Institute of Chemistry

College of Science
University of the Philippines, Diliman, Quezon City

General Chemistry II Laboratory Manual

Revision as of May 26, 2018

(Revision on-going)
 Table of Contents

Table of Contents i

List of Figures ii

List of Tables ii

Acknowledgement iii

Chemical Safety and Waste Disposal iv

Scientific Writing vii

E1 Calorimetry 1

E2 Chemical Kinetics 5

E3 Chemical Equilibrium 8

E4 Spectrophotometric Determination of the Equilibrium Constant of a Reaction 11

E5 Determination of Ka of Acetic Acid by pH Measurement 17

E6 Buffers 19

E7 Solubility Equilibrium of Calcium Hydroxide 22

E8 Separation of Anions by Selective Precipitation and Other Reactions 25

E9 Coordination Chemistry 28

E10 Synthesis of a Thermochromic Material 30

E11 Electrochemistry 32

Worksheets

COPYRIGHT STATEMENT:
All rights are reserved by the UPD-Institute of Chemistry. No part of this manual should be reproduced without
permission.

1
List of Figures
1 GHS pictograms used in chemical containers. From: schoolipm.tamu.edu . . . . . . . . . . v
2 Calorimeter setup for this experiment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
3 Block diagram of a single beam UV-Vis spectrophotometer . . . . . . . . . . . . . . . . . . . 12
4 A simple galvanic cell . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33

List of Tables
1 Reaction systems to be studied. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2 Standard enthalpies of formation of selected substances. . . . . . . . . . . . . . . . . . . . . 4
3 Components of the standard solutions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
4 Components of the unknown solutions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14

ii
 Acknowledgments

This is to acknowledge the faculty members who have handled General Chemistry II lecture and lab-
oratory classes and have worked in revising and evaluating the existing experiments in this manual since
AY 2015-2016.

R. Acero L. Payawan
K. Benito E. Ratilla
K. Custodio M. Santiago
P. Espino W. Santos
M. Fajiculay T. Talusan
L. Mella L. Trinidad
J. Nazareno R. Ugalino
G. Nuesca A. Yago
C. Pagtalunan

Further evaluation on experiments and content revision are still conducted up to this date.

iii
Chemical Safety and Waste Disposal

Chemical Safety Awareness

Most of the information regarding the risks and hazards associated with handling a certain substance
are summarized in its Material Safety Data Sheet - MSDS, for short. Before any experiment, the MSDS
for all the chemicals to be used should be reviewed to familiarize yourself with proper handling and
safety precautions. You can easily access MSDS online. Our laboratory rooms also have a compilation of
MSDS for all the chemicals to be used in our experiments.

In 1992, the United Nations created the Globally Harmonized System of Classification and Label-
ing of Chemicals (GHS). It aimed to supersede the various classification and labelling standards used
in different countries with a global system. A GHS label for a chemical contains: (i) hazard pictograms
which conveys key physical, health, and environmental hazard information, (ii) hazard statements which
further details the hazards, and (iii) precautionary state which discuss measures to minimize potential
damages (prevention, response to spillage and exposure, storage, disposal). GHS uses two sets of pic-
tograms - one for workplace hazards, and another for transportation hazards. In our setting, we will only
be concerned with the first.

In reading safety information, the student should be familiar with the following:

1. An explosive substance is capable of reacting so as to produce a gas at such reaction temperature,

pressure, and rate sufficient to cause damage to the surrounding.

2. A flammable substance can ”catch fire” under ambient conditions. Examples are organic solvents
like ethanol, toluene, and benzene.

3. Acute toxicity is assessed through five categories - with Category 1 substances being most severely
toxic. In our lab, most chemicals that will be handled would only be Category 4 or 5.

4. Skin corrosion means irreversible damage to the skin after application of the substance for up to 4
hours. Concentrated acids and bases pose this kind of hazard.

5. Sensitizers can induce allergic response upon contact with the skin and/or airways. Experimenters
should be aware of their allergy conditions before performing any experiment.

6. Carcinogens induce cancer or increase its incidence. Mutagens induce mutations in populations of
cells and/or organisms.

7. Reproductive toxicity includes adverse effects on sexual function and fertility in adults, as well as
developmental toxicity in offspring.

8. Environmental hazards are described in terms of aquatic toxicity. Acute aquatic toxicity deals
with injuries from short-term exposure, while chronic aquatic toxicity deals with adverse effects in
relation to the life cycle of the organism, including degradation and accumulation concerns.

Here, the chemicals to be used for each experiment are listed along with their risk and safety state-
ments (R/S phrases). The last page of the manual contains the list of all the R/S phrases to which the
students can refer to.

iv
 Figure 1: GHS pictograms used in chemical containers. From: schoolipm.tamu.edu

Protective Measures

1. Always wear your PPE. The prescribed personnel protective equipment (PPE) serves as the first
line of defense against exposure and accidental spills. A complete PPE should include: (i) a lab coat,
preferably white and with sleeves reaching the elbow, (ii) sleeved shirts, long pants and closed-toe
shoes, and (iii) safety goggles. Wearing face masks and gloves is also recommended.

v
 2. Use fume hoods in handling substances and performing reaction workups which may generate
fumes which are corrosive, toxic, and flammable.

3. NO eating, drinking, smoking, and wearing cosmetics in the lab!

4. Read labels. Treat all chemicals as hazardous!

First Aid and Emergency Procedures

There are different kinds of hazards that can occur inside chemical laboratory and therefore require
appropriate first aid measures.

1. In case of skin contact, use the sink to locally remove the substance using large amounts of water for
a minimum of 10 minutes. If a large part of the body is affected by the spill and clothing is affected,
take it off and use the emergency shower. Call for medical assistance if necessary.

2. In case of eye contact, use the eye washer and flush it with water for a minimum of 10 minutes. Call
for medical assistance if necessary.

3. In case of inhalation, move to fresh air and loosen all tight clothing. Call for medical assistance if
necessary.

4. In case of ingestion, call for medical assistance. Do not induce vomitting since it may be dangerous
the victim.

5. In case of heat burns, immerse the affected area in cold water and cover it with clean dressing.
Cold water or ice may be applied, but not grease or cream. In case of fire inside laboratory rooms,
immediately evacuate the area.

6. In case of chemical burns, flush skin with cold water for 15 minutes. Remove clothing from burnt
area and cover it with clean dressing.

7. In case of chemical spills, ventilate the area of spill or leak. Use appropriate spill kit or materials to
neutralize or absorb the spill.

Waste Disposal

Follow the Waste Disposal procedures stated for each experiment. When in doubt regarding disposal
procedures, confirm with the instructor first. REMEMBER THAT NOT ALL CHEMICALS CAN BE DIS-
POSED IN THE SINK!

Reference
Stepnowski, P. and Wilamowski, J. Safety in the Chemistry Laboratory - A Practical Guide for Teachers.
Fundacja Rozwoju Uniwersytetu Gdanskiego.

vi
Scientific Writing
In this course, a complete formal report (FR) should consist of the following parts in the indicated se-
quence (unless otherwise specified): (1) Abstract, (2) Introduction, (3) Methodology, (4) Results and Dis-
cussion, (5) Conclusion and Recommendations, (6) References, (7) Appendix.

General notes
The report should be a continuous narrative, with every main point written in a coherent and concise
paragraph. All chemical equations should be balanced and numbered. All mathematical equations pre-
sented should also be numbered, and the variables should be defined. Tables and figures should be
labeled properly as well. In general, table captions are placed above the table, while figure captions are
placed below the figure. Captions should be descriptive.

Abstract
The abstract is the condensed version of the entire paper. It should contain the four (4) essential aspects
of the report: purpose of the study, brief methodology, results and its significance, and important conclu-
sions. It consists of 100 to 200 words written in one paragraph. It is recommended to write the abstract
after writing the final draft of the formal report. Remember NOT to include the theory, detailed method-
ology, and sources of errors in your abstract.

Introduction
The introduction should present the theory behind the experiment, the chemical system being studied
and the pertinent working equations to calculate parameters needed. It should end with the statement of
purpose of the experiment.

Methodology
The methodology should report the procedures in such a way that any reader of equal skill can judiciously
reproduce the experiment performed by the author. Passive voice and past tense should be used.

Results and Discussion

The summary of the treated data should be presented. Raw data which may be not much relevant to the
discussion should be included in the Appendix section of your paper. Results are best presented in tables
or figures. Always interpret the results; results and discussions should come hand in hand. If a table
or figure is presented, its interpretation should immediately follow in your paper. Avoid straying away
from the purpose of the experiment. Do not include information that is not pertinent to the purpose of
the experiment. Explain clearly and briefly. Compare your result to literature values and provide expla-
nations when the two do not agree. Sources of errors should also be indicated, but DO NOT use human
error as one of the sources of errors.

Conclusion and Recommendation

This section summarizes the important results from the experiment. It should also highlight the signif-
icance of the result obtained and its implication to the method employed. This section is also used to
evaluate the success of the experiment. Suggestions for the improvement of the method used are also
written in this section.

vii
References
At least two (2) book references and one (1) journal article are required. Internet references are also al-
lowed provided that they came from reputable sources (i.e. Websites of universities here and abroad).
Wikipedia, Scribd and Yahoo Answer are among other internet sites that are not reputable hence should
NOT be used as reference. The references should be written using the ACS citation style.

