have different curves. Triethylamine/water system has a curve that has a
minimum critical solution temperature while nicotine/water system exhibits both upper and
lower critical solution temperatures. The diagram is called a closed solubility loop.

Figure 10.1 Solubility diagram of phenol/water system

10.3. Apparatus and Chemicals

Water bath for thermostat, immersion thermostat, accessory set for immersion thermostat,
hard glass test tubes, stirrer, phenol solution (90%).

43
 Figure 10.2 Experimental set-up

10.4. Method of Procedure

1. Set up the experiment as shown in Figure 10.2.

2. Place the phenol/water mixtures as listed in Table 10.1 in the water bath and set the
temperature of the bath to 75°C.

3. During heating, shake the mixtures time to time.

4. When clear solutions have formed in all test tubes, switch off the thermostat heating and
start the cooling function.

5. Record the temperatures at which the turbidity caused by separation becomes visible. Plot
the saturation temperatures against the composition of the mixtures as weight percentage
w/%.

10.5. Results and Calculations

1. List all the saturation temperature values you obtained in the following table.

2. Plot weight percentages (w/%) of the mixtures, versus temperature (°C).

3. Determine the "Critical Solution Temperature" from the maximum point of the solubility
diagram.

4. Compare the literature value with the measured experimental value. Calculate the

44
experimental error and comment on the reasons.

Phenol (w/%) Saturation Temp. (°C)

10 %
20 %
30 %
40 %
50 %
60 %
70 %
80 %

Critical Solution Temperature :…………°C

45
11.EXPERIMENT

DETERMINATION OF THE KINETICS OF A SECOND ORDER

REACTION SAPONIFICATION OF ETHYL ACETATE

11.1. Object

To determine the kinetics of a second order reaction and the rate constant k of the reaction.

11.2. Theory

A reaction is a second order reaction if the rate is proportional to the square of the
concentration of one reactant or is proportional to the product of the concentrations of two
reactants . For example, if the reaction is

A+B C

where the initial concentrations are "a" and "b" of the reactants A and B and "x" is the
concentration of each of the reactants reacted in time t. The rate of the reaction may be written
as;

𝑑𝑥
= 𝑘(𝑎 − 𝑥)(𝑏 − 𝑥)
𝑑𝑡

(11.1)

Integrating and solving for the rate constant k, we have;

2.303 𝑏(𝑎−𝑥)
𝑘 = 𝑡(𝑎−𝑏) log 𝑎(𝑏−𝑥)

(11.2)

When the initial concenrations of the reactants "a" and "b" are the same (a=b), the differential
rate equation (11.1) may be written as;

𝑑𝑥
= 𝑘(𝑎 − 𝑥)2 (11.3)
𝑑𝑡

which may be integrated after rearranging to give;

46
 1 𝑥
𝑘= (11.4)
𝑡 𝑎(𝑎−𝑥)

Sapofinication of ethyl acetate with a basic solution is a second order reaction and can be
represented by the following stoichiometric equation.

CH3COOC2H5 + NaOH CH3COONa+C2H3OH

In order to determine the rate constant of this reaction, ester and base solutions are added into
two different vessels in a thermostat. Once the temperature of the solutions is constant, these
two solutions are mixed together. Samples are collected from the reaction mixture in short
time intervals. First of all, these samples are poured into a standard acid solution, so
neutralization reaction occurs between the acid solution and the unreacted NaOH from the
sapofinication reaction. At the end of the neutralization, back titration with a standard base
solution yields the quantity of the unreacted acid and the quantity of the unreacted NaOH. The
amount of ethyl acetate is determined as the algebraic difference between the initial and final
concentrations of NaOH in the reaction. Reaction rate constant is calculated by using equation
(11.2). If the initial concentrations of the ester and base solutions are chosen to be equal to
each other in the experiment, equation (11.4) can be used to estimate the rate constant, k.

11.3. Apparatus and Chemicals

20 mL and 25 mL pipettes, 1 L volumetric flask, 500 mL graduated cylinder, erlenmeyer

flask, burette, beaker, ethyl acetate, 4/3 N NaOH solution, 1/30 N H2SO4 solution,
phenolphthalein indicator.

11.4. Method of Procedure

1. Prepare 1/30 M NaOH solution. For preparing solution, pipette 25 mL sample from 4/3 N
NaOH solution and pour it into 1 L of volumetric flask. Add distilled water to the volumetric
flask and fill up to the calibration mark.

2. Pour 500 mL of 1/30 M NaOH solution into the reaction vessel by using a graduated
cylinder.

3. Pipette 25 mL of 1/30 N H2SO4 solution into an erlenmeyer flask and add a few drops of
phenolphthalein indicator. Repeat this procedure for the other three erlenmeyer flasks.

4. Fill the burette with 1/30 N NaOH solution.

47
5. After adding 1.64 mL of ethyl acetate into the reaction vessel under constant stirring, start
the reaction time. Continue stirring until experiment is completed (In that case, the initial
concentration of ethyl acetate is 1/30 M).

6. Pipette 20 mL sample from the reaction vessel after 5 minutes. Pour the sample into the
erlenmeyer flask which contains 25 mL of 1/30 N H2SO4 solution. In the medium, there is
the quantity of H2SO4 solution which does not take part in the neutralization reaction.
Titrate unreacted H2SO4 in neutralization reaction with 1/30 M NaOH solution from
burette. Determine the volume of NaOH (V1).

7. Repeat this procedure for the reaction time intervals of 15, 25, 35 minutes to estimate the
volumes of 1/30 M NaOH solution V2, V3, V4 respectively.

11.5. Results and Calculations

1. Calculate the volume of the reacted and unreacted 1/30 M NaOH solution in the
saponification reaction for all the samples.

