Experiments for

Physical Principles Laboratory 1

(LBYCHEA)
 List of Experiments

Experiment # Title
1 Liquid Density and Viscosity
2 Variation of Viscosity with Temperature
3 Variation of Viscosity with Concentration
4 Melting Point Determination
5 Surface Tension
6 Colorimetry, Turbidimetry and Spectrophotometry
7 Refractometry
8 Polarimetry
9 Boiling Point Elevation
10 Freezing Point Depression
 Experiment #1
Liquid Density and Viscosity

Density
Materials are often identified based on their physical properties that do not vary with the amount
or shape of the material. One such property is density which is a measure of the “compactness”
of matter within a substance. Density is defined as the ratio of the mas of the material to its
volume.

There are several ways by which liquid density can be determined. The most basic method
involves determining the mass of a given volume of the sample, and then taking the ratio of the
two quantities. Although this can be accomplished using a graduated cylinder and a balance, a
very precise method involves the use of a pycnometer (Figure 1), a glass flask with a close-fitting
stopper with a capillary hole through it. The capillary hole releases a small amount of the liquid
after closing a filled pycnometer allowing accurate measurement of the volume. Pycnometers
are sometimes equipped with thermometers to measure the temperature of the test liquid since
density is temperature dependent.

(a) (b)
Figure 1. Pycnometers
(a) without thermometer, (b) with thermometer

The density of a liquid may also be determined through buoyancy tests. A hydrometer is a
hollow, graduated cylinder weighted at one end. This is shown in Figure 2. The instrument is
allowed to float in a sufficient quantity of liquid and the extent to which it sinks gives a
corresponding density reading. This test is quick and simple to execute but requires a somewhat
large quantity of sample.
 Figure 2. Hydrometer

Viscosity
Viscosity is defined as a fluid’s resistance to flow caused by internal friction between the
molecules of the fluid moving with different velocities. It is a fluid property that is important in
the transportation of fluids.

Viscosity can be measured in several ways. For liquids, three possible means of determination
are: the falling-ball method, which takes advantage of Stoke’s Law; the use of an Ostwald
viscometer; and the use of any of a variety of commercially available viscosimeters.

The falling-ball method involves allowing a series spherical body of different diameters to free-
fall through a column of the test liquid. The viscosity of the fluid may be calculated from Stoke’s
law which states that the force that impedes a sphere moving through a viscous fluid is
proportional to the velocity of the sphere, radius of the sphere and viscosity of the fluid. There is
however a limitation to the Stoke’s Law. It is applicable only when flow around the sphere is
laminar, specifically when the Reynolds number of the system is less than 1.0. The Stoke’s law
is given by equation 1.
.
2r 2    m g
 (1)
9v

where: µ = viscosity
 = density of the sphere
m = density of liquid
g = gravitational acceleration
r = radius of the spherical body
v = terminal velocity of body

The applicability of Stoke’s law can be confirmed by calculating the Reynold’s number of the
system. The Reynold’s number is given by equation 2.
 Dv
Re  (2)

where: D = diameter of the sphere
v = velocity of the fluid relative to the sphere
 = density of the fluid
 = viscosity of the fluid

The relative viscosity of a liquid is the ratio of its absolute viscosity to that of water at the same
temperature. This can be determined by means of an Ostwald viscometer (Figure 3), which
consist of a U-tube. In one arm of the U is a bulb (lower) which serve as a reservoir of the liquid.
In the other arm is another bulb (upper) with marks at the upper and lower portions. Below the
lower mark is a capillary. The test liquid from the lower bulb is drawn to the upper bulb passing
through the capillary by suction until it reaches above the upper park. The liquid is then allowed
to flow down the capillary to the lower bulb. The time it takes the liquid to flow from the upper
to the lower mark is proportional to the kinematic viscosity.

Figure 3. Oswald Viscometer

With this instrument, a relationship exists between the absolute viscosities of the two fluids, with
water as the reference liquid. Equation 3 relates the viscosities of two liquids.