Appendix
This includes the working equations, sample calculations done during data treatment, and sample calcu-
lations done in obtaining the parameters sought for. Raw data should also be included in the appendix.

viii
EXPERIMENT 1

Calorimetry
At the end of the experiment, the student will be able to:

1. measure the enthalpies of reaction, ∆H, as a function of temperature change;

2. apply the calculations to different types of reactions in aqueous media.

INTRODUCTION

Calorimetry is the measurement of heat exchanges accompanying physical or chemical processes us-
ing a device called calorimeter. There are different types of calorimeters. A constant-pressure calorime-
ter measures heat of a process maintained at constant pressure - usually, at atmospheric pressure. An
example is the simple coffee-cup calorimeter. In turn, a constant-volume calorimeter measures heat of a
process with no volume change accompanying it. An example is the bomb calorimeter which is widely
used in the industry. The measured heats of combustion of fuels and food products serve as indices of
their energy content.

Processes are accompanied by heat exchanges. A process that liberates heat is exothermic, while one
that absorbs heat is endothermic. The heat involved in a process carried out at constant pressure is equal
to the enthalpy change, ∆H, of that process. Heats of reaction are usually reported as reaction enthalpies,
∆Hrxn . Most reactions, especially those in aqueous solution, do not involve gases and occur under con-
stant, atmospheric pressure. Hence, ∆H can sufficiently describe the thermochemistry of such reactions.
In this experiment, heats of select reactions will be determined.

The working principle of calorimetry is to establish a function that relates the heat of a process, and an ob-
served temperature change in the calorimeter where such process is carried out. Once such function is established
for the calorimeter, any temperature change, ∆Tcal in the calorimeter measured for a process can be fed
to the function to calculate the heat involved, qrxn .

Figure 2: Calorimeter setup for this experiment

1
 Figure 2 shows the calorimeter to be used in this experiment. The reaction mixture will be placed in
the test tube and allowed to react; after which, ∆Tcal will be measured. The Styrofoam and rubber stopper
insulates the reaction mixture such that the entire setup (reaction mixture + calorimeter) is an adiabatic
system. An adiabatic system is one which cannot exchange heat with its surroundings. Hence, by con-
servation of energy, heat exchange occurs only between the reaction system, qrxn and the calorimeter, qcal ,
such that

qsetup = qrxn + qcal = 0 (1)

The entire setup is also isobaric, i.e. it is under constant pressure. Hence, all reactions carried out in this
setup will have heats equal to their enthalpy changes:

qrxn = n∆Hrxn (2)

where n is the amount, in moles, consumed in the reaction as it was carried out, and ∆Hrxn is the molar
enthalpy of reaction, characteristic of the reaction studied. In turn, the heat exchanged to the calorimeter
will be used to change the temperature of the calorimeter, according to:

qcal = Ccal ∆Tcal = Ccal (Tf − Ti ) (3)

where Tf and Ti are the final (after reaction) and initial (before reaction) temperature of the calorime-
ter, respectively, and Ccal is the heat capacity of the calorimeter. From equations (1)-(3), one can derive
a function that relates a measured ∆Tcal with the ∆Hrxn of the reaction carried out in the calorimeter used.

To fully apply the derived function, calibration is done to determine the Ccal , characteristic of the
calorimeter used. For this experiment, calibration is based on the reaction below of known ∆Hrxn =
−55.85 kJ mol-1

H + (aq) + OH − (aq) → H2 O(l) (4)

Once the ∆Tcal is measured when this reaction is carried out in the calorimeter, Ccal can already be calcu-
lated. With this Ccal value, the heats can be determined from measured ∆Tcal for any process carried out
in the calorimeter, provided that none of the parts of the setup changes in the course of the process. If the reaction
yields substances not present during calibration, Ccal must be corrected to account them. In general,
X
Ccal,corrected = Ccal + Ci (5)
i

where Ci are the heat capacities of the additional substances. This corrected Ccal,corrected should be the
one used in calculating ∆Hrxn for the particular reaction. For this experiment, assume that all aqueous so-
lutions have the same specific heat as water. Only excess solids need to be accounted for in correcting Ccal .

CHEMICALS

1.0 M CH3 COOH 1.0 M NH3 KCl solid

0.50 M Na2 CO3 1.0 M CaCl2 1.0 M BaCl2
1.0 M NaOH 1.0 M HCl

APPARATUS

Styrofoam calorimeter
Alcohol thermometer

2
PROCEDURE

Calibration of the calorimeter

1. Secure a 6-inch test tube where the reactions will be carried out. Make sure that it snugly fits into the
carved hole of the Styrofoam. Also, make sure that the rubber stopper (with the inserted thermome-
ter) seals the test tube. When reading temperatures, ONLY the rubber stopper with thermometer
should be visible on the surface of the Styrofoam.

2. Measure 10.00 mL 1.0 M NaOH and transfer into the test tube. Cover the test tube with the stopper.

3. Record the temperature of the calorimeter for 15 s intervals until the reading is constant for at least
2 min. Record this temperature as Ti .

4. Measure 5.00 mL 1.0 M HCl and rapidly transfer it to the test tube containing 1.0 M NaOH. Then,
immediately cover the test tube again with the stopper.

5. Record the temperature of the calorimeter for 15 s intervals until the reading is constant for at least 2
min or changing at a constant rate. If the temperature became constant, record this as Tf . If the tem-
perature was decreasing/increasing at a constant rate, record the maximum/minimum temperature
attained respectively, as Tf .

6. Perform 2 trials for the calibration.

Determination of ∆Hrxn

Table 1: Reaction systems to be studied.

Reaction system A B
1 10.00 mL 1.0 M CH3 COOH 5.00 mL 1.0 M NaOH
2 10.00 mL 1.0 M CH3 COOH 5.00 mL 1.0 M NH3
3 15.00 mL distilled water 1.30 g KCl solid
4 10.00 mL 0.50 M Na2 CO3 5.00 mL 1.0 M CaCl2
5 10.00 mL 0.50 M Na2 CO3 5.00 mL 1.0 M BaCl2

1. The reaction systems above will be divided among pairs. Refer to Table 1.

2. Transfer the assigned component A to the same test tube used in the calibration. Measure the Ti as
was done during calibration.

3. Rapidly transfer the assigned component B to the test tube already containing A. Then, immedi-
ately cover the test tube with the stopper.

4. Record the temperature of the calorimeter for 15 s intervals until the reading is constant for at least
2 min or changing at a constant rate. Swirl the reaction mixture occasionally while reading the
temperature. If the temperature became constant, record this as Tf . If the temperature was de-
creasing/increasing at a constant rate, record the maximum/minimum temperature attained re-
spectively, as Tf .

5. Perform 2 trials.

3
 Table 2: Standard enthalpies of formation of selected substances.
Substance ∆Hf◦ , kJ mol-1
Ba2+ (aq) −537.6
BaCO3 (s) −1216
Ca2+ (aq) −542.8
CaCO3 (s) −1207.0
CH3 COO- (aq) −486.01
CH3 COOH(aq) −485.76
CO3 2- (aq) −677.1
Cl- (aq) −167.2
H2 O(l) −285.8
NH3 (aq) −80.29
NH4 + (aq) −132.5
OH- (aq) −230.0
K+ (aq) −252.4
KCl(s) −436.7

Data treatment

1. Calculate the average Ccal of the calorimeter used.

2. Calculate the average experimental ∆Hrxn . For the reactions which involved excess solids, the heat
capacity of the solid X is CX = mX s(X), where mX is the mass of the solid, and s(X) is its specific
heat. Calculate mX through stoichiometry, assuming that the reactions proceeded completely. Also,
use the following specific heats: s(CaCO3 ) = 0.8181 J g-1◦ C-1 ; s(BaCO3 ) = 0.4325 J g-1◦ C-1 .

3. Calculate the theoretical ∆Hrxn using the standard enthalpies of formation, ∆Hf◦ , provided in Table
2.

4. Calculate the percent error for the ∆Hrxn values.

WASTE DISPOSAL

1. Dilute all resulting solutions (except those with Ba2+ ) with tap water and flush directly down the
sink with copious running water.

2. For mixtures which generated excess solids, dissolve first the solid with sufficient amount of HCl.
Then, dilute the resulting solution (except those with Ba2+ ) and flush directly down the sink with
copious running water.

3. Dispose all resulting solutions containing Ba2+ into INORGANIC WASTE.

REFERENCE
Petrucci, R. Herring, F., Madura, J., Bissonnette, C. General Chemistry: Principles and Modern Applications,
10th Ed.;Pearson: Toronto, Canada.

4
EXPERIMENT 2

Chemical Kinetics
At the end of the experiment, the student will be able to:

1. describe the kinetics of the reaction of I − and S2 O82− ;

2. use the initial rate method to determine the rate law of the reaction;

3. observe the effect of temperature on the reaction rate and calculate pertinent values of the Arrhenius
equation; and

4. observe the effect of a catalyst to the reaction rate.

INTRODUCTION
The rate of a chemical reaction is defined as the change of the concentration of a reactant or product per
unit time. The concentration of the reactants, temperature, and the presence of catalyst are the major fac-
tors that affect the rate of a chemical reaction.