Volume of unreacted 1/30 M NaOH solution= (25-V1) mL (11.6)

Volume of reacted 1/30 M NaOH solution= [20-(25-V1)] mL (11.7)

2. Mole number of the reacted NaOH solution in all samples which is collected from reaction
vessel=[20-(25-V1)/1000] x (1/30) mole/20 mL sample (11.8)

Mole number of reacted NaOH solution for 1 L reaction mixture is equal to the product of
the above expression by 1000/20. Thus;

xi=[20-(25-V1)]/(20x30) mol/L (11.9)

Calculate xi values from equation (11.9) for all the collected samples.

3. Calculate rate constants by using equation (11.4) for all the samples and take average of
these four values.

4. Plot a graph of xi/[a(a-xi)] versus time (t) which should be a straight line passingthrough
the origin. From the slope of the straight line, the rate constant k is determined. Compare
the results of the graphical rate constant value and average rate constant value.

5. Calculate the half life of the reaction, τ, by using the graphical rate constant value. The half
1
life for a second order reaction is 𝜏 = 𝑘𝑎

6. Plot a graph of (a - xi) versus time (t). Determine the time required for half of the initial

48
 NaOH concentration to react. Read this value from the graph. Compare your result with
the value obtained from equation (11.9).

1 1
7. Plot a graph of (𝑎−𝑥 ) versus time (t) which should be linear with a positive intercept .
𝑖 𝑎

Determine "a" value from the graph. Calculate the experimental percentage error by
comparing real and experimental values of "a".

49
12. EXPERIMENT

STEAM DISTILLATION

12.1. Object

To apply the principles of steam distillation and to determine the molecular weight of the less-
volatile component in a binary mixture by using their weights in the distillate.

12.2. Theory

Distillation is the process of separating components of a mixture by vaporization and then

condensing the vapor into liquid in a separate container. By using this process, components of
a mixture can be separated based on the difference between their boiling points. There are 4
methods of distillation depending on the application methods:

 Simple Distillation

 Vacuum Distillation

 Fractional Distillation

 Steam Distillation

In chemical technology, steam distillation is a very important technique used to separate and
purify liquids with high boiling points at lower temperatures than their boiling points. This
method is able to provide a much sharper and reliable result when the liquid to be separated is
immiscible with water.

Steam distillation is used for purification of substances that are insoluble in water, especially
in the production of essence oils in fruits and flowers.

The principle on which steam distillation is based is that when a mixture of two or more
immiscible liquids is heated, total vapor pressure of the system (P) equals the sum of the
partial pressures of substances PA and PB.

P = PA + PB (12.1)

50
The vapor pressure of the liquid mixture at the boiling point is equal to the external pressure.
By using of the ideal gas law and Dalton's Law of Partial Pressures, we can write for the
substance A and B which are present in V volume of the steam;

PA.V = nA.RT = (WA/MA ).RT (12.2)

PB.V = nB.RT = (WB /MB ).RT (12.3)

By dividing the above two equations side by side, we obtain

WA/WB = (PA.MA)/(PB.MB) (12.4)

where;

WA: weight of A in the distillate. WB: weight of B in the distillate.

PA: partial pressure of A at the distillation temperature (mmHg)

PB: partial pressure of B at the distillation temperature

MA: molecular weight of A (g.mol-1)

MB: molecular weight of B (g.mol-1)

In order to find the molecular weight of a substance immiscible with water, this substance is
distilled by steam. The weights of the collected material in the distillate and water are
calculated separately by the following equation.

W = Wi.di (12.5)

where;

Vi: volume of substance i in the distillate

Di: density of substance i in the distillate

Distillation temperature and the pressure under the experimental conditions are determined.
The partial pressure of water is determined from steam pressure curve given in Figure 12.2.

51
12.3. Apparatus and Chemicals

Experimental setup is shown in Figure 12.1.

Steam distillation apparatus is shown in Figure 3.1. The substance that you' ll find the
molecular weight is toluene.

Figure 12.1 Experimental set-up

12.4. Method of Procedure

1. Fill half of the first round bottom flask which is used as the steam generator with water and
close the safety valve with rubber septum and then connect to the distillatation flask (See
figure 12.1). Add 100 mL toluene and 50 mL pure water into the distillation flask, close
the distillation flask with rubber, place the thermometer and complete the condenser
connections. Check the water flow through the condenser.

2. Ignite the gas burners carefully. Heat the distillation flask very slowly at the beginning of
the experiment and if steam is able to pass to the second flask without condensation, put
out the gas burner under the distillation flask. When steam starts to exit from safety valve,
close the Mohr pense.

3. Record the atmospheric pressure at the beginning and end of the experiment (use
barometer).

4. Collect the first 5-10 mL of the distillate into an erlenmayer flask. Start collecting the
distillate into a graduated cyclinder when it starts dropping regularly. Continue this

52
 operation till 100 mL of distillate is collected in the graduated cylinder. Record the
temperature at which the sample is started collecting. Do not forget to record the
temperature in every minute during collecting the samples. At the end of the experiment,
release the Mohr penses, stop the water flow and put out gas burners.

12.5. Results and Calculations

1. Calculate the boiling point of the mixture by taking the avarage of all the recorded
temperatures.

tAVR =(t1+t2+….+tn)/n (12.6)

2. Find the vapor pressure of water at the boiling point of the mixture from figure 12.2.
Calculate the partial pressure of toluene by subtracting this value from the atmospheric
pressure.

3. Read the volumes of the collected phases in the graduated cylinder and calculate the
weights of toluene and water.

Top phase: toluene d: 0.867 g.cm-3

Bottom phase:water d:1.000 g.cm-3

4. Calculate the molecular weight of toluene by using Eq (12.4).

5. Compare the theoretical molecular weight of toluene to the experimentally determined one
and determine the relative error. Disscuss the reasons of these errors.

53
13. EXPERIMENT

CRYOSCOPY

13.1. Object

To determine the freezing point depression of acetic acid after dissolving benzoic acid in it
and to assess the molar mass of acetic acid by using the obtained value of freezing point
depression.

