Chemistry 2C

Laboratory Manual






Department of Chemistry
University of California - Davis
Davis, CA 95616



Fall 2012
Student Name ______________________ Locker Number____________



Laboratory Information

Teaching Assistant's Name _______________________

Laboratory Section Number _______________________

Laboratory Room Number _______________________

Dispensary Room Number 1060 Sciences Lab Building




Location of Safety Equipment Nearest to Your Laboratory

Safety Shower _______________________

Eye Wash Fountain _______________________

Fire Extinguisher _______________________

Fire Alarm _______________________

Safety Chemicals _______________________

i
TABLE OF CONTENTS

PREFACE ................................................................................................................................... ii
ACKNOWLEDGMENTS ........................................................................................................... iii
INTRODUCTION ....................................................................................................................... iv
A) Time Allocation and Grading of the Experiments ................................................... iv
B) Safety Policy ............................................................................................................ v

EXPERIMENTS:
Redox Titrations .......................................................................................................................... 1
Nomenclature of Transition Metal Complexes ........................................................................... 9
Electrochemical Cells .................................................................................................................. 11
EDTA Titrations .......................................................................................................................... 23
Introduction to Inorganic Qualitative Analysis ........................................................................... 31
Synthesis of a Transition Metal Coordination Complex ............................................................. 39
A Spectroscopy Study ................................................................................................................. 47
A Kinetics Study ......................................................................................................................... 67
Determination of Vitamin C Content Via a Redox Titration........................................................75

APPENDIX:
A) General Experimental Guidelines ............................................................................ A-1
1. Pre-Laboratory Preparation .......................................................................... A-1
2. Data Collection ............................................................................................. A-1
3. Unknowns ..................................................................................................... A-1
4. Writing A Laboratory Report ....................................................................... A-1
5. Statistical Treatment of Data ........................................................................ A-2
B) On-line Pre- & Post-Laboratory Procedures ............................................................ A-5
C) Late Reports & Make-Up Policy .............................................................................. A-12
D) Common Laboratory Procedures ............................................................................. A-13
E) Maps ......................................................................................................................... A-21
F) Dispensary Procedures .............................................................................................. A-23
1. Dispensing Policies.........................................................................................A-23
2. Waste Labels ................................................................................................. A-25
3. :Locker Inventory ......................................................................................... A-27


ii
PREFACE

Chemistry is an experimental science. Thus, it is important that students of chemistry do
experiments in the laboratory to more fully understand that the theories they study in
lecture and in their textbook are developed from the critical evaluation of experimental
data. The laboratory can also aid the student in the study of the science by clearly
illustrating the principles and concepts involved. Finally, laboratory experimentation
allows students the opportunity to develop techniques and other manipulative skills that
students of science must master.

The faculty of the Chemistry Department at UC Davis clearly understands the importance
of laboratory work in the study of chemistry. The Department is committed to this
component of your education and hopes that you will take full advantage of this
opportunity to explore the science of chemistry.

A unique aspect of this laboratory program is that a concerted effort has been made to use
environmentally less toxic or non-toxic materials in these experiments. This was not only
done to protect students but also to lessen the impact of this program upon the
environment. This commitment to the environment has presented an enormous
challenge, as many traditional experiments could not be used due to the negative impact
of the chemicals involved. Some experiments are completely environmentally safe and
in these the products can be disposed of by placing solids in the wastebasket and
solutions down the drain. Others contain a very limited amount of hazardous waste and
in these cases the waste must be collected in the proper container for treatment and
disposal. The Department is committed to the further development of environmentally
safe experiments which still clearly illustrate the important principles and techniques.

The sequence of experiments in this Laboratory Manual is designed to follow the lecture
curriculum. However, instructors will sometimes vary the order of material covered in
lecture and thus certain experiments may come before the concepts illustrated are covered
in lecture or after the material has been covered. Some instructors strongly feel that the
lecture should lead the laboratory while other instructors just as strongly believe that the
laboratory experiments should lead the lecture, and still a third group feel that they
should be done concurrently. While there is no "best" way, it is important that you
carefully prepare for each experiment by reading the related text material before coming
to the laboratory. In this way you can maximize the laboratory experience.

