Physical Chemistry Lab II

Experiment No. 1
THERMODYNAMICS OF MIXTURES:
DETERMINATION OF PARTIAL MOLAR ENTHALPY

Objectives
1. To determine the effect of composition of the different components of the mixture
on the molar enthalpy of the solution.
2. To evaluate the partial molar enthalpy of the different components of the mixture.

Apparatus
PARR 1455 Solution Calorimeter, 100 ml graduated cylinder

Reagents
Distilled water, Ammonium chloride

Procedure

1. Prepare the molar enthalpy vs. concentration profile of ammonium chloride-water

solution by preparing different amounts (mass) of ammonium chloride to be
dissolved in the same volume of water.
2. Start with at least 0.1 g sample of ammonium chloride (make 6 different samples
with doubling the mass of each sample) and place it in the Teflon dish.
3. Measure 100 mL of distilled water and place it in the Dewar flask.
4. Set up the PARR 1455 Solution Calorimeter.
5. Press F1 to start the initialization stage.
6. Note the sample ID and press ENTER.
7. Input the exact weight of the sample and press ENTER.
8. Wait for the first beep and fire the push rod and press ENTER.
9. Wait for the second beep and press DONE.
10. Browse the result using the arrow up (↑) and arrow down (↓) keys.
11. Repeat procedures for the next samples.

Treatment of Results:

Plot the molar enthalpy vs. mole fraction and get the equations of the trend line. Use this
equation to evaluate the partial molar enthalpy of the components (1 and 2) of the binary
mixture using partial differential equation. Plot the partial molar enthalpy of each
component vs. mole fraction of the first component.

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School of Chemical Engineering and Chemistry
 Physical Chemistry Lab II

Group No._________
Date:_______________________
Instructor:________________________

Name Signature
Leader: ____________________________ ______________________________
Members: ____________________________ ______________________________
____________________________ ______________________________
____________________________ ______________________________
____________________________ ______________________________

FINAL DATA SHEET

Ammonium Chloride (a) and Water (b) solution

Mass of (a) Mass of (b) Mole fraction

Run Mole of (a) Mole of (b)
(g) (g) of (a)
1
2
3
4
5
6
7
8
9
10

Molar Partial Partial

Mole Specific
Average enthalpy of molar molar
fraction of enthalpy of
MW Solution enthalpy of enthalpy of
(b) Solution (cal/g)
(cal/mol) (a), [cal/g] (b), [cal/g]

Room Temperature: ________°C Density of Water:_________g/cm3

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School of Chemical Engineering and Chemistry
General Procedure Manual for the Laboratory Experiments

Physical Chemistry 2 (Laboratory)

Experiment 2: Turbidity

Objective:

At the end of the experiment, the students are expected to:

1. apply the use of a turbidimeter to measure the clarity (turbidity) of water samples.

Procedures:

1. Prepare various concentrations of barium sulfate solutions by mixing appropriate amounts of 1%

(w/w) barium chloride dihydrate solution with 1% (v/v) sulfuric acid. Consult with the instructor
to the proper volumes of the solutions.
2. Calibrate the turbidimeter. You may ask for the assistance of the laboratory assistant.
3. After calibrating the turbidimeter, measure the prepared BaSO4 concentrations.
4. Record the turbidity in the data sheet.

Mapúa University – School of Chemical, Biological, Materials Engineering and Sciences

General Procedure Manual for the Laboratory Experiments

Physical Chemistry 2 (Laboratory)

Data Sheet:

Group No.
Members

Instructor
Date

Sample Turbidity (NTU)

1.0% (v/v) BaCl2 + H2SO4
2.0% (v/v) BaCl2 + H2SO4
4.0% (v/v) BaCl2 + H2SO4
6.0% (v/v) BaCl2 + H2SO4
8.0% (v/v) BaCl2 + H2SO4

Mapúa University – School of Chemical, Biological, Materials Engineering and Sciences

 Physical Chemistry Lab II

Experiment No. 3
SPECTROPHOTOMETRY

Objectives
1. Examination of the essential components in a simple spectrophotometer- the
Jenway 6100 & Perkin Elmer Lambda 40
2. Determination of absorption spectrum of a solution
3. Preparation of Beer’s Law Plot

Apparatus
Spectrophotometer, Test tubes, Test tube rack

Reagents
Cobalt (II) Nitrate, Distilled water

Procedure

Operation of the Spectrophotometer

In a few brief procedures, the spectral characteristics of the

Spectrophotometer will be examined, and the visible spectrum of a simple substance
will be recorded. It must be emphasized that handling of cuvettes are very important.
Any variation in the cuvettes, such as stains, scratches, or changes in glass curvature
will cause varying results. Thus it is essential to follow several rules:
1. Do not handle the lower portion of the cuvette through which the light
passes.
2. Always rinse the cuvette with several portions of the solution to be
measured before taking measurements.
3. Wipe off any liquid drops or smudges with a clean tissue before placing the
cuvette in the spectrophotometer.
4. When inserting a cuvette, always do so with the index mark facing the front
of the instrument, and after the cuvette is seated, line up the index marks
exactly.