13.2. Theory

A solution has different properties than the solvent and the solute of which it is comprised.
These properties may be divided into two main groups as colligative and non-colligative
properties. Colligative properties depend on the number of solute particles in a solution and
not their characteristics. Colligative properties include solution properties such as vapor
pressure lowering, freezing point depression, boiling point elevation and osmotic pressure.
Non-colligative properties depend on the characteristics of both the solvent and the solute and
are associated with the taste, colour, viscosity etc. of the solution.

Freezing point of a solution is lower than that of the pure solvent. Experimental determination
of the freezing point depression with a suitable apparatus is called cryoscopy. If the properties
of a solvent are known, the molar mass of the solute can be determined. Freezing point
depression results from the difference in chemical potentials of the pure solvent and the
solution. The chemical potential of a solvent in a solution may be written as;

𝜇(𝑥1 ) = 𝜇 0 + 𝑅𝑇 ln 𝑥1 (13.1)

In the above equation μ(x1) corresponds to the chemical potential of the solvent in solution
and μ0 corresponds to the chemical potential of the pure liquid solvent. Since the mole
fraction of the solvent in a solution, x1, is always between 0 and 1, lnx1 is always negative.
Therefore the second term of equation (13.1) is always negative. Thus, the chemical potential
of a solvent in a solution is always smaller than that of the pure solvent by ∆𝜇 = −𝑅𝑇 ln 𝑥1 .

Lowering of the solvent's chemical potential causes a decrease in vapor pressure of the
solvent. This change in vapor pressure can be expressed by Raoult's Law (13.2). According to
this law, the partial pressure of a solvent in vapor phase equals the product of its mole fraction

54
in the solution and the vapor pressure in its pure state.

𝑃 = 𝑥1 𝑃∗ (13.2)

Figure 13.1 shows the change in freezing point in accordance with the decrease in solvent's
vapor pressure.

At pressure P and at the freezing point with the temperature T, pure solid is in equilibrium
with its solution. So the equilibrium condition is;

𝜇1 (𝑥1 ) = 𝜇𝑠 (𝑝𝑢𝑟𝑒) (13.3)

Figure 13.1 The phase diagram of a pure solvent and its solution

Rearranging equation (13.3) by neglecting the pressure dependence of chemical potential and
using equation (13.1) leads to the following equation:

𝜇𝑙0 + 𝑅𝑇 ln 𝑥𝑙 = 𝜇𝑠 (𝑝𝑢𝑟𝑒) (13.4)

Since the chemical potentials of pure substances are the molar free energies G0, for P=1
equation (13.4) becomes;

0
∆𝐺𝑓𝑢𝑠𝑖𝑜𝑛
𝐺𝑙0 − 𝐺𝑠0 = −𝑅𝑇 ln 𝑥𝑙 or − = 𝑇 ln 𝑥𝑙 (13.5)
𝑇

Gibbs-Helmholtz equation for constant pressure may be written as:

55
 𝐺
𝑑( ) 𝐻
𝑇
=− (13.6)
𝑑𝑇 𝑇2

Differentiating equation (13.5), we obtain;

∆𝐻𝑓𝑢𝑠𝑖𝑜𝑛 𝑑 ln 𝑥1 ∆𝐻𝑓𝑢𝑠𝑖𝑜𝑛 1 1 ∆𝐻𝑓𝑢𝑠𝑖𝑜𝑛 𝑇−𝑇0

= and − ln 𝑥1 = (𝑇 − 𝑇 ) = (𝑇𝑇) (13.7)
𝑅𝑇 2 𝑑𝑇 𝑅 0 𝑅 0

Freezing point depression ΔT= T0 -T, is a very small quantity proportional to the freezing
point of the pure solvent T0, so the term T.T0 can be expressed as T02 . Also when the mole
fraction of the solvent, x1 , is expressed as the solute's mole fraction, x2, as in x1=1-x2 for
ideal dilute solutions, then lnx1 = ln(l-x2) = -x2 can be obtained. If equation (13.7) is
rearranged with these assumptions, the freezing point depression, ΔT, may be expressed as;

𝑅𝑇02
∆𝑇 = ∆𝐻 𝑥2 (13.8)
𝑓𝑢𝑠𝑖𝑜𝑛

When the solute's mole number is so small compared to the solvent's in dilute solutions, it can
be neglected and mole fraction of the solute can be written as follows:

𝑛 𝑚 𝑚𝑀
𝑥2 = 𝑛2 = 1000/𝑀 = 10001 (13.9)
1 1

In equation (13.9), mole fraction of the solute is expressed in terms of molality. Molality, m,
is the number of moles of solute in 1000 grams of solvent.

The freezing point depression is expressed as:

𝑀1 𝑅𝑇02
∆𝑇 = ∆𝐻 𝑚 or ∆𝑇 = 𝐾𝑓 𝑚 (13.10)
𝑓𝑢𝑠𝑖𝑜𝑛 .1000

In this equation;

Kf : Molar freezing point depression constant or the cryoscopic constant

m : Molality

M1 : Molar mass of the solvent

ΔHfusion: The enthalpy of fusion of the solvent

56
R : Ideal gas constant

13.3. Apparatus and Chemicals

Magnetic stirrer, temperature meter, 1000 mL beaker, the experimental assembly consisting
of cylindrical inner and outer glass tubes, a two-necked adapter, temperature probe, protective
sleeve for temperature probe, pipettes, ice, acetic acid, benzoic acid, ethanol, spatula and
clamp.

13.4. Method of Procedure

1. Set-up the apparatus as seen in Figure 13.2.

2. The medium between the inner and outer tubes ensures uniform heat conductance. Fill this
area with approximately 35-40 mL of ethanol.

3. Place the two-necked adapter on top of the inner tube. The upper opening of the adapter is
for the temperature probe and the opening on the side is for introducing the substance to be
dissolved.