The kinetics of the reaction between persulfate, S2 O2− −

8 , and iodide, I ions will be studied in this experi-
ment:
S2 O82− + 2I − → 2SO42− + I2 (1)
The rate expression of this reaction can be written as the decrease in concentration of reactants, S2 O2− 8 or
I− , or the increase in concentration of the products, SO2− 4 or I2 with time. This is given by the following
rate law:
d[S2 O82− ] 1 d[I − ] 1 d[SO42− ] d[I2 ]
rate = − =− = = = k[S2 O82− ]x [I − ]y (2)
dt 2 dt 2 dt dt
where k is the rate constant and the powers x and y are the orders of the reaction with respect to S2 O2−
8
and I− , respectively. These variables can be determined experimentally using the method of initial rates.
Such method involves performing the reaction at controlled conditions, i.e. varying concentrations of one
reactant while keeping the concentration of the other constant, and measuring the rate at each case.

The effect of temperature on the reaction rate is given by the Arrhenius equation:

Ea
lnk = lnA − (3)
RT
where A is the Arrhenius constant, Ea the activation energy of the reaction, T the temperature in Kelvin,
and R the universal gas constant (8.314 J mol−1 K −1 ). From the rate constants and reaction temperatures,
Ea and A of the reaction of S2 O2− −
8 and I can be determined.

In this experiment, the rate of I2 formation will be measured to describe the rate of the reaction. The I2
formed from the S2 O2− − − 2−
8 /I reaction is reduced back to I by S2 O3 ions.

2S2 O32− + I2 → S4 O62− + 2I − (4)

When all the S2 O2−

3 is used up, free I2 starts to form in solution. By measuring the time taken for the
known amount of S2 O2−
3 to be consumed, the rate of the formation of I2 during that time can be calculated.

5
MATERIALS/APPARATUS
Ice Stopwatch/timer Thermometer

CHEMICALS
KI KCl K2 SO4
K2 S2 O8 Na2 S2 O3 · 5H2 O CuSO4
Starch

GLASSWARES
Volumetric flasks (5-, 500-mL) Measuring pipettes (10-mL) Beakers (50-mL)

EQUIPMENT
Top loading balance Hot plate

PROCEDURE

Solution Preparation
Prepare the following solutions by class:

1. 250.0 mL 0.2 M KI

2. 250.0 mL 0.2 M KCl

3. 250.0 mL 0.1 M K2 S2 O8

4. 250.0 mL 0.1 M K2 SO4

5. 250.0 mL 4.0 mM Na2 S2 O3 (from Na2 S2 O3 · 5H2 O)

6. 20.0 mL of 1% (w/v) fresh starch solution

Moisten 0.20 g of soluble starch with a small amount of H2 O until a smooth paste is obtained. Pour
slowly into 20.0 mL of boiling water. The starch solution must be freshly prepared.
NOTE: Keep the solution at 90◦ C–100◦ C to avoid starch solution from drying up.

7. 50.0 mL 0.01 M CuSO4

Effect of Persulfate and Iodide Concentrations on the Reaction Rate

NOTE: Runs 1-5 SHOULD be done one at a time. For each run, label two 50-mL beakers as “A” and “B.”

1. Prepare the contents of beakers A and B according to the volumes presented in the following table:

6
 2. Pour the contents of beaker A into beaker B. Immediately start timing the reaction. Stop the timer
once the mixture turns blue. Measure the temperature of the reaction mixture.
Effect of Temperature on the Reaction Rate
1. Prepare two more sets of “run 2” (referred to as sets 2 and 3).
2. In a water bath, heat beakers A and B of run 2 (set 2) at around 50◦ C (40◦ C-60◦ C). Mix the contents
of beaker A and beaker B. Immediately start timing the reaction until the mixture turns blue.
3. Cool beakers A and B of run 2 (set 3) in an ice bath. Once the temperature has already reached
around 5◦ C (0◦ C-10◦ C), pour the contents of beaker A into beaker B and start timing the reaction.
Stop the timer after a blue solution is observed.
Effect of Catalyst on the Reaction Rate
1. Prepare a fourth set of run 2.
2. Add 4 drops of 0.01 M CuSO4 immediately after the contents of beaker A is added to the contents
of beaker B. Time the reaction until the reaction mixture turns blue. Compare the reaction time with
set 1.

WASTE DISPOSAL
1. Dispose Cu(II) solutions in inorganic waste jars.
2. All other solutions can be discarded in the sink along with copious running water.

DATA TREATMENT
Prepare the following graphs:
1. ln rate versus ln[S2 O2− −
8 ] for runs 2,4, and 5 (constant [I ]) with the slope of the line equal to the rate
2−
order of S2 O8
2. ln rate versus ln[I− ] for runs 1, 2, and 3 (constant [S2 O2−
8 ]) with the slope of the line equal to the rate
order of I−

3. ln k versus 1/T for sets 1, 2, and 3 of run 2 with the slope multiplied with R equal to the activation
energy

CALCULATIONS
Determine the:
1. rate for each setup (M/s) by using the concentration of S2 O2−
3 since it acts as the limiting reactant

2. rate law for reaction between I− and S2 O2−

8

3. activation energy and Arrhenius constant for the reaction

REFERENCES
1. Petrucci, R. Herring, F., Madura, J., Bissonnette, C. General chemistry: Principles and Modern Applica-
tions, 10th Ed.;Pearson: Toronto, Canada.
2. Moews, P. Jr. and Petrucci, R.J. Chem. Educ., 1964, 48, 10, 549.
3. Massachusetts Institute of Technology Lab 3 - Chemical Kinetics [Online]
https://ocw.mit.edu/courses/chemistry/5-302-introduction-to-experimental-chemistry-january-
iap-2005/labs/ (accessed October 9, 2016)

7
EXPERIMENT 3

Chemical Equilibrium
At the end of the experiment, the student will be able to:

1. determine the effect of changes in concentration, including pH, and temperature of a system in equi-
librium.

INTRODUCTION
Reaction systems tend to proceed to a state of chemical equilibrium. This tendency to attain equilib-
rium dictates whether a reaction will proceed spontaneously or not. Reactions can only proceed two ways
- forward or reverse. If the direction of reaction proceeds towards the state of chemical equilibrium, it will
be spontaneous. Otherwise, such direction is non-spontaneous. Once reaction systems attain chemical
equilibrium, they intend to remain so such that the concentrations of species remain constant. Note how-
ever that chemical equilibrium is a dynamic equilibrium, that is, although the concentrations of products
and reactants appear to remain constant, the forward and reverse reactions are continuously in progress
but are of equal rates such that their ”net outputs” cancel out.

Le Chatelier’s Principle states that when a stress is applied to a reaction system in a state of chemical equi-
librium, the system reacts in a direction (forward or reverse) such that the stress is relieved and equilibrium is
re-established. More commonly, it is said that in response to a stress, a reaction system shifts in the for-
ward/reverse direction to establish equilibrium again. Le Chatelier’s principle just reiterates the concept
that all reaction systems will always tend towards a state of chemical equilibrium. Stress may come in the
form of change in reactant/product concentration, pressure, volume, and temperature.

In this experiment, the following equilibria in aqueous solution will be studied: (1) Fe(II)-Ag(I), (2)
Cu(II)-ammonia, (3) chromate-dichromate, (4) Fe(III)-thiocyanate, and (5) Co(II)-chloride.

CHEMICALS

Chemical Concentration Risk phrases Safety phrases

FeSO4 0.10 M None listed None listed
AgNO3 0.10 M 36/38, 50/53 26,57,60
K3 Fe(CN)6 0.10 M None listed None listed
KSCN 0.10 M None listed None listed
HCl 12.1 M (concentrated) 34,37 26,45
CuSO4 0.10 M None listed None listed
NH3 1M None listed None listed
K2 CrO4 0.10 M 25,36/37/38,43,46,49 None listed
K2 Cr2 O7 0.10 M 45,46,20/21,51/53 53,36/37,45,61
H2 SO4 2.0 M None listed None listed
NaOH 2.0 M None listed None listed
FeCl3 0.10 M 22,38,41 26,39
CoCl2 0.10 M 49,60,68,42/43,51/53 23,36/37,45,61

8
APPARATUS

Hotplate

PROCEDURE

Iron(II)-silver ions system

1. Mix 1 mL each of 0.10 M FeSO4 and 0.10 M AgNO3 in a test tube. Shake thoroughly.

2. Decant the supernate. In separate test tubes, test this supernate for the presence of Fe2+ , Ag+ and
Fe3+ using the following test reagents:

Ion Fe2+ Fe3+ Ag+

Test reagent 0.10 M K3 Fe(CN)6 0.10 M KSCN 1.00 M HCl

Copper(II)-ammonia system

1. Place 1 mL 0.1 M CuSO4 into a test tube. Then, add 5 drops 1.00 M NH3 . Observe what happens.

2. To the mixture in (1), add excess 1.00 M NH3 . Observe what happens.

Chromate-dichromate system

1. Prepare a clean spot plate and label four wells. Place 5 drops of 0.10 M K2 CrO4 into wells 1 and 2,
and 5 drops of 0.10 M K2 Cr2 O7 into wells 3 and 4.