A. The Visible Light

Place a dry cuvette containing a strip of plane white paper into the instrument
and rotate the cuvette until the beam reflects upward to view (except for Jenway,
cuvette is optional). Observe and record the color of the beam in 50 nm intervals from
350 to 650 nm. Adjust the light control if necessary to see the beam.

B. Visible Spectrum of a Solution

Obtain a standard solution of Cobalt (II) Nitrate. Set the spectrophotometer to

a wavelength of 375 nm and adjust it to 100% transmittance when containing a
distilled water cuvette. Be sure to use the same distilled water cuvette for all future

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School of Chemical Engineering and Chemistry
 Physical Chemistry Lab II

readings. Fill a second cuvette about one third full with the salt solution and take the
% transmittance and absorbance readings also at 375 nm. Change the wavelength dial
to 400 nm. Again set 100% T reading for distilled water cuvette and take the % T and
A readings of the same samples

C. Beer’s Law Plot

Continue the procedure at the maximum absorbance of the solution. Set the %
T reading to 100 using distilled water cuvette. Take the absorbance reading of a
0.05M Cobalt (II) Nitrate. Dilute the 0.05 M salt solution to 0.04M, 0.03M, 0.02M,
0.01M, and 0.005M, and get the absorbance reading of Cobalt (II) Nitrate solution of
unknown concentration from your instructor. Determine the concentration of the
unknown from the Beer’s Law plot.

Treatment of Results

1. Plot the absorption spectrum, that is %T and A versus wavelength of the

Cobalt Nitrate solutions. Locate and record the wavelength at which
absorption maximum occur. Also plot the absorbance reading versus the
wavelength in a single graph.
2. Prepare a graph of the Beer’s Law using the data taken. Prepare one graph
of %T versus concentration on a semilog paper, with %T on the log axis,
and third graph of absorbance versus concentration on the linear graph. On
the absorbance versus concentration plot draw the best straight line through
the points using the least square method of curve fitting. Use the plot to
determine the concentration of your unknown.

9
School of Chemical Engineering and Chemistry
 Physical Chemistry Lab II

Group No._________
Date:_______________________
Instructor:________________________

Name Signature
Leader: ____________________________ ______________________________
Members: ____________________________ ______________________________
____________________________ ______________________________
____________________________ ______________________________
____________________________ ______________________________

FINAL DATA SHEET

A. Visible Light

Wavelength Color
350
400
450
500
550
600
650

B. Visible Spectrum of a Solution

Wavelength Absorbance Wavelength Absorbance Wavelength Absorbance Wavelength Absorbance

375 500 610 720
400 510 620 730
410 520 630 740
420 530 640 750
430 540 650 760
440 550 660 770
450 560 670 780
460 570 680 790
470 580 690 800
480 590 700
490 600 710

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School of Chemical Engineering and Chemistry
 Physical Chemistry Lab II

C. Beer’s Law Plot

Wavelength: ______________

Concentration, M Absorbance
0.05
0.04
0.03
0.02
0.01
0.005
Unknown
Concentration of
Unknown

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School of Chemical Engineering and Chemistry
 Physical Chemistry Lab II

Experiment No. 4
CONDUCTIMETRY: DETERMINATION OF THE ELECTRICAL
PROPERTIES OF SOLUTIONS

Objectives
1. To determine the relative mobility of some monovalent ions by measuring the
conductance of solutions of electrolytes.
2. To determine the dissociation constant of a weak electrolyte.

Apparatus
Conductivity meter, 50 ml beakers, 10 ml graduated cylinder

Reagents
Deionized water, 0.1M HCl, 0.1M NH4Cl, 0.1M NaCl, 0.1M NaC2H3O2, 0.1M
NaOH

Procedure

A. Electrolytic Conductance and Ionic Mobility

The speed of migration of the ions is one of the factors, which determines
the conductance of an electrolyte solution. The current flowing through the
solution is carried by the ions moving towards the electrodes. The current flowing
through the solution will be estimated by measuring the conductance of the
solution through the following procedures:
1. Assemble the set up for conductance measurement.
2. Prepare 10 ml of each of the following solutions in a test tube:
a. 0.1M ammonium chloride solution
b. 0.1M hydrochloric acid solution
c. 0.1M sodium chloride solution
d. 0.1M sodium acetate solution
e. 0.1M sodium hydroxide solution
3. Measure the conductance of each of the electrolyte solutions by immersing
the electrode in the solution.
4. Wash the electrode with deionized water then dry it with a tissue paper
before immersing it into another solution.