4. Place a 15 mm long magnetic stirring bar in the inner tube.

5. Press the substance whose molar mass is to be calculated into an approximately 600 mg
pellet and note the pellets weight.

6. Pour 50 mL of pure acetic acid into the inner tube with a pipette.

Figure 13.2 Experimental set-up

7. Place the protective temperature sleeve on top of the two-necked adapter and drop a few

57
 drops of raw alcohol onto the protective sleeve to improve heat transfer. Place the
temperature probe and connect it to the temperature meter.

8. When the apparatus is assembled, fix the device to the support rod.

9. Fill the 1000 mL beaker with ice and place the second temperature probe into the ice-
filled beaker. Place a magnetic stirring rod into this beaker and set the stirring speed as
medium.

10. Place the experimental apparatus in this beaker.

11. Set the beaker's temperature at about -10°C.

12. When the temperature of the inner tube reaches approximately -1°C, set the digital
temperature meter to measure the change in temperature, ΔT and start recording the
temperatures every minute.

13. With the obtained data, plot a cooling curve as seen in Figure 13.3 and record pure acetic
acid's freezing point. (The freezing point is the maximum level on the cooling curve.)

14. After the cooling curve of pure acetic acid is obtained, remove the apparatus out of the
ice-filled beaker and wait until the acetic acid in the inner vessel is completely melted.

15. After the liquification is completed, place the benzoic acid pellet into the inner tube and
let it dissolve in acetic acid completely.

16. Once again place the apparatus into the beaker and start measuring the temperature.

Figure 4.3 Cooling Curve of Water – Table Salt Mixture

17. Plot a second cooling curve and determine the freezing point of the solution, T.

58
13.5. RESULTS AND CALCULATIONS

1. Using the T and T0 values obtained from the cooling curves, calculate the freezing point
depression, ΔT.

2. With the calculated ΔT, the Kf=3.58 K/m and equation (13.10), find out the molality of the
solution, m.

3. Calculate molar mass of benzoic acid using the determined value of m and equation (13.9).

4. Compare the real molar mass value of benzoic acid and your experimentally calculated
result. Comment on the results.

59
14. EXPERIMENT

EFFECT OF TEMPERATURE ON REACTION RATE AND

DETERMINATION OF THE ACTIVATION ENERGY OF A
CHEMICAL REACTION

14.1. Object

To determine the relation between the rate of a chemical reaction and the temperature and to
calculate the activation energy of the reaction by the help of this relationship.

14.2. Theory

According to the experimental values, the rate of a chemical reaction generally increases with
increase in temperature. A change in the reaction rate can be expressed in terms of the change
in the reaction rate constant which depends upon temperature. The minimum energy that the
reactant molecules must have before the reaction takes place is known as the threshold
energy. This energy is defined as "activation anergy" and the molecule having this enegy is
defined as "activated complex". The activated complex has the most suitable configuration of
atoms which corresponds energetically to the top of the energy barrier forming the products.
There is a significant difference between this activated complex and the normal molecular
species. In activated complex, some new bonds are formed, while some bonds are broken.
The number of activated molecules can be increased by increasing the temperature.

Potential energy surface of a chemical reaction is given in Figure 14.1. The minimum points
of the curve correspond to the reactants and the products. The activated complex is always at
the maximum point of the energy curve and forms an enegy barrier which separates the
reactants from the products. If this energy barrier has a low energy, the reaction will take
place more rapidly.

Figure 5.1 Potential energy surface of a chemical reaction

60
The relation between the rate constant k and temperature for elementary reactions is
represented by Arrhenius equation.

𝑘 = 𝐴𝑒 −𝐸𝑎 ⁄𝑅𝑇 (14.1)

In this equation; k: Reaction rate constant, A: Frequency factor, Ea: Activation energy,
R:Ideal gas constant, T: Absolute temperature

Converting equation (14.1) to the logarithmic form, we have;

𝐸
ln 𝑘 = ln 𝐴 − 𝑅𝑇𝑎 (14.2)

The time (t) required to complete a certain reaction is inversely proportional to the rate
constant. Therefore, when 1/t term is written instead of k in equation (14.2), we obtain;

𝐸
ln 𝑡 = −ln 𝐴 + 𝑅𝑇𝑎 (14.3)

According to this equation, the activation energy of a reaction can be calculated by

determining the time required to complete this reaction at different temperatures.

𝐾𝐵𝑟𝑂 + 5 𝐾𝐵𝑟 + 3 𝐻2 𝑆𝑂4 → 3 𝐾2 𝑆𝑂4 + 3 𝐵𝑟2 + 3 𝐻2 𝑂

The above reaction proceeds slowly at room temperature. The time required to complete the
reaction can be determined by adding phenol and methyl red indicator into the medium. At
the end of the reaction, bromine is produced and it reacts quickly with phenol to form
tribromophenol. After the whole amount of phenol is consumed, the color of the indicator
disappears due to the remaining bromine in the medium.

14.3. Apparatus and Chemicals

A thermostat, test tubes, 3 pipettes, a chronometer, 0.01 M phenol, bromide bromate solution
(0.0833 M KBr + 0.0167 M KBrO3 solution corresponds to 0.05 M bromine), 0.5 H2SO4,
methyl red indicator.

14.4. Method of Procedure

1. Add 5 mL phenol, 5 mL bromide bromate solution and 5 drops of methyl red indicator
into a test tube.

61
2. Add 2.5 mL of H2SO4 solution into a second test tube.

3. Place each of the test tubes into the water bath at 25°C. When the solutions in the tubes
reach this temperature, stir the solutions and determine the disappearance time of the pink
color.

4. Repeat this procedure for the temperatures 35°C, 45°C and 60°C.

14.5. RESULTS AND CALCULATIONS

1. List the experimental data, time (t), ln t, temperature (T) and 1/T in the below table.

2. Plot a graph of ln t versus 1/T. Determine the equation for the straight line y=mx+n that
best fits through linear regression by using a computational program.