2. Add 2 drops of 2.0 M H2 SO4 into wells 1 and 3.

3. Add 2 drops of 2.0 M NaOH into wells 2 and 4.

4. Observe the colors of the solutions.

Iron(III) chloride-thiocyanate system

1. Prepare a stock solution by adding 2 mL 0.1 M FeCl3 , and 2 mL 0.1 M KSCN to 100 mL distilled
water in a 250-mL beaker. Note: The instructor will assign only one pair to prepare this stock solution
for the whole class.

2. Prepare 4 test tubes (T1,T2,T3,T4). To each of the test tubes, add 2 mL of the stock solution. T1 will
serve as the control.

3. To T2, add 10 drops 0.1 M FeCl3 . To T3, add 10 drops 0.1 M KSCN. To T4, add 3 drops 2.0 M NaOH.

4. Observe the colors of solutions and solids formed, if any.

Cobalt(II) chloride system

1. Prepare two test tubes (T1,T2). T1 serves as the control.

2. To both test tubes, add 1 mL 0.10 M CoCl2 . Note the color of the solution.

3. To T2, add concentrated HCl dropwise until a color change occurs.

9
 4. Immerse T2 in the boiling water bath. Note the color of the solution.

5. Cool T2 by placing the test tube in a water bath containing tap water at ambient temperature. Note
the color of the solution.

6. Place the cooled T2 in an ice bath. Note the color of the solution.

WASTE DISPOSAL

1. Collect all precipitates formed and dispose them in the SOLID WASTE.

2. Dispose all solutions into INORGANIC WASTE.

REFERENCE
Petrucci, R. Herring, F., Madura, J., Bissonnette, C. General Chemistry: Principles and Modern Applications,
10th Ed.;Pearson: Toronto, Canada.

10
EXPERIMENT 4

Spectrophotometric Determination of the Equi-

librium Constant of a Reaction
At the end of the experiment, the student will be able to:
1. quantitatively prepare solutions from solid and liquid reagents;
2. properly operate a single beam UV-Vis spectrophotometer in determining absorbance spectrum and
absorbance of solutions;
3. determine the Keq of a reaction by calculating the concentratiions obtained from absorbance values
via Beer’s Law.

INTRODUCTION
When chemical species react, the reaction proceeds to a state of equilibrium wherein the rates of for-
ward and reverse reactions are equal. In this state, both the concentrations of reactants and products do
not vary with respect to time. The measure of the extent of a reaction reaching equilibrium state at a
certain temperature can be determined by the equilibrium constant, Keq .
In this experiment, the equilibrium constant of the formation of Fe(SCN)2+ complex from Fe3+ and
SCN− ions will be determined.

Fe3+ (aq) + SCN− (aq) *

) Fe(SCN)2+ (aq) (1)
This complexation reaction has an equilibrium constant expression of

[Fe(SCN)2+ ]eq
Keq = (2)
[Fe3+ ]eq [SCN− ]eq
where [X]eq are the concentrations of species X at equilibrium. For any reaction system that is at equilib-
rium, the concentrations of the species involved in such equilibrium will satisfy the condition given by (2).

In calculating for the Keq of reaction (1), the reaction system should be allowed first to attain equilib-
rium such that the equilibrium concentrations of the chemical species involved can be determined. Given
that FeSCN2+ is a blood red complex which absorbs intensely in the visible region of the electromagnetic
radiation, the equilibrium concentration of the said complex can be determined using spectrophotometric
analysis.

Spectrophotometry is a technique involving the measurement of absorbance (A), the amount of light
absorbed by a colored chemical species at a specific wavelength. In this process, an absorbing species se-
lectively attenuates certain frequencies of an incident radiation (Io ); thus, a lower intensity of transmitted
radiation (It ) will pass through the species. In order for absorption to occur, the energy of the incident
radiation must exactly be the same with the energy difference between the ground state and one of the
higher energy states of the absorbing species. The absorbance of such chemical species is defined as:

It
 
A = − log (3)
I0
Absorbance can be related to another measurement of the amount of attenuated radiation called trans-
mittance by A = −logT .

11
 The amount of light absorbed by the chemical species can be used to quantify its concentration in
a given sample by Beer-Lambert Law. This states that the absorbance is directly proportional to the
concentration of the absorbing species and the path length of the absorbing medium.

A = bc (4)
where b is the path length (length traversed by the incident light through the sample), and  is the molar
absorptivity characteristic of the absorbing species.

Beer-Lambert law will only be valid if:

1. The incident light source is monochromatic, that is, it has only a single wavelength.

2. There are no competing reactions which may affect the equilibrium concentration of the absorbing
species.

3. Only dilute sample solutions (< 0.5 M) are used.

The analytical wavelength commonly used is one at which the absorbance of the sample is maximum.
This is usually referred to as λmax .

Spectrophotometric analysis employs the use of either a single- or double-beam UV-vis spectropho-
tometer. A typical single-beam UV-vis spectrophotometer has the following components:

Figure 3: Block diagram of a single beam UV-Vis spectrophotometer

1. Stable source of radiation

2. Wavelength selector is used to isolate the desired wavelength band from the incident radiation.

3. Sample container is commonly known as cell or cuvette. It should be transparent to the wavelength
of interest.

12
 4. Radiation detector / transducer converts radiation power absorbed to a measurable quantity.

5. Signal processor / Readout is an electronic device which amplifies the signal from the radiation
detector.

In using instruments such as the UV-vis spectrophotometer, calibration is necessary in order to estab-
lish the relationship between a response signal and concentration. In order for calibration to be done, a
set of standard solution with reasonable range of known concentrations should be prepared and read its
response signal. Subsequently, a plot of the response signal as a function of concentration, known as the
calibration curve, should be accomplished to determine the equation for the best fit line by using least
squares method (linear regression). In this experiment, a graph of absorbance against concentration is
plotted to obtain a function:

A = mc + k (5)
where m = b is the slope and k is the intercept. Calibration is done to establish functions like (5). By
having a set of standards which has known concentrations (established independently through other
methods), and their absorbances, these data could be fit into the function in (5). Once the parameters m
and b are established, such calibration function can be used to determine unknown concentrations of the
absorbing species for any sample, provided that the same instrument was used, and same conditions are
involved.

In this experiment, equilibrium reaction mixtures based on (1) will be prepared. After equilibration,
spectrophotometry will be used to determine the equilibrium concentrations of the absorbing Fe(SCN)2+
in these mixtures. In turn, the equilibrium concentrations of Fe3+ and SCN− can be determined from their
initial concentrations and reaction stoichiometry. Note that for every 1 mol Fe(SCN)2+ produced, 1 mol
each of Fe3+ and SCN− is consumed. Finally, these equilibrium concentrations can be used in equation
(2) to calculate Keq .

CHEMICALS

Chemical Amount Risk phrases Safety phrases

FeCl3 solid 22-34 25-36/37/39-45
KSCN solid 20/21/22-32-52/53 13-61
HCl 12.1 M 34-37 1/2-26-45

APPARATUS

UV-Vis Double-beam spectrophotometer

Cuvettes (path length: 1 cm)

PROCEDURE

Note: The procedure will be performed independently by 2 big groups.

Preparation of stock solutions

Prepare the following solutions. Note: Use pipettes in obtaining the necessary volumes!

1. 500 mL 0.1 M HCl from concentrated HCl (12.1 M)

13
 2. 50 mL 0.2 M KSCN
Weigh an appropriate amount of solid KSCN in a beaker. Add 20 mL 0.1 M HCl, then stir to dissolve
the crystals. Quantitatively transfer this solution into a 50 mL volumetric flask. Dilute to mark with
0.1 M HCl.

3. 100 mL 0.002 M KSCN

Transfer an appropriate volume of 0.2 M KSCN into a 100 mL volumetric flask. Dilute to mark with
0.1 M HCl.

4. 50 mL 0.2 M FeCl3
Weigh an appropriate amount of solid FeCl3 in a beaker. Add 20 mL 0.1 M HCl, then stir to dissolve
the crystals. Quantitatively transfer this solution into a 50 mL volumetric flask. Dilute to mark with
0.1 M HCl.

5. 100 mL 0.002 M FeCl3

Transfer an appropriate volume of 0.2 M FeCl3 into a 100 mL volumetric flask. Dilute to mark with
0.1 M HCl.

Preparation of standard solutions for calibration

Prepare the solutions in Table 1 by mixing the indicated reagent volumes in 6-inch test tubes. Note:
Prepare the Standard Blank in duplicate.

Table 3: Components of the standard solutions

Solution mL 0.002 M FeCl3 mL 0.20 M KSCN mL 0.10 M HCl
Standard Blank 0 1.00 9.00
S1 0.10 1.00 8.90
S2 0.20 1.00 8.80
S3 0.50 1.00 8.50
S4 1.00 1.00 8.00
S5 2.00 1.00 7.00

Preparation of unknown solutions for measuring equilibrium concentration of Fe(SCN)2+

Prepare the solutions in Table 2 by mixing the indicated reagent volumes in 6-inch test tubes. Note:
Prepare the Unknown Blank in duplicate.

Table 4: Components of the unknown solutions

Solution mL 0.002 M FeCl3 mL 0.002 M KSCN mL 0.10 M HCl
Unknown Blank 0 5.00 5.00
U1 3.00 5.00 2.00
U2 4.00 5.00 1.00
U3 5.00 5.00 0

General technique for loading solutions into the instrument

1. A double-beam spectrophotometer has both reference and sample cells. The reference cell should
always contain the blank against which the sample absorbance will be measured.