Treatment of Results
1. Write the equations for the dissociation of each of the electrolyte used.
2. Tabulate in increasing order the conductance of the solutions containing chloride
ions. Infer from these results the order for the relative mobility of the cations in
the solutions.
3. Tabulate in increasing order the conductance of the solutions containing sodium
ions. Infer from these results the order for the relative mobility of the anions in the
solutions.

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School of Chemical Engineering and Chemistry
 Physical Chemistry Lab II

B. Determination of Dissociation Constant of a Weak Electrolyte

The dissociation constant of aqueous ammonia, a weak electrolyte, will be

determined through a conductimetric method. The concentration of the ions in the
ammonia solution will be obtained from the concentration of a potassium
hydroxide solution exhibiting the same conductance. Potassium hydroxide is a
strong electrolyte whose ions exhibit the same mobility as those in aqueous
ammonia. The following procedures must be followed:

1. Prepare the following mixtures in a 50 ml beaker:

Vol. 0.01M KOH,

MIXTURE Vol. Water, ml
ml
1 25.0 0.0
2 20.0 5.0
3 15.0 10.0
4 10.0 15.0
5 5.0 20.0
6 1.0 25.0

2. Measure the conductance of the above mixtures.

3. Pour 10 ml each of 1.0M and 0.1M ammonia solution into two separate test
tubes, and then measure the conductance of each solution.

Treatment of Results
1. Calculate the concentration of potassium hydroxide in each of the mixtures
prepared.
2. Tabulate the concentration and the conductance of the potassium hydroxide
solutions.
3. Plot the concentration versus conductance of the potassium hydroxide solutions.
4. Determine from the graph the concentration of the potassium hydroxide solution
that exhibits the same conductance as each of the ammonia solutions used. This
concentration is equal to the concentration of ammonia ionized in the solution.
5. Write the chemical equation for the dissociation of ammonia into ions in aqueous
solution.
6. Using the concentration data obtained for each of the solutions used, calculate the
dissociation constant of ammonia solution.

4
School of Chemical Engineering and Chemistry
 Physical Chemistry Lab II

Group No._________
Date:_______________________
Instructor:________________________

Name Signature
Leader: ____________________________ ______________________________
Members:____________________________ ______________________________
____________________________ ______________________________
____________________________ ______________________________
____________________________ ______________________________

FINAL DATA SHEET

A. Electrolytic Conductance and Ionic Mobility

Solution Conductance
0.1 M NH4Cl
0.1 M HCl
0.1 M NaCl
0.1 M NaC2H3O2
0.1 M NaOH

B. Determination of Dissociation Constant of a Weak Electrolyte

Volume Volume 0.01M

Mixture Conductance Concentration
Water KOH
1
2
3
4
5
6

Sample Conductance Dissociation Constant

1 M NH4OH
0.01 M NH4OH

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School of Chemical Engineering and Chemistry
General Procedure Manual for the Laboratory Experiments

Physical Chemistry 2 (Laboratory)

Experiment 5: Ternary System

Objective:

At the end of the experiment, the students are expected to:

1. apply the ternary phase diagram to determine the tie lines and equilibrium concentrations of
three component solutions.

Procedures:

1. Prepare 50-mL of various concentrations of acetone in water solutions referring to Table 1 of

the data sheet. Then, titrate the solution using ethyl acetate until a stable cloudiness in the
solution has been observed. Record the volume of the titrant used in the data sheet.
2. Repeat the titration for acetone in ethyl acetate solutions (referring to Table 2 of the data
sheet). Titrate this solution with distilled water until a stable cloudiness in the solution
has been observed. Record the volume of the titrant used in the data sheet.
3. Lastly, prepare 100-mL solutions containing acetone, ethyl acetate, and water. Refer to Table 3
of the data sheet for the various proportions of the compounds. Transfer the solution in a
separatory funnel. Let it stand until two distinct phases are observed. Separate the bottom
phase (which is the heavy phase) from the upper phase (which is the light phase). Determine
the density of the two phases separately.
4. Titrate separately the heavy and light phases with 0.2 M NaOH (indicator: phenolphthalein)
until a salmon pink end point has been obtained.
5. Record the volume of titrant used in the data sheet.