3. Determine the activation energy of the reaction from the slope of the straight line (m) and
calculate the frequency factor (A) by using equation (14.3).

°C t (sec) ln t T (K) 1/T

30
40
50
60
70

62
15. EXPERIMENT

KINETICS OF THE DECOMPOSITION REACTION OF a,a'-

AZOBISISOBUTYRONITRILE

15.1. Object

To determine the reaction rate constant for the thermal decomposition of a,a'-
azobisisobutyronitrile (AIBN) in dimethylformamide at several different temperatures and the
activation energy of the reaction using the temperature dependence of the resulting rate
constants.

15.2. Theory

When heated in inert solvents, a,a'-azobisisobutyronitrile (AIBN) decomposes into equivalent

quantities of isobutyronitrile radicals and nitrogen. This reaction can be kinetically monitored
via the volumetric determination of the quantity of gas evolved over time.

In a rate-determining unimolecular elementary reaction, the thermal decomposition of a,a'-

azobisisobutyronitrile (AIBN) results in the formation of stoichiometric quantities of nitrogen
and isobutyronitrile radicals which are subject to an additional sequence of rapid reaction
steps.

For this reason, the decomposition rate complies with a simple first order rate law (Eq. 15.1)
and at constant temperature is determined only by the concentration cAIBN of a,a'-
azobisisobutyronitrile at time t and the concentration independent (but temperature
dependent) reaction rate constant k.

𝑑[𝐴𝐼𝐵𝑁]0
𝑅𝑎𝑡𝑒 = − = 𝑘[𝐴𝐼𝐵𝑁] (15.1)
𝑑𝑡

Integration results of equation (15.1) between limits 0 and t in the following:

63
 [𝐴𝐼𝐵𝑁]0
ln [𝐴𝐼𝐵𝑁]
= 𝑘𝑡 (15.2)

where;

[AIBN]0 : The initial concentrations of AIBN at time (t0)

[AIBN] : The concentrations of AIBN at time (t).

t0 and t which are contained in equation (15.2) can be expressed by gas volumes V∞ and V
present at time t or after complete reaction of the reactants, respectively.

𝑉∞
ln 𝑉 = ln 𝜑 = 𝑘𝑡 (15.3)
∞ −𝑉

ln(𝑉∞ − 𝑉) = −𝑘𝑡 + ln 𝑉∞ (15.4)

According to this, rate constant (k) can be determined from the slope of the line obtained by
𝑉∞
plotting ln 𝑉 versus t (time).
∞ −𝑉

The dependence of the thus-determined rate constant k on the temperature T is described by

the empirically established Arrhenius equation:

𝑘 = 𝐴𝑒 −𝐸𝑎⁄𝑅𝑇 (15.5)

where;

Ea: Activation energy

A : Frequency factor

In accordance with the correlation obtained by taking the logarithm of equation (15.5);

𝐸𝑎 1
ln 𝑘 = − + ln 𝐴 (15.6)
𝑅 𝑇

the activation energy can be determined graphically from the slope of the linear relationship
between ln k and 1/T .

Also the activation energy can be determined by use of the equation (15.7), obtained from
(15.6) for only two known pairs of values for the rate constants (k1 and k2) and temperature
(T1 and T2).

64
 𝑇 𝑇 𝑘
𝐸𝑎 = 𝑇 1−𝑇2 𝑅 ln 𝑘2 (15.7)
2 1 1

15.3. Apparatus and Chemicals

Magnetic heating stirrer, electronic temperature control, thermocouple, magnetic stirrer bar,
volumetric flask (50 mL), pippette, round bottom flask, condensor, α,α’-
azobisisobutyronitrile, N,N-dimethylformamide, rubber caps, syringe, Silicone fluid for
heating bath, gas syringe, stopwatch.

15.4. Method of Procedure

1. Set up the experiment as shown in Figure 15.1.

2. Prepare the 1 molar α,α’-azobisisobutyronitrile solution required for the experiment as

follows: Weigh 8.212 g of α,α’-azobisisobutyronitrile into a 50 mL volumetric flask, dissolve
it in dimethylformamide and top it off to the calibration mark. Store the prepared solution in
the brown, narrow-neck bottle to prevent decomposition due to the action of light.

3. Pour 50 mL of N,N-dimethylformamide (DMF) into the round-bottom flask which is

immersed in a heating bath filled with silicone fluid, and put in magnetic stirrer bars. Fix two
glass tubes in the lateral necks of the flask and close them with rubber caps. Puncture one of
these caps with a thin needle and insert the thermocouple (the other one will be later pierced
when injecting α,α’-azobisisobutyronitrile). Heat the apparatus to 90 °C under constant
stirring. Exactly measure the temperature with the digital thermometer.

Figure 15.1 Expermental set-up

65
4. When a constant temperature has been reached, open the three-way cock of the gas
syringe to the atmosphere and inject 5 mL α,α’-azobisisobutyronitrile. Wait until the
temperature is again constant and gas evolution is evident, then turn the three-way cock so
that it is closed to the atmosphere and open to the apparatus, and simultaneously start the
stopwatch. Record the gas volume (V) evolved at regular intervals., until it has become
almost constant. Exactly determine the final volume (V∞).

5. Repeat the measurements at further temperatures between 90 and 115 °C. In each case,
correct the DMF volumes in the reaction vessel to the initial volume by pipetting off 5 mL.

15.5. Results and Calculations

𝑉∞
1. Using V and V∞ obtained in experiment, calculate ln 𝑉 for each temperature. Then, plot
∞ −𝑉

lnQ versus t (min.) for each temperature.