2. Handle the cuvettes such that only the opaque sides are touched. Avoid contact with the transparent
sides.

14
 3. Rinse the cuvette three times with distilled water.

4. Rinse the cuvette once with the solution to be loaded into the cuvette. That is, rinse the reference
cell with the blank, and the sample cell with the sample to be analyzed.

5. Fill at least 3/4 of the cuvette with the solution, but NOT to the brim to prevent spills when the
cuvettes are already placed in the instrument.

6. Wipe the surface of the cuvette to ensure that it is dry and nothing obstructs the transparent side.
Also, make sure that the solutions do NOT have suspended particles and bubbles.

7. Place the cuvette in the cell holder such that the light source hits the transparent faces of the cuvette.

Determination of the analytical wavelength

1. Set the Single-beam UV-Vis Spectrophotometer to SPECTRUM MODE.

2. Load the Standard Blank into the cell holder. Perform Baseline Correction.

3. Dispose Standard Blank and load S5 to the cell holder.

4. Scan the absorption spectrum of the solution from 350 nm to 750 nm. From the spectrum, determine
the analytical wavelength, λmax , for the analysis.
Determination of the calibration curve
1. Set the Single-beam UV-Vis Spectrophotometer to PHOTOMETRIC MODE.

2. Set the wavelength of the analysis at λmax .

3. Load the Standard Blank into the cell holder. Perform Auto-zero.

4. Dispose Standard Blank and load S1. Read the absorbance of the solution. Repeat this for solutions
S2 to S5.
Determination of Keq
1. Load Unknown Blank into the reference cuvette. This will be the new blank solution.

2. Read the absorbances at λmax of solutions U1 to U3.

WASTE DISPOSAL
1. Neutralize the HCl solution with a suitable amount of base, then flush the neutralized solution
down the sink with copious amounts of running water.

2. Dispose other chemical wastes to INORGANIC WASTE.

DATA TREATMENT
1. Calibration curve: Plot absorbance measurements of standard solutions as a linear function of
[Fe(SCN)2+ ]. Assume that in preparation of the standards, all Fe3+ was converted to Fe(SCN)2+ .
Report the equation of the line and R2 using y = mx + b where y = A (absorbance), m = slope of
the line = b (molar absorptivity times path length), x = c (concentration of the solution) and b =
y-intercept.
Report the experimental molar absorptivity of Fe(SCN)2+ from the calibration function. Compare
this the literature value for . (CITE YOUR SOURCE)

15
 2. Concentration of unknown solutions

(a) [Fe(SCN)2+ ]: Solve for the equilibrium concentration of Fe(SCN)2+ by substituting the mea-
sured absorbance of the unknown solutions to the previously established calibration function.
(b) [Fe3+ ] and [SCN− ]: Solve for the initial concentrations of Fe3+ and SCN− for each unknown
solutions. From the calculated equilibrium concentration of Fe(SCN)2+ and initial concentra-
tions of Fe3+ and SCN− , solve for the equilibrium concentrations of Fe3+ and SCN− .

3. Equilibrium constant, Keq : Using the equilibrium constant expression, calculate Keq for the 3 un-
known solutions. Report the average of these 3 values as the experimental Keq . Compare this to the
literature vale of Keq (CITE YOUR SOURCE) for this reaction, and calculate percent error.

REFERENCES

1. Skoog, D.A.; West, D.M.; Holler, F.J.; Crouch, S.R. Fundamentals of Analytical Chemistry, 8th ed.;
Brooks/Cole: USA, 2004. pp 710-716

2. Harvey, D.; Analytical Chemistry 2.0; Department of Chemistry and Biochemistry, DePauw Univer-
sity: USA. 2008

3. OConnell, L.; Experiment 16: Spectrophotometric Determination of an Equilibrium Constant;

Boston College: USA, 2016.
http://www.bc.edu/schools/cas/chemistry/academics/undergrad/gen/spring/Equilibrium.pdf (ac-
cessed October 10, 2016)

4. Fossum, C.; Determination of an Equilibrium Constant. In Chem 1B Laboratory Manual; Laney Col-
lege: USA, 2012. http://www.laney.edu/wp/cheli-fossum/files/2012/01/034.pdf (accessed Octo-
ber 10, 2016)

16
EXPERIMENT 5

Determination of Ka of Acetic Acid by pH Mea-

surement
At the end of the experiment, the student will be able to:

1. determine Ka of a weak acid such as acetic acid;

2. operate pH meter properly;

3. employ serial dilution in solution preparation.

INTRODUCTION
The acid dissociation constant, Ka , is an equilibrium constant for the hydrolysis of a weak acid shown
below.
HA(aq) + H2 O(l) * ) H3 O+ (aq) + A− (aq) (1)
For the above reaction, the acid dissociation constant can be expressed as

[H3 O+ ][A− ]
Ka (HA) = (2)
[HA]

Using I-C-E table, Ka can be expressed as shown in Equation 3, where [H 3 O+ ] = x

[H3 O+ ]2
Ka (HA) = (3)
[HA]i
Taking the negative logarithm of both sides of the equation,

pKa p[HA]i
pH = + (4)
2 2

Therefore, by plotting pH against p[HA]i , a line with slope of 0.5 and y-intercept equal to pKa /2 will
be generated.

In this experiment, the Ka of acetic acid will be determined through pH measurement of acetic acid
solutions of varying concentrations.

17
CHEMICALS

10 M CH3 COOH

APPARATUS

pH meter

PROCEDURE

Solution preparation

1. From 10 M stock acetic acid solution, prepare 100.00 mL each of the following acetic acid solutions
through serial dilution: 5.0 M, 1.0 M, 0.5 M, 0.1 M, 0.05 M and 0.01 M.

pH measurements

1. Place 25 mL sample in 50-mL beaker. Just make sure that the pH probe can be submerged completely
in the sample for the reading.

2. Keep the sample covered (use watch glass) until its pH can already be measured.

3. Using a calibrated pH meter, measure the pH of the assigned sample.

Calculations

1. Make a plot of pH versus p[HA]i .

2. From the y-intercept, calculate pKa and Ka of acetic acid.

WASTE DISPOSAL

1. Dilute all resulting solutions with tap water and flush directly down the sink with copious running
water.

REFERENCES

1. Nyasulu, F., Moehring, M., Arthasery, P., Barlag, R. J. Chem. Educ., 2011, 88, 5, 640-642.

18
EXPERIMENT 6

Buffers
At the end of the experiment, the student will be able to:

1. prepare buffer solutions from solid/liquid reagents or partial neutralization;

2. operate pH meter properly;

3. observe buffer action upon addition of strong acid or base.

INTRODUCTION

A buffer is a solution that resists appreciable change in pH upon addition of small amounts of strong
acid or base. It usually consists of solutions containing a weak acid and its conjugate base or a weak base
and its conjugate acid. Both acid and base components should predominate in equilibrium, that is, they
do not neutralize each other appreciably. The ability of a buffer to counteract small additions of acid or
base lies on its two components: a basic component which can neutralize any added acid, and an acidic
component which can neutralize any added base. This property of buffers to resist pH changes is called
buffer capacity.

The Henderson-Hasselbach equation provides the relative amounts of buffer components that can
give a desired pH. Consider a HA-A− buffer system, with Ka as the acid dissociation constant of HA.
Manipulating the Ka expression, the Henderson-Hasselbach equation can be derived as

[A− ]
!
pH = pKa + log (1)
[HA]
A similar derivation from the Kb expression for the pOH of a B-BH+ buffer system gives:
!
[BH+ ]
pOH = pKb + log (2)
[B]
To be suitable for a particular application, a buffer must meet the following requirements:

1. Buffer pH must be within one unit of the pKa of the acidic component. This means that the ratio
of the amounts of the buffer components should be within 10 to 0.1. Buffer capacity is maximum
when buffer pH is equal to pKa which happens when the concentrations of the acidic and basic
components are equal.

2. Buffer components must be appreciably soluble in water.

3. Buffer components should not react with each other.

4. Buffer concentration should be sufficiently high. The higher the concentrations of the buffer com-
ponents, the larger the buffer capacity.

General steps in preparing buffers

1. Choose an appropriate buffer system. The weak acid component should have a pKa closest to the
desired buffer pH to ensure maximum buffer capacity.

19
 2. Apply mass balance. The total buffer concentration, cT , should equal the sum of the concentrations of
the buffer components. Say, for a HA-A− buffer: cT = [HA] + [A− ]. For a buffer with concentration
cT and volume V , the mass balance condition can also be expressed in terms of moles. Say, for a
HA-A− buffer: cT V = mol HA + mol A− .

3. Apply Henderson-Hasselbach equation, as in equations (8) or (9). Since the buffer components occupy
the same solution volume, [A− ]/[HA] = mol A− /mol HA.

4. Steps 2 and 3 will give two equations through which the two unknowns, [HA] and [A− ], or mol HA
and mol A− can be calculated.

5. From step 4, mix the appropriate amounts of reactants (say mass of solid or volume of solution).

6. Read the pH of the buffer using a pH meter. If it deviates from the target pH, add strong acid or
base to adjust the pH to the desired value.