1 1t1
 (3)
 2  2t 2

where: µ1, µ2 = viscosity of water and the other liquid, respectively

1, 2 = density of water and the other liquid, respectively
t1, t2 = time required for the liquid to travel through constriction

Commercial viscometers determine viscosity from the torque required to move a rotor at a fixed
speed through the liquid. The rotor rotating at a constant speed is immersed into the liquid to be
tested. The rotational resistance is a measure of the viscosity of the liquid. The viscosity is
displayed directly on the meter.
Equipment and Materials
pycnometer, hydrometer, Ostwald viscometer, rotational viscometer, thermostatic bath, stop
watch, Vernier caliper, balance, graduated cylinder, spherical beads of different diameters,
distilled water, acetone, ethanol, methanol, vegetable oil (or any liquid)

Objectives
1. To demonstrate various techniques of measuring density, and to assess the accuracy of
each method.
2. To determine the viscosity of liquids using different methods.
3. To compare the experimental data (density and viscosity) with the theoretical values.
4. To compare the results obtained from the different methods.

Procedure

A. Determination of Density
1. Weigh several clean, dry pycnometers. Fill these with the test liquids, ensuring that there
are no voids or bubbles. Immerse the pycnometers in a thermostatic bath and leave them
to equilibrate for 15 minutes. Remove them from the bath, dry the outsides, and weigh.

2. Put the same test liquids in individual graduated cylinders and determine their densities
using the hydrometer.

Note: The density of the oil is determined by using only the hydrometer. Do not use the
pycnometer to measure the density of oil.

B. Viscosity
B.1 Use of Ostwald Viscometer
1. Calibrate the Ostwald viscometer with materials of known viscosity such as water.

2. Pipette about 5ml of water into the lower bulb and suspend the viscometer in a thermostat
(a large beaker of water may be used). Allow 15 minutes to attain thermal equilibrium.

3. Draw the liquid up to a point above the upper graduation of the bulb on the small arm.

4. Allow the liquid to flow down and measure the time necessary for the meniscus to pass
from the upper graduation to the lower. Use a stop watch for timing.

5. Repeat the procedure using different test liquids.

 B.2 Application of Stoke’s Law
Measure the diameter of several glass beads of different sizes using a Vernier caliper,
then determine the weight of each. Fill a graduated cylinder with 500 ml of the viscous
liquid such as oil. Drop consecutively the glass beads into the liquid and determine
velocity of each bead as it falls through the oil. Repeat the procedure three times.

B.3 Use of commercial viscometer

1. Put the liquid to be tested in a beaker.
2. Assemble the rotational viscometer with the measuring cup attached to the rotor.
3. Immerse the rotor up to the dip mark (on the rotor shaft) into the liquid.
4. Read the measured value from the display.

Analysis
Compare the experimentally determined liquid densities and viscosities to the respective
established values; which method is more accurate? Note any potential sources of erroneous
readings, and suggest precautions to minimize their occurrence.
 Experiment #2
Variation of Viscosity with Temperature

The viscosity of liquids is related to the ease with which the molecules can move with respect to
one another. The momentum transfer between molecules is dependent on the cohesive forces
between the molecules. When the liquid is heated, the average kinetic energy of the molecules
increases overcoming the cohesive forces that holds the molecules together. This results in a
decrease of the viscosity of the liquid.

The viscosity of a liquid always decreases with increase in temperature. The relationship
between viscosity and temperature maybe represented by the Andrade-Guzman Equation
(equation 4):

  AeB / T (4)
where A and B are constants and T is the absolute temperature. The equation may be linearized
by expressing it in logarithmic terms (equation 5).

B
ln   ln A  (5)
T

Equation 5 maybe represented graphically as shown in Figure 4.

ln

Slope = B

lnA

Figure 4. Dependence of Temperature on Viscosity

Equipment and Materials

Ostwald viscometer, stopwatch, thermostatic bath, thermometer, pycnometer, distilled water,
ethanol

Objective
To determine the effect of temperature on the viscosity of liquids
Procedure
Determine the viscosity and density of water and ethanol at the following temperatures: 30,
35, 40, 45, 50, and 55 ºC.

Analysis
Plot the viscosity-temperature curve for water and ethanol. Formulate an empirical correlation in
the form of a polynomial model. Compare the result with theoretical values.
 Experiment #3
Variation of Viscosity with Concentration

The addition of a solute can alter the viscosity of a liquid. A dissolved macromolecule will
increase the viscosity of a solution because it disrupts the streamlines of the flow. The exact
effect depends on the nature of the solute introduced, as well as on the concentration of the
resulting solution. There are solutions whose viscosity increases linearly with concentration,
others exhibit increase in viscosity non-linearly. Still others have viscosity that changes non-
linearly with concentration demonstrating a maximum on a bell-shaped viscosity-concentration
curve.