2. Calculate the rate constants (k) from the slope of the obtained lines.

3. Plot ln k versus 1/T and calculate activation energy (Ea) from the slope of the obtained
line.

4. Compare the values you have obtained by using graphical methods and from the literature.
Discuss your results.

66
16. EXPERIMENT

REFRACTION FIRST ORDER REACTIONS POLARIMETRIC

METHOD

16.1. Object

To determine the kinetics of a first order reaction and the rate constant of the reaction by
means of the polarimetric method.

16.2. Theory

The rate of a chemical reaction is defined as the rate of change of its degree of extent per unit
volume with respect to time. This change is also defined as the concentration change per unit
time of a substance multiplied by the reverse of its stoichiometric coefficient. For a first order
reaction, the reaction rate depends on the concentration of only one reactant.

Suppose that the reaction given below is of first order with respect to substance A.

𝐴 + 𝐵 → 𝐶 + 𝐷

The differential rate equation for the first order rate law is;

𝑑[𝐴]
− = 𝑘[𝐴] (16.1)
𝑑𝑡

Rearrangement and integration of equation 16.1 gives the integrated form of the first order
rate law.

ln[𝐴] = −𝑘𝑡 + ln[𝐴]0 (16.2)

where

[A]0 :Initial concentration of the reactant

[A] :Concentration of the reactant remaining at time t

t :Time

k :Rate constant

67
Rate constant can be determined by various methods. Polarimetric method is the one of these
methods. This method is suitable for optically active substances such as sugar.

Light is composed of a large number of electromagnetic waves vibrating at right angles to the
direction of propagation with all directions being equally probable. Light is plane polarized
when the electric and magnetic fields each oscillate on a single plane. The plane of
polarization may be oriented in any direction around the direction of propagation with the
electric and magnetic fields perpendicular to that direction (and perpendicular to each other).
An alternative mode of polarization is circular polarization, in which the electric and magnetic
fields rotate around the direction of propagation in either a clockwise or a counter-clockwise
sense but remain perpendicular to it and to each other.

Plane polarized light represents a vectorial sum of two circularly polarized lights which have
the same oscillation extensions and one rotating clockwise other rotating counter-clockwise.
When plane-polarized light passes through samples of certain kinds of matter, the plane of
polarization is rotated around the direction of propagation. Substances that can rotate plane-
polarized light to left or right are called optically active substances.

In order to be optically active, the substance should not have a symmetry plane or a centre of
symmetry. Moreover, it should be non-superimposable with its mirror image. Optically active
substances have an asymmetric carbon atom. If the four groups bonded to the central carbon
atom are different from each other, the central carbon atom is called asymmetric carbon atom
or chiral carbon atom. Substances that rotate the plane-polarized light clockwise are called
"dextro-rotatory compounds" whereas the ones that rotate counterclockwise are termed "levo-
rotatory compounds".

The parameters that affect the angle of rotation are;

 Temperature

 Wavelength of the light

 Distance light travels

 Structure of the compound

 Concentration of the compound

68
In this experiment, kinetics of the inversion of sucrose will be examined. As the inversion of
sucrose progresses, a change is observed in sucrose concentration and in the optical rotation
angle of the system. Thus, the rate constant of the reaction may be obtained.

A polarimeter is used for the measurement of the change in the angle of rotation of polarised
light during the inversion reaction of sucrose over time. The inversion reaction of sucrose is
as follows:

𝐻+
C12 H22 O11 + H2 O → C6 H12 O6 + C6 H12 O6

Sucrose Glucose Fructose

The rate of this reaction depends on the concentrations of sucrose and of water and also upon
the concentration of hydrogen ion which acts as a catalyst in this reaction. The concentration
of water may be regarded as constant because of its excess amount in the medium. water is
used in large excess that its concentration does not change appreciably. H+ ion concentration
remains unchanged during the reaction. Under these conditions, this reaction corresponds to a
first order reaction with respect to sucrose. All the substances involving in the reaction except
water are optically active substances. Sucrose and glucose rotate the plane of polarized light
to the right, while fructose rotates it to the left. Fructose has a greater molar rotation than
glucose and the products have 1:1 stoichiometry. Consequently, the mixture of products
rotates polarized light to left totally. In the beginning of the inversion reaction, the angle of
rotation is to the right and it decreases while the reaction proceeds. At the end of the reaction,
the reaction mixture rotates polarized light to left.

The angle of rotation is determined at the beginning (α0) and at the end of the reaction (α∞),
and the algebraic difference between these two readings is a measure of the original
concentration of sucrose. The sucrose concentration remaining unchanged at time t is
proportional to the algebraic difference between the angle of rotation of sucrose solution at
time t (αt) and (α∞).

[𝐴] = αt − α∞ (16.3)

Therefore, the concentration terms in equation 16.2 are replaced by the angular rotation terms
to determine the rate constant k of the inversion reaction of sucrose.

69
16.3. Apparatus and Chemicals

100 mL beaker, 25 mL pipette, graduated cylinder, 20 % sucrose solution, 1N HCl solution

and a polarimeter.

16.4. Method of Procedure

1. Pipette 25 mL of 20 % sucrose solution into two different 100 mL beakers and add 1-1.5
mL of 1N HCl into the solution. Mix the solution and record the time. Take this time as the
initial time of the reaction.

2. Fill the sample tube of the polarimeter with the solution of the first beaker. Measure the
angle of rotation of the solution after 15 minutes the reaction starts.

3. Record subsequent measurements at about every 15 min for the first hour. These four
measured angles of rotation values are defined as (αt).

4. Heat the acidic sucrose solution in the second beaker to 65°C, so inversion rate increases.
Cool the solution to room temperature and measure the angle of rotation of the solution.
This value is defined as (α0).

16.5. Results and Calculations

1. Plot the observed angles (αt) versus time (t). Read the angle of rotation at t=0 (α0) by
extrapolating.

2. Calculate [A] and [A]0 values for all the measured values.

[𝐴]0 = α0 − α∞ [𝐴] = αt − α∞
[𝐴]
3. Plot ln [A]0 versus time (t) and determine the rate constant (k) from the slope of the straight

line.