7. Quantitatively transfer the solution to an appropriate volumetric flask. Dilute to the target buffer
volume.

CHEMICALS

0.20 M NaH2 PO4 0.20 M Na2 HPO4 0.10 M NH3

1.0 M HCl 1.0 M NaOH

APPARATUS
pH meter

PROCEDURE

Buffer preparation

1. Each group will be assigned to prepare a 100 mL 0.10 M buffer of a particular pH. The only available
reagents are: 0.20 M NaH2 PO4 , 0.20 M Na2 HPO4 , 1.0 M HCl, 1.0 M NaOH. The group should first
propose to the instructor how they will prepare the buffer, along with the necessary calculations.
Use the following constants for H3 PO4 : pKa,1 = 2.15, pKa,2 = 7.20, pKa,3 = 12.68

2. Prepare the buffer, then measure its pH. If its pH deviates from the target pH, adjust it by using 1.0
M HCl or 1.0 M NaOH.

Observing buffer action

1. Transfer two 25.00 mL portions of 0.10 M NH3 to separate 50-mL beakers. Read its initial pH. To the
first portion, add 0.1 mL 1.0 M HCl twice. Read the pH after every addition of 0.1 mL of the acid.
To the second portion, add 0.1 mL 1.0 M NaOH twice. Read the pH after every addition of 0.1 mL
of the base. Note: Only one group will do this step.

2. Transfer two 25.00 mL portions of the prepared buffer to separate 50-mL beakers. Read the initial
pH. To the first portion, add 0.1 mL 1.0 M HCl twice. Read the pH after every addition of 0.1 mL of
the acid. To the second portion, add 0.1 mL 1.0 M NaOH twice. Read the pH after every addition of
0.1 mL of the base. Note: Each group will do this step for the buffer they prepared themselves.

20
WASTE DISPOSAL
Dilute all resulting solutions with tap water and flush directly down the sink with copious running water.

REFERENCES
Petrucci, R. Herring, F., Madura, J., Bissonnette, C. General Chemistry: Principles and Modern Applications,
10th Ed.;Pearson: Toronto, Canada.

21
EXPERIMENT 7

Solubility Equilibrium of Calcium Hydroxide

At the end of the experiment, the student will be able to:
1. determine the Ksp of calcium hydroxide; and
2. explain the effects of temperature, presence of common and diverse ions, and solvent polarity on
solubility of sparingly soluble salts.

INTRODUCTION
Sparingly soluble salts, when placed in water, are partially dissociated to form its ions, until equilib-
rium is established between the ions and the salt:

) xAy+ (aq) + yBx− (aq)

Ax By (s) * (1)
The equilibrium constant for reactions like (1) is the solubility product constant, Ksp . For Ax By (s):

) xAy+ (aq) + yBx− (aq)

Ax By (s) * (2)

Ksp = [Ay+ ]x [Bx− ]y (3)

Ksp is also related to the molar solubility of the sparingly soluble salt. Molar solubility, (s) is defined
as the number of moles of the salt dissolved to form a liter of saturated solution. By stoichiometry, a
saturated solution of Ax By (s) has:

[Ay+ ] = xs; [Bx− ] = ys (4)

Factors affecting the solubility of salts in aqueous solution include: (1) temperature, (2) presence of com-
mon ions, (3) presence of diverse ions, and (4) change in solvent polarity.

Temperature affects solubility because Ksp , as with all equilibrium constants, varies with temperature,
T , according to the van’t Hoff equation

∆H ∆S
ln K = −
+ (5)
RT R
where ∆H and ∆S are the enthalpy and entropy changes for the reaction, respectively, and R is the gas
constant, 8.314 J K−1 mol−1 .

The effect of diverse ions on solubility is governed by the ionic strength it provides to the reaction
system. Ionic strength, µ, is defined as:
1X 2
µ= ci zi (6)
2 i
where ci is the molarity of ion i, zi is its charge, and the summation is over all ions present in the system.

In this experiment, the solubility equilibrium of calcium hydroxide will be investigated.

) Ca2+ (aq) + 2OH− (aq)

Ca(OH)2 (s) * (7)

22
CHEMICALS

Chemical Amount Risk phrases Safety phrases

HCl 0.10 M 34-37 1/2-26-45
Ca(OH)2 solid 37/28-41 22-26-29
KCl 0.50 M None listed None listed
CaCl2 0.10 M None listed None listed
Ethanol 95% 11 7-9-16-33
Phenolphthalein 1% in ethanol 22-40 36/37-45

APPARATUS

Hot plate and burettes

PROCEDURE

Determination of molar solubility of calcium hydroxide in various conditions

1. Prepare the following media in 250-mL beakers:

A = 50 mL distilled water, room temperature (RT)
B = 50 mL distilled water, heated
C = 50 mL distilled water, in cold water bath
D = 50 mL 0.10 M CaCl2 , RT
E = 50 mL 0.50 M KCl, RT
F = 45 mL distilled water + 5 mL 95 % ethanol, RT
Note: Record the temperatures of the media A, B and C.

2. While stirring vigorously, add Ca(OH)2 solid to each medium until no more solid dissolves. At this
point, the solution is taken to be saturated.

3. Continue stirring for 5 minutes, then leave the suspension for 10 minutes.

4. Filter the suspension. For suspensions prepared in media B and C, make sure that the receiving
flasks are of the same temperature as the suspensions.

5. Draw a 25-mL aliquot of the filtrate and transfer to a 125-mL Erlenmeyer flask. Add 3 drops of 1 %
phenolphthalein. Titrate this with 0.10 M HCl until the phenolphthalein color vanishes to colorless.
Record the titrant volume in mL as Vtit Perform this step for 2 trials for each medium, if possible.

Data treatment

1. From Vtit , calculate the molar solubility, s, of Ca(OH)2 for ALL the media.

2. From s, calculate Ksp for media A, B, and C.

3. Use the calculated Ksp for different temperatures to construct a linear plot based on the van’t Hoff
equation. Report the equation of the line, along with r2 value.

4. Using the function determined in (3), calculate the Ksp at 298 K. Report this as the experimental Ksp .
Compare this to the literature value of Ksp (CITE YOUR SOURCE!) and calculate the % error.

5. Still, using the function in (3), calculate the experimental ∆H and ∆S for the dissolution of calcium
hydroxide. Compare them to the literature values and calculate the % errors.

23
WASTE DISPOSAL

1. Collect excess HCl from the burette and HCl used in rinsing the burette. Use this to dissolve all
Ca(OH)2 precipitate. Dilute the resulting solution with plenty of water and flush directly down the
sink with copious running water.

2. Dilute all titrated solutions with plenty of water and flush directly down the sink with copious
running water.

3. Dispose the used filter paper into the SOLID WASTE container.

REFERENCE

1. Petrucci, R. Herring, F., Madura, J., Bissonnette, C. General Chemistry: Principles and Modern Applica-
tions, 10th Ed.;Pearson: Toronto, Canada.

2. Euler, W., Kirschenbaum, L., Ruekberg, B. J. Chem. Educ., 2000, 77, 8, 1039.

24
EXPERIMENT 8

Separation of Anions by Selective Precipitation

and Other Reactions
After this experiment, the student will be able to:

1. selectively separate anions based on their Ksp and reactivity;

2. demonstrate centrifugation, precipitation and complexation as methods of separation.

INTRODUCTION
Most samples collected for analysis contain ions that are not the ones of interest. These ions may inter-
fere with the analysis hence they should be removed from the solution. One way of separating ions is by
selective precipitation. Selective precipitation exploits the difference in solubilities of salts in water and
other common solvents in chemistry. Some ions can be precipitated with a certain precipitating agent that
does not precipitate the other ions that are also present in the solution. The solids formed can easily be
separated through centrifugation and decantation. The solids can be further separated using acid-base,
complex formation, or redox reactions.

CHEMICALS

Test solutions (0.10 M)

NaCl NaBr NaI NaNO3
Na2 CO3 NaCH3 COO Na2 C2 O4 Na2 SO4
Na2 CrO4 Na3 PO4

Test reagents
0.10 M BaCl2 0.10 M AgNO3 3.0 M HNO3 6.0 M NH3
0.10 M CaCl2 3.0 M CH3 COOH 6.0 M H2 SO4 concentrated NH3

Chemical Concentration Risk phrases Safety phrases

Na2 CrO4 0.10 M 45,60,61,46,26,25,48/23,34,21,42/43,50,53 None listed
Concentrated NH3 13 M 34,50 1/2,16,36/37/39,45,61

APPARATUS

Centrifuge

PROCEDURE

Precipitation by BaCl2

1. Place 10 drops of each test solution in separate 4-inch tubes. Dilute each solution with 10 drops of
distilled water.

2. To each, add 5 drops of 0.10 M BaCl2 and shake thoroughly. Take note of the test solutions which
produced precipitate. Take note of the color of the precipitates.

25
 3. Discard solutions that did not give a precipitate with BaCl2 . For those with precipitate, centrifuge,
then decant the supernate.

4. To the precipitate, add 10 drops of 3.0 M CH3 COOH. Take note of the precipitate which dissolved
and other observations.

Precipitation by CaCl2
Note: Perform this only for test solutions that precipitated with BaCl2 .