Mapúa University – School of Chemical, Biological, Materials Engineering and Sciences

General Procedure Manual for the Laboratory Experiments

Physical Chemistry 2 (Laboratory)

Data Sheet:

Group No.
Members

Instructor
Date

Table 1: Acetone in Water Solution (Titrant: Ethyl Acetate)

% Acetone (w/w) Volume of Titrant (mL)
10%
25%
40%
60%

Table 2: Acetone in Ethyl Acetate (Titrant: Water)

% Acetone (w/w) Volume of Titrant (mL)
10%
25%
40%
60%

Mapúa University – School of Chemical, Biological, Materials Engineering and Sciences

General Procedure Manual for the Laboratory Experiments

Physical Chemistry 2 (Laboratory)

Table 3: Tie-line Determination (Titrant: 0.2 N NaOH with phenolphthalein indicator)

Solution Mass of Mass of Volume Volume Density Density Volume Volume
Composition the light the of the of the of the of the of of
phase heavy light heavy light heavy titrant titrant
(g) phase phase phase phase phase (light (heavy
(g) (mL) (mL) (g/mL) (g/mL) phase) phase)
in mL in mL
10% (w/w)
acetone + 45%
ethyl acetate +
water
20% (w/w)
acetone + 45%
ethyl acetate +
water
30% (w/w)
acetone + 45%
ethyl acetate +
water
40% (w/w)
acetone + 45%
ethyl acetate +
water

Mapúa University – School of Chemical, Biological, Materials Engineering and Sciences

General Procedure Manual for the Laboratory Experiments

Physical Chemistry 2 (Laboratory)

Experiment 6: Adsorption

Objective:

At the end of the experiment, the students are expected to:

1. determine the data necessary to draw an adsorption isotherm for a substance adsorbed from the
solution into a porous solid.

Procedures:

1. Weigh approximately 1 – 2 g of activated carbon. You may consult with the instructor for the
proper mass to be used in the experiment.
2. Prepare 0.5 M of acetic acid stock solution. Dilute the stock solution several times. Refer to the
data sheet for the proper concentrations of acetic acid.
3. Put the activated carbon in 100-mL of the acetic acid solutions. Let it stand for one hour.
4. Meanwhile, standardize the acetic acid solutions by titrating with 0.1 M of NaOH solution.
5. After 1 hour has elapsed, filter out the activated carbon. Take around 10 – 20 mL of aliquot from
the solution. Titrate with 0.1 M of NaOH solution until a salmon pink end point has been obtained.
6. Record the volume of the titrant used.

Mapúa University – School of Chemical, Biological, Materials Engineering and Sciences

General Procedure Manual for the Laboratory Experiments

Physical Chemistry 2 (Laboratory)

Data Sheet:

Table 1: Standardization of Acetic Acid

Trial 1 Trial 2 Trial 3 Average
Volume of Acetic
Acid (in mL)
NaOH
concentration (in
mol/L)
Vol. of NaOH
used (in mL)
Concentration of
Acetic acid

Table 2: Equilibrium concentration of acetic acid in carbon

Original Final
Volume of Volume of
Weight of CH3COOH CH3COOH
Solution CH3COOH, NaOH
sample (m), g concentration concentration
mL used, mL
(C1), mol L–1 (C2), mol L–1
N/2 2.00
N/4 1.80
N/8 1.60
N/16 1.40
N/32 1.20
N/64 1.00

Table 3: Adsorption Isotherm

Solution x (in grams) x/m log (x/m) log (C2) C2/(x/m)
N/2
N/4
N/8
N/16
N/32
N/64

Mapúa University – School of Chemical, Biological, Materials Engineering and Sciences

 Physical Chemistry Lab II

Experiment No. 7
CHEMICAL KINETICS:
THE HYDROLYSIS OF METHYL ACETATE

Objectives
1. To evaluate the hydrolysis of methyl acetate by studying its chemical kinetics.
2. To quantify the activation energy requirement of the reaction.
3. To determine the change in enthalpy and change in entropy of the reaction/

Apparatus
Electronic Water Bath, timer, Erlenmeyer flasks, graduated cylinders, buret, pipet,
test tubes

Reagents
Distilled water, methyl acetate, 1.0M HCl solution, standard NaOH solution,
phenolphthalein

Procedure

Note: Careful pipetting and titrating techniques are essential if good data are to be
obtained. The temperature should be controlled as precisely as possible.

1. Obtain about 50 mL methyl acetate in a large test tube and 300 mL 1.0 M HCl in
an Erlenmeyer flask. Allow these solutions to equilibrate in 25°C bath. Also
equilibrate a flask containing about 200 mL of deionized water.