4. Calculate rate constant (k) values for all the recorded time (t) periods by using equation
(16.4) and calculate the average rate constant (k).
1 α −α
𝑘 = 𝑡 ln α0−α ∞ (16.4)
t ∞

70
17. EXPERIMENT

EBULLIOSCOPY

17.1. Object

To measure the increase in the boiling point of water as a function of the concentration of
table salt (NaCl), to investigate the relationship between the elevation of the boiling point and
the number of pellets and to determine the molecular weight of the solute from the
relationship obtained.

17.2. Theory

A solution is a homogeneous mixture which consists of a dissolved substance and a solvent.

Only the solvent is capable of vaporization, if the solute is nonvolatile, the vapor pressure of
the solute is practically zero. When a substance dissolves in a solvent, additional forces result
and these must be overcome by solvent molecules before they can pass into the gas phase.
Less solvent molecules can therefore vaporize from a solution than from the pure solvent.
Raoult's law states that the vapor pressure of the solvent over a solution is equal to the product
of the vapor pressure of the pure solvent and the mole fraction of the solvent. In this
experiment, vapor pressure of the solution is equal to the vapor pressure of the solvent over
the solution, because the solute is involatile;

𝑛1
𝑃=𝑛 𝑃∗ (17.1)
1 +𝑛2

Where;

P : Vapor pressure of the solution

P*: Vapor pressure of the pure solvent

n1 : Number of moles of the pure solvent

n2 : Number of the dissolved substance

Boiling point of a solution is higher than that of the solvent because chemical potential of the
solvent is less in the solution than that in the pure form. A liquid boils when its vapor pressure

71
equals the ambient pressure. Phase diagram of the pure solvent and the solution can be seen in
Figure 17.1. The vapor pressure of water reaches an ambient pressure of 1 atm at a
temperature of 100°C. When a substance is dissolved in water, its vapor pressure lowers, and
so it is less than 1 atm at 100°C. Heat must now be provided to increase the kinetic energy of
the molecules, to raise the temperature so that the solution comes to boiling. The reason for
the higher energy requirement for the solution than that for the pure solvent is because
additional forces, mutual attractive forces between solute and solvent molecules, must be
overcome in the solution.

Figure 17.1 Phase diagram of pure solvent and solution

The solution does not boil at T0, but at a higher temperature T. The difference between these
two temperatures is the boiling point elevation ΔT.

∆𝑇 = 𝑇 − 𝑇0 (17.2)

The dependence of the temperature difference (elevation of the boiling point) on the
concentration of the solute can be determined by using a suitable apparatus. The method is
called "Ebullioscopy". Boiling point elevation is dependent on the amount to which the vapor
pressure is lowered, and so on the concentration of the solute.

AT = Kb .m (17.3)

Kb is the ebullioscopic constant, which depends only on the properties of the solvent.
Molality is used here as the concentration unit, i.e. the number of moles of solute dissolved in

72
1 liter of solvent. Molality is independent of temperature.

17.3. Apparatus and Chemicals

Temperature meter, temperature probe, experimental setup consisting inner and outer tubes,
heating hood, round flask (250 ml), silicone tubing, glass beaker (250 ml), adapter, distilled
water, sodium chloride (NaCl), spatula and forceps.

17.4. Method of Procedure

1. Set up the experiment as shown in Figure 17.1.

2. Weigh the dry inner vessel of the boiling point apparatus and note the exact mass (m1).

3. During measurement, steam is to enter the inner vessel through the lateral aperture, so
pay attention that it is not covered.

4. Fill the round flask with 150 to 200 mL of water and connect it to the assembled
apparatus.

5. Slip two short pieces of silicone tubing onto the two gas outlets of the outer vessel and
place the lengths in a 250 mL glass beaker with the free ends at about the middle of the
beaker.

6. Attach a pinchclip to the lower of the two tubes coming from the outer vessel, but for the
time being leave it opens.

7. Pour approximately 40 ml of water into the inner vessel. Close the vessel at the top by
fixing the temperature probe in position.

8. Weigh out five portions of each substance (NaCl), each of approximately 700 mg. and
record the values (mNaCl).

9. Heat the water in the flask to boiling. The vapor evolved rises up into the outer vessel and
heats up the inner vessel. Control the heating rate with the power control.

10. The temperature in the inner vessel is displayed on the digital temperature meter in °C.
After some minutes, when the temperature in the inner vessel has nearly reached the
boiling point and no longer increases, lower the heating hood for a few seconds until
boiling stops and the condensate on the outer vessel returns to the round flask.

11. Raise the heating hood again.

12. When boiling recommences, close the pinchcock. The (slightly superheated) steam now

73
 flows through the water in the inner vessel.

13. Set the digital temperature meter to measure the change in temperature ΔT. Wait until the
value displayed remains constant. Now carefully open the inner vessel (screw cap), add
the first substance pellet, and close the opening immediately.

14. The temperature first drops slightly and then rises again while the pellet dissolves. When
the value has again become constant, record it.

15. Repeat this procedure for the next portion of the substance.

16. After five concentration steps have been measured, first open the pinchcock and then
switch off the heating. This is important to avoid solution being sucked from the inner
vessel into the flask containing water while cooling down.

17. Remove the inner vessel, dry its outer surface, remove the temperature probe and re-
weigh it. Record the value (m2).

17.5. Results and Calculations

1. Calculate the mass of water by using m1, m2 and mass of 5 NaCl pellets;

mH20 = m2 – m1 - 5mNaCl (17.4)

2. Plot the increase in boiling point (ΔT) against the quotient of the mass of the dissolved
substance (mNaCl) and the mass of water (mH2O) for each substance as shown in Figure
17.3.