1. Place 10 drops of each test solution in separate 4-inch tubes. Dilute each solution with 10 drops of
distilled water.

2. To each, add 5 drops of 0.10 M CaCl2 and shake thoroughly. Take note of the test solutions which
produced precipitate. Take note of the color of the precipitates.

3. If precipitate formed in the test solution, centrifuge then decant. To the precipitate, add 10 drops of
3.0 M CH3 COOH. Take note of the precipitates which dissolved and other observations.

4. If precipitate DID NOT FORM in the test solution, add 10 drops of 3.0 M HNO3 followed by 5 drops
0.10 M BaCl2 . Record observations.

Precipitation by AgNO3
Note: Perform this only for test solutions that DID NOT PRECIPITATE with BaCl2 .

1. Place 10 drops of each test solution in separate 4-inch tubes. Dilute each solution with 10 drops of
distilled water.

2. To each, add 5 drops of 0.10 M AgNO3 and shake thoroughly. Take note of the test solutions which
produced precipitate. Take note of the color of the precipitates.

3. If a precipitate forms, centrifuge the solution, then decant the supernate.

4. To the precipitate, add 20 drops 6.0 M NH3 . If precipitate dissolves, record observations and stop
the analysis for that test solution. Otherwise, proceed to the next step.

5. Centrifuge the mixture, then decant the supernate. To the undissolved precipitate, add concentrated
NH3 . Record observations.

Reaction with H2 SO4

Note: Perform this only for test solutions that DID NOT PRECIPITATE with both BaCl2 and AgNO3 .

1. Place 10 drops of each test solution in separate 4-inch tubes. Dilute each solution with 10 drops of
distilled water.

2. Add 5 drops 6.0 M H2 SO4 . Heat the solutions in a water bath. Record the smell of the solution.

WASTE DISPOSAL
1. All solutions containing H2 SO4 and HNO3 should be disposed of in the ACID WASTE container
except those containing chromate/dichromate.

2. All other solutions should be disposed in the INORGANIC WASTE.

26
REFERENCES

1. Petrucci, R. Herring, F., Madura, J., Bissonnette, C. General Chemistry: Principles and Modern Applica-
tions, 10th Ed.;Pearson: Toronto, Canada.

27
EXPERIMENT 9

Coordination Chemistry
At the end of the experiment, the student will be able to:

1. illustrate the effect of Le Chatelier’s Principle in complexation reactions;

2. illustrate how complexes change colors by varying ligands;

3. assess the strength of ligands based on the complex’s color;

4. illustrate amphoterism of metal hydroxides.

INTRODUCTION
One of the more interesting properties of transition metals that separate them from main group metals
is their ability to form coordination compounds. This property makes them essential components of some
products such as paints, inks, and medicine.

Energy is inversely proportional to wavelength; therefore, the color which has the highest energy
and thus, has the smallest wavelength, is violet while the color which has the lowest energy and has the
longest wavelength is red. When a substance absorbs light of one or more wavelengths in the visible
region, it transmits light with the wavelength of the complementary color, e.g. a substance that appears
red absorbs green color. This is the reason for the variety of colors displayed by different substances.

By definition, coordination compounds are formed when a metal atom or ion, and a molecule with
one or more unshared electron pairs, called a ligand, interact. One theory that can explain the various
colors of coordination complexes is the crystal field theory or CFT. In a metal ion surrounded by ligands,
the d orbitals are at different energy levels compared to when they are in an isolated metal ion. The effect
of the crystal field on the d orbitals vary depending on which direction the ligands approach the metal
ion. CFT proposes that the degeneracy (degenerate means they have the same energy) of the d orbitals
is removed when electrons on the ligands repel electrons on the metal ion d orbitals. For an octahedral
complex, this leads to splitting of the orbitals into two sets, the higher energy set (dx2 −y2 and dz 2 orbitals)
and the lower energy set (dxy, dxz, and dyz orbitals). For tetrahedral complexes, the order is reversed.
Between the two sets is an energy separation called the crystal field splitting energy (CFSE or ∆). In
octahedral complexes, ∆ is proportional to the crystal field strength of the ligands interacting with the
metal ion. That is, the stronger the ligand field strength, the greater the ligand electrons repel the metal
ion electrons and the larger the CFSE.

Coordination compounds appear colored because the magnitude of the orbital splitting energy matches
the energy of photons of visible light. Light is absorbed by the sample and electrons on the lower energy
d orbitals are promoted to a higher energy state. This transition is called a d-d transition and is one of
the reasons why transition metal complexes are colored. Other explanations regarding the color of some
complexes such as charge transfer and spin-forbidden transitions will not be discussed since they are be-
yond the scope of the course.

For coordination compounds therefore, the greater the field strength of the ligand, the larger the split-
ting energy, and the shorter the wavelength absorbed by the compound. As a rough generalization,
changing the ligand also changes the color of the coordination compound. Ligands can be arranged in
order of increasing field strength in what is called the spectrochemical series. A ligand with a high field

28
strength is called a strong-field ligand and forms low-spin complexes. On the other hand, a ligand with a low
field strength is called a weak-field ligand and generally forms high-spin complexes.

CHEMICALS

Chemical Amount Risk phrases Safety phrases

Ni(NO3 )2 0.10 M 49-61-20/22-38-41-42/43-48/23-50/53-68-8 53-45-60-61
Zn(NO3 )2 0.10 M 8-22-38 17-26
NaOH 6.0 M 35 1/2-37/39-26-45
NH3 6.0 M 36/37/38 24/25-26-46
Ethylendiamine, en 10-21/22-34-42/43 23-26-36/37/39-45

PROCEDURE

Nickel(II) complexes

1. Place 10 drops of 0.1 M Ni(NO3 )2 in three separate test tubes.

2. To the first test tube, add 20 drops of ligand solution X.

3. To the second test tube, add 20 drops of ligand solution Y.

4. To the third test tube, add 20 drops of ligand solution Z.

5. Observe the color of resulting solutions. The ligands used in this part are: (a) water, (b) NH3 and (c)
ethylenediamine. Match these ligands with the identities of X, Y, and Z.

Zinc complexes

1. Place 10 drops of 0.1 M Zn(NO3 )2 in two separate test tubes.

2. To the first test tube, add 6.0 M NaOH until precipitate formed completely dissolves.

3. To the second test tube, add 6.0 M NH3 until precipitate formed completely dissolves.

4. Observe the color of resulting solutions.

Qualitative tests for cations

1. Cr3+ . To 10 drops of 0.1 M Cr3+ , add 20 drops 6.0 M NaOH. Add 3% H2 O2 until the color of the
solution changes. Observe color of the resulting solution.

2. Co2+ . Acidify 10 drops of a 0.1 M Co2+ using 20 drops 6.0 M CH3 COOH. Add a pinch of solid
NaNO2 and place in a warm water bath. Observe the color of the solution.

3. Ni2+ . Add dimethylglyoxime dropwise to 10 drops 0.1 M Ni2+ . Record observations.

WASTE DISPOSAL
Dispose all solutions in the INORGANIC WASTE container.

REFERENCES

1. Petrucci, R. Herring, F., Madura, J., Bissonnette, C. General Chemistry: Principles and Modern Applica-
tions, 10th Ed.;Pearson: Toronto, Canada.

29
EXPERIMENT 10

Synthesis of a Thermochromic Material

At the end of the experiment, the student will be able to:

1. synthesize a thermochromic complex;

2. account whether the material demonstrates reversible thermochromism.

INTRODUCTION
Thermochromic substances are a class of materials that change color with respect to a change in tem-
perature. This is most often due to transitions in crystalline phase, change in geometry, or a change in
number of ligands in the coordination sphere. Thermochromic materials can be applied in heat sensors.
In this experiment, the coordination compound [(CH3 CH2 )2 NH2]2 [CuCl4 ] will be synthesized in a non-
aqueous media. Crystals will be collected using suction filtration. This techniques increases the speed of
the filtration process without compensating the thickness of the filter medium.

CHEMICALS

Chemical Concentration Risk phrases Safety phrases

CuCl2 solid 21/22,38,41,50 None listed
Diethylamine HCl solid 36/37/38 None listed
Absolute ethanol 11 7,16,26,33,23,36/37
Isopropyl alcohol 11,36,67 None listed

APPARATUS

Magnetic stirrer Suction flask Buchner funnel Microtest tube

PROCEDURE

1. In two separate dry beakers, weigh 0.70 g CuCl2 and 1.10 g diethylamine HCl.

2. Add 2 mL absolute ethanol to the beaker containing CuCl2 .

3. Add 6 mL isopropyl alcohol to the beaker containing diethylamine HCl.

4. Place a stir bar in the beaker containing diethylamine HCl and heat the solution to about 40◦ C, while
stirring until the solid completely dissolves.

5. Then, add the solution containing CuCl2 dropwise to the diethylamine HCl while continuously
stirring the solution.

6. Heat the solution, while stirring, until about only 4.0 mL solvent is left in the beaker.
Note: Steps 3 to 6 should be done in fume hood!

7. Remove the spin bar. Place the beaker in an ice bath for crystallization. Scratch the wall of the
container to invoke crystallization.

8. Add 6 mL ice cold isopropyl alcohol. Then, break up the solids formed.

30
 9. Collect the product using suction filtration. Dry the crystals in the fume hood.