2. Into a dry 250 mL Erlenmeyer flask pipet 50 mL of the HCl and 50 mL of water.
To initiate the reaction add from a pipet 10 mL of methyl acetate. Start the timer
when the pipet is half emptied. Mix the solution thoroughly and keep it in the
bath.

3. As soon as possible, withdraw a 5 mL aliquot of the reaction mixture and transfer

it to a 150 mL Erlenmeyer which contains approximately 50 mL of water. The
receiver should be pre-chilled in an ice bath to make sure that the hydrolysis is
sufficiently slowed. Note the time at which the pipet has been half emptied.

4. Titrate the diluted aliquot as soon as possible with standard NaOH using
phenolphthalein as the indicator.

5. Repeat steps 3 and 4 at 10 minute intervals for one hour and for 20 minute
intervals for another hour, if possible. Make sure that the pipet used to withdraw
each 5 mL aliquot is clean and dry.

6. At some convenient time titrate 2 or 3 aliquots of the equilibrated HCl so that the
molarity at 25°C will be known accurately.

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School of Chemical Engineering and Chemistry
 Physical Chemistry Lab II

7. Repeat the above procedure using 100 mL 1.0 M HCl and 10 mL methyl acetate
as the reaction mixture. This reaction will proceed more rapidly, so aliquots
should be withdrawn at shorter intervals. Duplicate runs should be performed if
possible. An efficient student pair should be able to follow two or more properly
spaced reactions at the same time.

8. Repeat the procedure at 35°C using the reaction conditions given in step 2.
Remember that the rate will be about double that at 25°C, so aliquots will have to
be withdrawn at shorter intervals. Determine the molar concentration of the HCl
at 35°C.

Treatment of Results

1. For each aliquot calculate Ct (or a quantity proportional to Ct). (The density of
methyl acetate is 0.9273 g/mL at 25°C and 0.9141 g/mL at 35°C, and the
molecular weight is 74.08) Plot ln Ct versus t for each set of data. Evaluate the
acid-dependent rate constant, kH, in seconds-1. Use the uncertainty in the slope to
evaluate the 95% confidence limits of kH.

2. From runs at 25°C with different concentrations of HCl determine the order with
respect to H3O+ and its uncertainty. Use the nearest whole-number value of q to
calculate kF’ for each run. Also obtain the uncertainty in kF’. (Assume negligible
error in q for these calculations.)

3. Evaluate Ea, ΔH°↕, and ΔS°↕ using the temperature dependence data.

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School of Chemical Engineering and Chemistry
 Physical Chemistry Lab II

Group No._________
Date:_______________________
Instructor:________________________

Name Signature
Leader: ____________________________ ______________________________
Members: ____________________________ ______________________________
____________________________ ______________________________
____________________________ ______________________________
____________________________ ______________________________

FINAL DATA SHEET

A. Determination of Hydrolysis Rate at Room Temperature and Lower

Concentration of HCl

Estimated Actual Moles of Concentratio

Time of Volume Concetration
Reaction Reaction Acetic n of Methyl
Withdrawa of NaOH of Acetic
Time, Time, Acid in Acetate Left,
l of Aliquot used, mL Acid, mol/L
min min Aliquot mol/L
0
10
20
30
40
50
60
80
100
120

Concentration of HCl is reaction mixture, mol/L = ____________________________

B. Determination of Hydrolysis Rate at Room Temperature and Higher

Concentration of HCl

Estimated Actual Moles of Concentratio

Time of Volume Concetration
Reaction Reaction Acetic n of Methyl
Withdrawa of NaOH of Acetic
Time, Time, Acid in Acetate Left,
l of Aliquot used, mL Acid, mol/L
min min Aliquot mol/L
0
10
20

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School of Chemical Engineering and Chemistry
 Physical Chemistry Lab II

30
40
50
60
80
100
120

Concentration of HCl is reaction mixture, mol/L = ____________________________

C. Determination of Hydrolysis Rate at High Temperature and Lower

Concentration of HCl

Estimated Actual Moles of Concentratio

Time of Volume Concetration
Reaction Reaction Acetic n of Methyl
Withdrawa of NaOH of Acetic
Time, Time, Acid in Acetate Left,
l of Aliquot used, mL Acid, mol/L
min min Aliquot mol/L
0
10
20
30
40
50
60
80
100
120

Concentration of HCl is reaction mixture, mol/L = _______________________

Acid-dependent rate constant at low HCl concentration = _____________________

Acid-dependent rate constant at high HCl concentration = _____________________

Order of reaction with respect to HCl concentration = _____________________

Eact of the reaction = _____________________

ΔH° of the reaction = _____________________

ΔS° of the reaction = _____________________

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