Equipment and Materials

Ostwald viscometer, balance, stopwatch, volumetric flask, distilled water, sucrose, sodium
chloride, ethanol

Objective
To determine the effect of the type of solute and its concentration on the viscosity of a
solution

Procedure

1. Prepare sucrose solutions of the following concentrations: 5, 10, 15, 20, 25%(w/w).
Determine the densities and viscosities of these solutions.

2. Repeat (1) with sodium chloride solutions with the following concentrations: 1, 3, 7, 10,
15 (w/w).

3. Repeat (1) with water-ethanol mixtures with the following proportions: 15, 30, 45, 60,
75% (w/w) ethanol.

Analysis
Plot the viscosity-concentration curves of the three solutions tested, and note the trends
therein. Describe the viscosity-concentration profile of the three solutions. Compare the
viscosities of the sucrose and sodium chloride solutions. Does viscosity increase or decrease
with concentration?
 Experiment #4
Melting Point Determination

The melting point (MP) of a substance is the temperature at which the material changes from
solid to liquid state. Pure crystalline substances have a clear, sharply defined melting point.
During the melting process, all of the energy added to a substance is consumed as heat of fusion,
and the temperature remains constant.

A pure substance melts at a precisely defined temperature, characteristic of every crystalline

substance. However, the presence of impurities can alter the melting point of the substance.

Equipment and Materials

Melting point apparatus, thermometer, capillary tubes with one end closed and the other end
open, mortar and pestle, balance, acetanilide, benzoic acid, urea, salicylic acid or any other
organic substances available in the laboratory.

Objective
To demonstrate the application of melting point measurement for substance identification
and purity assessment

Procedure
1. Before the laboratory class, obtain the melting point of the substances to be tested. This
will serve as basis for the starting temperature of the oil bath.

2. Place a minute quantity of each sample in a capillary tube. Make sure that the substance
is dry, homogeneous and in powder form.

3. To fill a capillary tube with a sample, press the open end of the capillary gently into the
substance several times. Then push the powder to the bottom of the tube by repeatedly
and gently pounding the bottom of the capillary against a hard surface (preferred
method). Alternatively, the capillary tube can be dropped onto a table through a glass
tube of about 1 m in length. A sample packing wire can be used at the end to further
compact the sample and improve the reproducibility of the measurements.

In addition to tight packing, maintaining a fixed level in the fill is also a very important
requirement. Taller samples take extra heat to completely melt and usually display larger
melting ranges than their shorter counterparts. A sample height between 2.0 mm and 3.0
mm is recommended for optimum results and reproducibility.

4. Preheat the oil in the melting apparatus to a temperature just below the expected melting
point of the samples. When the temperature becomes stable, insert the sample tubes
individually in each sample port. Up to five samples can be accommodated by the heating
block simultaneously. For improved reproducibility of results, it is recommended that
 five tubes be inserted even if not all capillary tubes contain a sample. For a more accurate
and reproducible results, the five capillary tubes may contain the same sample and then
getting the average of the melting point temperatures.

5. Gradually increase the temperature of the oil bath while keeping well agitated. Note the
temperature at which the sample starts to melt (T1), as well as the temperature at which
the sample becomes completely liquid (T2).

6. Combine any two samples, using various proportions (5/95, 10/90, 15/85). Repeat steps
1-4.

7. An unknown organic substance will be given by the instructor. Determine the melting
point following steps 1-4.

Analysis
 Compare the melting points of the substances tested with the theoretical values and
explain the deviations, if any.
 Describe the change in the melting points of the combined samples at various
proportions. What is the profile?
 Identify the unknown sample based on the obtained melting point.
 Experiment #5
Surface Tension

The surface films of liquids behave under tension due to the lateral attraction between the
molecules at the surface. The surface tension of a liquid is affected by the presence of solutes,
which tend to change the surface film through preferential adsorption or desorption. For dilute
solutions, the Gibbs Adsorption equation describes this correlation

C d
 
RT dC (18)

where  = surface excess of solute (moles/area)

C = concentration of solution (moles/volume)
 = surface tension of the solution (force/length)
R = gas constant
T = absolute temperature (temperature)

There are a number of ways to measure the surface tension of a liquid. One method is to measure
the force needed to pull a submerged body of specified dimensions through the surface film. This
principle is the basis for the operation of the ring tensiometer.