74
18. EXPERIMENT

MOLECULAR WEIGHT DETERMINATION BY THE VICTOR

MEYER METHOD

18.1. Object

To determine the molecular weight of an unknown liquid (acetone) using the Victor Meyer
method.

18.2. Theory

The new atomic weights system is based on C-12 which is the most abundant isotope of
carbon. In this system, the atomic weight of C-12 is accepted as 12.000 and the other atomic
weights are determined according to this acceptance. For example, the atomic weight of
oxygen is 15.999 and the molecular weight of oxygen is 31.998. Molecular weights of other
gases can be calculated by using the molecular weight of oxygen and Avogadro's Law.
According to Avogadro's Law, equal volumes of all gases have equal numbers of molecules at
the same temperature and pressure. The volume of 1 mole oxygen determined experimentally
under certain conditions is equal to the volume of other gases at the same conditions.
Actually, weight of the gas in this volume is the molecular weight of the gas.

Density of oxygen is 1.4276 g.L-1 under normal conditions (1 atm, 273.15 K) and the molar
volume of oxygen at the same conditions is 31.998/1.4276 = 22.413 L.mol-1. This value is the
molar volume of an ideal gas under normal conditions. To determine the molecular weight of
any gas, the weight of 22.413 L gas must be found under normal conditions. However, real
gases do not behave like an ideal gas so an appropriate correction must be used in
experimental measurements.

The main methods used to find the molecular weight of gases are; Berthelot Method,
Regnaults Method, Dumas Method, Hoffman Method, Limiting Density Method and Victor
Meyer Method. Victor Meyer Method is the most common one among these methods. The
method was first found in 1878 by Professor Victor Meyer from Zurich University. This is a
commonly used and easily applied method to find out the molecular weights of volatile
liquids. The reason can be attributed to the fact that to weigh liquids is much easier than to
weigh large volumes of gases. The Victor Meyer Method is based on the principle of

75
measuring the volume of a known weight volatile liquid. This volume is equal to the air
volume which is displaced by vaporizing liquid. By measuring the air volume displaced by
the vapor, the molecular weight of the liquid is calculated by the ideal gas law. In this
equation:

𝑊
𝑃𝑉 = 𝑅𝑇 (18.1)
𝑀

W :Weight of liquid (g)

M :Molecular weight (g.mole-1)

R :Ideal gas constant

T : Absolute temperature (K)

V :Air volume (L)

P :Partial pressure of dry air

𝑃 = 𝑃1 − 𝑃𝐻2 𝑂 (18.2)

In this equation:

P1 :Barometer pressure (atm)

PH20 :Vapor pressure of water (atm)

18.3. Apparatus and Chemicals

The experimental setup is shown in Figure 18.1. It consists of four parts: a chamber which
contains a capillary tube (G), vaporizing tube (H), a gas burette for measuring the volume of
dry air displaced by the vapor (C), a steam generator (A) connected to a steam jacket
surrounding the vaporizer tube (B). The liquid which will be used in this experiment is
acetone.

76
 Figure 18.1 The Victor Meyer experimental set-up

18.4. Method of Procedure

1. Read the barometer pressure, P (atm).

2. Weigh the chamber (G) when it is empty and record the value (W1).

3. Fill the chamber with acetone and weigh it. Record the value (W2).

4. Boil the water in the flask used as a steam generator and allow the steam to pass holding
the vaporizing tube 30-40 minutes in steam jacket.

5. Place the chamber into the apparatus and close the stopper.

6. Acetone vaporizes completely when the temperature is 90°C. The steam generated causes
a little air to pass through the burette (C). Ensure that the air pressure in the burette
reaches the initial pressure by moving the column (D) up and down. Read the air volume
V (mL) from the burette in this position.

7. Read the barometer pressure, P (atm) again.

18.5. Results and Calculations

1. Calculate the amount of acetone (W) used in the experiment.

W = W2 – W1 (18.3)

2. Read the vapor pressure of water PH2O at the experimental temperature from Table 18.1
and calculate the partial pressure of dry air by using Equation 18.2.

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 Tablo 18.1 Vapor pressure values of water at different temperatures

T (°C) PH2O (mmHg) T (°C) PH2O (mmHg) T (°C) PH2O (mmHg)

10 9.209 16 13.364 22 19.827
11 9.844 17 14.530 23 21.068
12 10.518 18 15.477 24 22.377
13 11.231 19 16.477 25 23.756
14 11.987 20 17.535 26 25.209
15 12.788 21 18.650 27 26.739

3. Calculate the molecular weight of acetone by placing the values you have found into
Equation 18.1.

4. Calculate the relative error by comparing the actual molecular weight of acetone and the
value that you have found and comment on the error sources.

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REFERENCES

1. Alberty R.A., Physical Chemistry, 6th Ed., John Wiley and Sons, New
York,1983.
2. Atkins, P.W., Physical Chemistry, Oxford University Press, 1998.
3. Berkem, A.R., ve Baykut, S., Fizikokimya, istanbul Universitesi Yayinlari,
istanbul 1994.
4. Cebe M., Fizikokimya, Cilt 1, Uludag Universitesi Basimevi, 1987.
5. Castellan G.W., Physical Chemistry, 2nd Ed., Addison-Wesley Publishing
Company, Maryland, 1973.
6. CRC Handbook of Chemistry and Physics; CRC Press LLC, 2004.
7. Davies D.G. and Kelly T.V.G., Experimental Physical Chemistry, Mills and
Moon Lim., London,1967.
8. Mortimer,R.G., Physical Chemistry, Third Ed., The Benjamin/Cummings
Publishing Company Inc.,USA, 2000.
9. Schafer, W., Klunker J., Schelenz T., Meier T., Symonds A., Laboratory
Experiments in Chemistry, Phywe-Series of Publications, 2007.
10. Şenvar C., Kimyasal Kinetik ve Makromolekuller, Marmara Universitesi
Yayinlari, istanbul, 1985.

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