10. Place the crystalline product in a micro test tube. Seal it using a foil or stopper.

11. Fix the microtest tube with thermometer and immerse in water bath.

12. Heat the water bath until the color of compound changes. Record the temperature at which the
color change is observed.

13. Remove the microtest tube in hot water bath, and place it in a cooler water bath. Then, immerse it
again in the hot water bath. Verify if the thermochromism is reversible.

WASTE DISPOSAL
Dispose the filtrate into the INORGANIC WASTE. Submit the microtest tube containing the synthesized
material to the instructor.

REFERENCES

1. Choi, S., Larrabee, J. J. Chem. Educ., 1989, 66, 9, 774.

31
EXPERIMENT 11

Electrochemistry
After this experiment, the student will be able to:

1. perform and assess spontaneity of redox reactions;

2. set-up electrochemical cells and demonstrate how these work;

3. calculate cell potentials using Nernst equation.

INTRODUCTION
An oxidation-reduction or redox reaction occurs if the reactants undergo a change in oxidation num-
ber. Oxidation involves an increase in the oxidation number resulting from loss of electrons. Reduction,
on the other hand, is described by a decrease in the oxidation number, a process resulting from gaining
electrons. Oxidizing agents are substances that cause oxidation of other substances. They themselves are
reduced and gain electrons. Typical oxidizing agents include metal ions, free nonmetals and oxycom-
pounds. Reducing agents are substances that cause reduction of other substances. They themselves are
oxidized and lose electrons. Typical reducing agents include metals, metal ions in low oxidation states,
nonmetal ions and molecules or ions containing an element in low oxidation state combined with oxy-
gen. The ability of substances as reducing or oxidizing agents is governed by their standard reduction
◦ . In general, the more positive the E ◦ accessible to a substance, the better suited it is as
potential, Ered red
an oxidizing agent, that is, it is more readily reduced.

Study on numerous redox reactions gave rise to electrochemistry. Electrochemistry involves chemical
reactions that can produce electricity as well as chemical changes driven by applied electric current. For
instance, when a piece of Zn metal is dropped into a CuSO4 solution, part of the Zn metal dissolves, and
Cu metal deposits on the undissolved Zn:

Zn(s) + Cu2+ (aq) → Cu(s) + Zn2+ (aq) (1)

In a mixed system, there is direct transfer of electrons from the Zn atom to the Cu2+ ion but the
work done by the system is not harnessed. However, if contact between the oxidizing agent (Cu2+ ) and
the reducing agent (Zn) is confined to a wire connection, then electron transfer is converted to useful
electrical work which is equivalent to the ∆G of the reaction. The device used for this purpose is called
a galvanic or voltaic cell. In this cell, a spontaneous chemical reaction occurs, yielding a positive cell
potential, Ecell . A common galvanic cell is the Daniel cell shown below:

32
 Figure 4: A simple galvanic cell

Oxidation on the Zn surface yields electrons that flow to the Cu surface where reduction occurs. The
direction of the electron flow indicates that the Zn electrodes polarity is negative (-) whereas that of the
Cu electrode is positive (+).

The Nernst equation gives the dependence of the cell potential, Ecell , on the concentrations of the
species involved and temperature:

◦ RT
Ecell = Ecell − log Q (2)
nF
where R is the gas constant (8.314 J K−1 mol−1 ), T is the absolute temperature in K, n is the moles of
electrons transferred, F is the Faraday’s constant (96485 C mol−1 ), Ecell ◦ is the standard cell potential, and
◦
Q is the reaction quotient for the cell reaction. Ecell is the potential of the cell if all of its components are in
standard-state (all aqueous species have 1 M concentration). The standard cell potential is characteristic
of the cell reaction and is given by E ◦ = E◦ − E◦ , where E ◦ and E ◦ are the
cell cathode anode cathode anode
standard reduction potentials of the cathode and anode half-reaction, respectively. Standard reduction
potentials are usually reported in the literature.

The cell potential is a measure of the tendency of a cell reaction to occur. If Ecell is positive, the for-
ward reaction is spontaneous. If Ecell is negative, the reverse reaction is spontaneous. If it is zero, the the
system is at equilibrium. As the cell reaction proceeds, the potential falls until it reaches equilibrium.

Electrolysis is the process by which nonspontaneous reactions are forced to take place by applying
potential from an external source. An electrolytic cell consists of a container for the reaction mixture
wherein electrodes are immersed and connected to a source of direct current. Faraday’s law states that the
amount of substance that undergoes oxidation or reduction at each electrode during electrolysis is directly propor-
tional to the total charge that passes through the cell. Say, consider the electrolysis of KX to generate aqueous
halogen X2 : 2X− → X2 (aq) + 2e− . The moles of the halogen produced via electrolysis can be calculated
using the equation below which is based on Faradays Law:

It 1 mol X2
 
mol X2 = (3)
F 2 mol e−

33
where I is the average current in amperes, t is the duration of electrolysis in seconds, and F is Faradays
constant. The term, It, gives the total charge applied to the electrolytic cell, and F serves as a factor that
converts this total charge into the equivalent moles of electrons that would give such total charge.

CHEMICALS
0.10 M KMnO4 3.0 M H2 SO4 1.0 M Na2 SO3 6.0 M NaOH
0.10 M FeCl3 0.10 M KSCN Zn dust MnO2 solid H2 O2
0.10 M CuSO4 0.20 M FeSO4 0.20 M FeCl3 0.10 M ZnSO4 0.10 M KCl
0.10 M KBr 0.10 M KI Cu wire Zn metal

APPARATUS

Multimeter

PROCEDURE

A. Redox Reactions

Reaction between sulfite and permanganate

1. Add 2 drops of 0.10 M KMnO4 to 1.0 ml of 0.1 M Na2 SO3 in test tube A.
2. In test tube B, acidify 1.0 ml of 0.1 M Na2 SO3 with 3.0 M H2 SO4 . Then add 2 drops of 0.1 M KMnO4 .
3. In test tube C, repeat step 2 using 6.0 M NaOH instead of 3.0 M H2 SO4 .
Reaction between ferric ion and thiocyanate with zinc
1. Add 5 drops of 0.1 M KSCN to 10 drops of 0.1 M FeCl3 solution in test tube D. Take note of the color
of the complex formed.
2. Repeat step 1 for test tube E but this time, add Zn dust gradually and in small amounts until a
visible change occurs.
Catalytic decomposition of hydrogen peroxide
1. Add 20 mL of hydrogen peroxide and small amount of liquid detergent into a 100-mL graduated
cylinder.
2. Add one (1) spatula-full of Manganese (IV) oxide (MnO2 ) to the graduated cylinder. Observe what
will happen.

B. Electrochemical Cells

Constructing the galvanic cells

1. Each group will be assigned a galvanic cell to prepare. Refer to the Worksheet for the cell notations.
2. To prepare the cells containing X2 , a solution of KX must first be electrolyzed. Prepare 30 mL of KX
solution.
3. Attach alligator clips to the leads of the multimeter. Attach a graphite electrode to the alligator
clip connected to the red wire lead. Connect the negative end of the battery to the black wire lead.
Attach the positive end of the battery to another alligator clip. Attach a graphite electrode to the
other end of this alligator clip.

34
 4. Turn on the multimeter and set to ammeter mode.

5. Dip these electrodes into the KX solution for 3.0 min. Using the ammeter, measure the average
current passing through the cell during the course of electrolysis.

6. Disconnect the electrolysis cell. This will now serve as the half-cell for the galvanic cells involving
X2 .

7. To prepare the half-cell containing Cu(NH3 )2+

4 , just mix 10 mL 0.1 M CuSO4 with 20 mL 1.0 M NH3 .

8. DO NOT FORGET TO INCLUDE SALT BRIDGES. Prepare the salt bridge by immersing paper fans
from filter paper in the electrolyte solution provided by the instructor.

Measuring Ecell

1. Turn on the multimeter. Set to voltmeter mode.

2. Connect the red wire lead (plugged into VΩ) to the cathode. Connect the black wire lead (plugged
into COMM) to the anode.

3. Obtain the first, stable reading of Ecell . Report this as the experimental value.
◦
4. Compare this to the theoretical Ecell calculated through the Nernst equation and literature Ered
values. Also, compute the % error. Use the reported values in the Appendix of Petrucci, 10th Ed,
for calculations of theoretical Ecell .

WASTE DISPOSAL

1. Collect all solutions containing permanganate and dispose into the container provided by the in-
structor. Also, collect all MnO2 solid and submit to the instructor for disposal. All other solutions
should be disposed in INORGANIC WASTE.

2. All solutions should be disposed of into INORGANIC WASTE. All contaminated solid waste (salt
bridge, graphite electrode) should be disposed of into SOLID WASTE.

REFERENCES

1. Petrucci, R. Herring, F., Madura, J., Bissonnette, C. General Chemistry: Principles and Modern Applica-
tions, 10th Ed.;Pearson: Toronto, Canada.

2. Gerken, M., Chemistry 2810 Lecture Notes. Retrieved from:

http://classes.uleth.ca/200501/chem2810a/lecture20.pdf

3. Decomposition of Hydrogen Peroxide. Retrieved from: http://infohost.nmt.edu/HydrogenPeroxide.pdf

35