Equipment and Materials

Ring tensiometer, beakers, 10-ml volumetric flasks, distilled water, sucrose, sodium chloride,
surfactant

Objective
To correlate surface tension and surface excess with solution concentration

Procedure
1. Measure the surface tension of distilled water using the ring tensiometer. This is done by
submerging a spring-loaded ring in the sample liquid. Then, the spring tension is
gradually increased until the ring is pulled clear off the liquid. The force needed to
accomplish this is directly proportional to the sample’s surface tension, which can then be
read from a calibrated scale on the instrument.

2. Prepare sucrose solutions with the following concentrations: 0.001, 0.002, 0.003, 0.004,
0.005M. Measure the surface tension of each solution following the procedure in No. 1.

3. Prepare sodium chloride solutions of the same concentrations as above. Measure the
surface tension of each solution.
 4. Prepare solutions of surfactant with varying concentration (5 concentrations) up to a
maximum of 5%. When preparing the solution, stir the solution lightly so as not to
produce so much suds. Measure the surface tension as before.

Analysis
Plot the surface tension versus concentration for the three sets of solution tested (for both
theoretical and experimental data). The resulting correlations should be roughly linear. Note
any differences between the effects of the three solutes. Calculate the surface excess values
of the solutes and plot these values against concentration. Plot all data using Excel and show
the equation of the line and the value of the R2. Include error bars for the experimental data.
 Experiment #6
Colorimetry, Turbidimetry and Spectrophotometry

One useful and often used method of determining the concentration of a chemical in a solution, if
it has a color, is to measure the intensity of the color and relate the intensity of the color to the
concentration of the solution. This is called colorimetry. If the solution is colorless, the addition
of a suitable indicator is necessary. A variant of this approach is known as turbidimetry, wherein
a precipitating agent is added to the solution. The precipitate makes the solutions turbid
(cloudy), and the concentration of the sample can be determined from the extent of the turbidity.

Ocular colorimetric analysis involves the correlation between the color of a solution and its
concentration. The procedure can be modified using a spectrophotometer to make more accurate
measurements of the “transparency” of the standard and sample solutions.

A spectrophotometer passes a beam of light of a specified wavelength (color) through a known

quantity of sample, and compares the intensity of the beam before and after it passes through the
sample. At a particular wavelength, absorbance may be measured as a function of concentration.
Beer-Lambert’s Law summarizes the correlation according to equation 6.

A  log 10 (1 / T )  log 10 ( I o / I )
(6)
A  cl

Where A = absorbance
T = transmittance
I0 = intensity of light entering the solution
I = intensity of light leaving the solution
absorptivity, L/mol-cm or M-1cm-1
c = concentration, M
l = path length, cm

In determining the concentration of a species in a solution, standard solutions of various

concentrations are prepared and their absorbance is measured. A plot of absorbance against
concentration is accurately linear and passes through the origin. This is the calibration curve. The
absorbance of a sample of unknown concentration is measured and its concentration is
determined from the calibration curve.

Equipment and Materials

Potassium permanganate solution (1g/L), zinc nitrate, concentrated hydrochloric acid,
potassium ferrocyanide, water, volumetric flasks, test tubes, and spectrophotometer.

Objective
To determine the concentrations of solutions using colorimetry, turbidimetry and
spectrophotometry
Procedure:

1. Prepare the following standard solutions of potassium permanganate with the following
concentrations 25, 50, 75, 100, 125 and 150 mg/L. Use serial dilution starting with 150
mg/L. Use volumetric flasks in the preparation of the solutions for accuracy in the
concentration.

2. Measure the absorbance of each standard solution at 525nm using a spectrophotometer.

Use distilled water as blank.

3. Obtain a sample of “unknown concentration” of potassium permanganate from the

instructor. Approximate its concentration by matching its color with those of the
standards. Get the absorbance of the unknown at 525nm.

4. Prepare zinc nitrate solutions with the same concentration as the potassium permanganate
solutions. Place each standard in a test tube. To each test tube, add 20 - 25 drops of
concentrated HCL then 12 - 15 drops of 3% (w/w) K3Fe(CN)6 solution. Wait for about 5
minutes or until a bluish-white turbidity becomes apparent. Get the absorbance of the
standard solutions at 635 nm. Use distilled water as blank.

5. Obtain again zinc nitrate solution of unknown concentration from the instructor and put
10 ml in a test tube. Add concentrated HCl and K3Fe(CN)6 solution just like the
standard. Measure the absorbance.

Analysis:
Prepare the calibration curves for potassium permanganate and zinc nitrate by plotting the
absorbance vs. concentration of the standard solutions. Determine the concentration of the
unknown samples using the appropriate calibration curve.
 Experiment #7
Refractometry

Refractometry is a spectral analysis in which the incident radiation changes direction. Refraction
occurs when a beam of light is passed from one medium to another causing a change in the
velocity of light due to the different media. Each medium slows down light at different amounts.
If the velocity of light is lower in the second medium, the beam bends inwards; if it is higher, the
beam bends outwards. The capacity of a medium to bend light is usually expressed as the
refractive index (or index of refraction). The refractive index is the ratio of the velocity of light
in a vacuum to that in the medium in question. The presence of a solute can significantly alter the
refractive index of a liquid. Consequently, refractive indices can be used as a means of
determining the concentration of solutions.

A refractometer is a measuring instrument used to measure the refractive index of a substance. It

utilizes a prism which has a much higher refractive index than the sample solution to be
measured. The refraction occurs at the interface of the prism and sample solution.

Equipment and Materials:

Refractometer, volumetric flasks, test tubes, beakers, sucrose, ethanol

Objective:
To determine the refractive indices of solutions, and to use refractive index as a means of
determining the concentration of solutions.

Procedure:
1. Prepare standard solutions of sucrose with the following concentrations: 5, 10, 15, 20,
25%, (w/w) using serial dilution.

2. Prepare standard solutions of ethanol with the following concentrations: 10, 15, 20, 25,
30%(w/w).

3. Calibrate the refractometer using water. Compare the readings obtained to that of the true
value from the handbook or any reference materials. Calculate the relative error.

4. Determine the refractive indices of the test solutions. A few drops of the sample is
placed in the instrument and pressed between glass plates. Light passing obliquely
through the sample is refracted at an angle that depends on the refractive index. The
refractometer is calibrated to display the refractive index. Correct the values obtained
using the relative error.

5. Obtain sample solutions of sucrose and ethanol of unknown concentration from the
instructor, and determine their respective refractive indices.
Analysis:
1. Compare the concentration values estimated from the refractive index data with the true
values found in the handbook or standard reference materials.

2. Prepare a calibration curve for the sucrose and ethanol solutions and determine the
concentration of the unknown solutions using the calibration curve.

3. Determine the difficulties associated with refractometric analysis, and suggest possible
refinements.

4. Identify possible application of this method in industrial processes.

 Experiment #8
Polarimetry

Polarimetry is the technique for measuring the extent by which the plane of polarization of a
plane-polarized light is rotated by passing it through an optically active medium. The light is
polarized when it is passed through an optically active medium and the waves tend to vibrate in
only one direction.

Optically active compounds have chiral centers, that is, a carbon that has 4 different groups
attached to it. Depending on the orientation of these four different groups about the chiral
carbon, the compound may rotate plane polarized light to the left or to the right. If an optically
active compound rotates the plane of polarized light in a clockwise direction, it is called
dextrorotatory (+); if it rotates in a counter-clockwise direction, it is called levorotatory (– ).

The amount of rotation can be measured by using an instrument called a polarimeter. Optically
active organic molecules are placed in a sample tube, plane polarized light is passed through the
tube, and rotation of the plane occurs. The light then goes through a second polarizer known as
the analyzer. By rotating the analyzer until light passes through it, the new plane of polarization
and the extent at which polarization has occurred can be determined.

Each optically active substance has its own specific rotation as defined in Biots law (equation 7).

 T  100
l c  (7)

 T= specific rotation which is referred to sodium light and 20oC

 = measured angle of rotation in degrees of a circle; degree Ventzke (oZ)
l = length of tube in decimeter (dm)
c = concentration; grams of optically active ingredient in 100ml of solution

The international standard sugar scale provides that 100oZ of sugar content is equivalent to
34.626o angle of rotation of sugar solution corresponding to a solution of 26 g pure sucrose
dissolved in water to make 100 ml solution and poured into a 2 dm long observation tube.

Materials and Instrument

Polarimeter, volumetric flasks, balance, pure sucrose, impure sucrose, optically active
compound soluble in water, distilled water

Objectives
1. To classify an optically active compound as dextrorotatory or levorotatory.

2. To determine the purity of known optically active compound

Procedure
A. Pouring sample on the observation tube
1. On one side of the observation tube, remove the rubber ring and deck glass.

2. While holding the tube vertically, fill it with water or sample until the sample surface
becomes round due to surface tension.

3. Gently slide the deck glass to slice off the liquid surface and put the rubber ring and
tighten the fastening ring to seal the tube. Make sure that there are no air bubbles in
the tube.

B. Calibrating the Polarimeter

1. Place the observation tube filled with distilled water on the center part of the sample
stage. Make sure that the ZERO SET READY lamp is on. If this is off, the zero point
is off by 6o or more in angle of rotation.

2. Equalize the brightness of the right and left translucent semicircular fields with the
appropriate switches while observing the field through the eyepiece.

3. When the right semicircular field is brighter, press the right hand ROTATE switch
continuously until the right and left fields are the same in brightness (Fig. 5a).

4. When the left circular field is brighter, press the left-handed ROTATE switch
continuously until the left and right circular sides are the same in brightness (Fig. 5b).

(a)

(b)

Figure 5. Equalization of brightness of semicircular fields

5. When the translucent semicircular fields are equalized in brightness, press the ZERO
switch.

6. Set the indication selector to a desired position, angle of rotation or the international
standard sugar scale.
C. Experimental Procedure
 1. Prepare a solution of pure sucrose by dissolving an accurately weighed sample (20
grams) in enough water to make exactly 100ml of solution.

2. Put sample solution in a 2-dm tube and place at the center of the sample stage of the
polarimeter. Make five readings of the zero point. In taking the readings, the two
halves of the field are matched when they are equally dark or equally bright.

3. Take similar readings on an impure sucrose solution and on an optically active

substance.

4. Obtain an unknown optically active sample from the instructor and measure the
degree of rotation

Analysis
1. Classify the samples as dextrorotatory or levorotatory.
2. Calculate the specific rotation of the unknown optically active substance.
3. Calculate the %purity of the impure sample of sucrose.
4. Identify the unknown sample as dextrorotatory or levorotatory
 Experiment #9
Boiling Point Elevation

The boiling point of a solvent is defined at a given vapor pressure. When a non-volatile solute is
dissolved in a solvent the solution exhibits a higher boiling point than that of the pure solvent.
The difference between the boiling point of the solution and that of the solvent is called the
boiling point elevation.

The increase in boiling point of the solution is a direct consequence of the vapor pressure
lowering of the solvent which is determined by the fraction of liquid molecules that can escape.
In a solution the surface is composed of molecules of both solvent and solute. Since there are less
solvent molecules at the surface in solution than in a pure solvent, less solvent molecules will
escape. In order to reach the boiling point at a given external pressure, the solution has to be
heated to a temperature at which the vapor pressure of the solvent and solution becomes equal.
This can be illustrated in Figure 6.

Po
Vapor Pressure

Solvent

Solution

To T
Temperature
Figure 6 Boiling point elevation due to solute

The boiling point elevation exhibited by solutions of non-electrolytes and solutions of

electrolytes is not the same. This is because colligative properties are dependent on the number
of particles dissolved in solution. Since electrolytes dissociate when in solution, they show
greater changes than those of non-electrolytes. When electrolytes dissociate in solution, after
some time the ions re-associate and this becomes more prevalent as concentration increases.
Therefore, the number of particles present in solution is concentration dependent.

The boiling point elevation of non-electrolytes is given by equation 8.

T b  kb m (8)

where: Tb = boiling point elevation (temperature)

kb = ebullioscopic constant (degrees/molal)
m = molality of the solution
For solutions of electrolytes, equation 8 must be modified by the insertion of the van’t Hoff
factor to correct for the dissociation of the solute molecules into ions. This is given by equation
9. For ideal solutions, the van’t-Hoff factor is equal to the number of ions per formula unit.

Tb  kb mi (9)

where: i = van’t Hoff factor

Equipment and Materials:

Boiling point elevation apparatus (Cottrell) , Beckmann thermometer, distilled water,
sucrose, sodium chloride.

A purpose-built boiling point elevation apparatus is essentially a vessel with a port for the
attachment of a Beckmann thermometer as shown in Figure 7. The latter is a thermometer
with a finely-calibrated temperature scale, and with a provision for the adjustment of the
working temperature range. The entire assembly is heated by a bunsen burner until the liquid
content boils, and the temperature is read on the thermometer scale.

Beckman thermometer

Bunsen burner

Figure 7 Cottrell boiling point apparatus

Objectives:
1. To evaluate empirically the ebullioscopic constant of a given solvent.
2. To determine the degree of ionization of electrolyte based on boiling point elevation.

Procedure:
 1. Insert the Beckman thermometer so that the top of the bulb is just below the side
tabulation of the thermometer shield.

2. Pour a measured amount of distilled water until the tip of the shield is just immersed. Put
the condenser in place and allow the water to flow in.

3. Heat the water gently by means of a Bunsen burner until the water boils. Record the
reading in the Beckman thermometer. Allow the water to boil and get the thermometer
reading every 30 seconds until ten readings are obtained.

4. Weigh about 1-2 grams of sodium chloride and add to the distilled water in the boiling
point apparatus. Repeat the procedure used for the pure water.

5. Add a second sample of 1-2 grams sodium chloride and repeat the procedure.

6. Repeat the whole procedure using an unknown sample of solute obtained from the
instructor.

Analysis
1. Using the boiling point of distilled water and the sodium chloride solution, calculate the
ebullioscopic constant of water. Compare this with the established value.
2. Calculate the van’t Hoff factor, and compare this with the established values.
3. Determine the concentration of the unknown sugar solution.
 Experiment #10
Freezing Point Depression

Freezing point depression is another colligative property that is very similar to boiling point
elevation. When a solute is dissolved in a solvent, the freezing point of the solution is lower than
that of the pure solvent. This is a direct consequence of the lowering of the vapor pressure of the
solvent due to the dissolved solute.

The freezing point of a solvent or solution is determined by placing the solvent or solution in the
smaller of two concentric tubes and immersing in a cold bath as shown in Figure 8.

thermometer
Stirring rod

Air space
Liquid whose freezing point
is to be determined

Ice with salt

Figure 8 Freezing point apparatus

For solutions of non-electrolytes the correlation is given by equation 10.

Tf = -kf m (10)

where: Tf = freezing point depression (temperature)

kf = cryoscopic constant (temperature/ molality)
m = molality of the solution (molality)

For solutions of electrolytes, equation 10 is modified by the van’t Hoff factor, i, which accounts
for the dissociation of each molecule into ions:

Tf = -kf m i (11)

where; i = van’t Hoff factor (dimensionless)
Equipment and Materials
Freezing point apparatus, stirring rod, thermometer, glacial acetic acid, benzoic acid, ice,
water

Objective
To evaluate empirically the cryoscopic constant of the solvent using freezing point
depression in a given solvent-solute system

Procedure:
1. Set up the freezing point apparatus shown in Figure 8. Put glacial acetic acid in the inner
tube and immerse this in the ice bath. Stir the acetic acid vigorously and note the
temperature at which it starts to freeze.

2. Repeat this procedure with 0.5 % (w/w) and 1.0 % (w/w), and 1.0%(w/w) solutions of
benzoic acid in acetic acid.

Analysis:
Plot the observed freezing point of the liquids versus concentration (converted to the
appropriate units). A linear correlation whose slope should be equal to the product of kf and
i, should be evident. Compare the results with the known value of the cryoscopic constant of
acetic acid. Is there evidence of the dissociation of benzoic acid in this system? Is ionization
of benzoic and/or acetic affect the freezing point lowering? Cite and discuss practical
application of this method.