Questions are presented throughout each experiment. It is important that you try to
answer each question as it appears in the manual, as it will help you understand the
experiment as you do it. In addition, you are encouraged to complete the report as soon
after laboratory as possible, as this is much more efficient than waiting until the night
before it is due.

In conclusion, we view this manual as one of continual modification and improvement.
Over the past few years many improvements have come from student comments and
criticisms. We encourage you to discuss ideas for improvements or suggestions for new
experiments with your TA. Finally, we hope you find this laboratory manual helpful in
your study of chemistry.


iii
ACKNOWLEDGMENTS

This manual is the culmination of the efforts of many individuals. Many faculty
members have provided ideas for the creation of these laboratories and have made
numerous suggestions regarding their implementation. Stockroom Dispensary
Supervisors, both past and present, have had a role in helping to develop these
experiments and, in particular, helping to ensure that the experiments are tailored to our
laboratories here at UC Davis. In addition, many undergraduates have been involved in
the development of experiments as part of undergraduate research projects.







































iv
INTRODUCTION

A) Time Allocation of the Experiments
Below is an indication of the time allocation of each experiment. At the end of the
quarter, the students TA will sum the scores and give this to the instructor, who will
modify it as described in the course syllabus.

Title of Experiment Lab Periods
Allocated
Redox Titrations 1
Nomenclature N/A
Electrochemical Cells 1
EDTA Titrations 1
Qualitati ve Analysis 2
Syntheses of TM
Compounds
1
Spectroscopy 1
Kinetics 1
Vitamin C 1
On-Line Prelab Quizzes (seven)
Lab Notebooks - Pre-lab (eight)


*On Line Pre-laboratory Quizzes: Each 2 point pre-lab quiz must be completed at least 1 hour prior to attending the
students scheduled lab class. All three quiz questions must be answered correctly before the student will be allowed to
perform the laboratory experiment. If the quiz is failed on the first attempt, the student may take the quiz a second
time. Because the questions are chosen randomly, different questions may be generated on the second attempt.
Students who fail these quizzes are considered unprepared and unsafe to work in the laboratory and will not be allowed
to begin the laboratory procedure until the TA is convinced the student is prepared. The TA will check the pre-
laboratory write-up and quiz the student. The TA will allow entry into the laboratory only if the student answers the
questions correctly and the pre-laboratory write-up is complete. This policy will be strictly enforced.


B) Safety Policy
It is critical that you prepare for each experiment by reading it carefully before entering
the laboratory. Not only will this ensure that you get the maximum benefit of the
experience, but it also makes for a safer environment in the laboratory. This is important
not only for your own safety but also for those around you. A number of policies have
been developed in order to make sure that the laboratory is safe and that it runs smoothly.

In each experiment specific hazards are indicated by bold type and procedures are
described that must be adhered to. Accidents commonly occur when the following rules,
as approved by the Chemistry Department Safety Committee, are not followed.

Safety Rules for Laboratory Work
The following rules are designed for your safety in the laboratory. The Laboratory
Instructor (LI = TA, Laboratory Supervisor, and/or Course Instructor) is required to
enforce these rules and has the full backing of the Department of Chemistry Staff and
Faculty. The LI is also required to enforce all laboratory experiment-specific safety
procedures in carrying out the laboratory work. Violations of these rules will result in
expulsion from the laboratory.
1. No one is allowed in the laboratory without the supervision of a LI. No laboratory
work will be done without supervision. Perform only authorized experiments, and
only in the manner instructed. DO NOT alter experimental procedures, except as
instructed.
2. Approved safety goggles must be worn by all persons at all times. At NO TIME are
safety glasses of any kind acceptable in the laboratory. Goggles must be worn by
EVERY person in the lab until EVERYONE has finished with the experimental procedure
and has put away ALL glassware. Safety goggles may not be modified in any manner.
3. Closed-toe, closed-heel shoes must be worn at all times.
4. Clothing (baggy sleeves and pant legs are NOT allowed) that completely covers your
arms and legs must be worn at all times in the laboratory (long skirts, tights, or
leggings do NOT qualify). inadequate protection often leads to injury. Avoid wearing
expensive clothing to lab as it may get damaged.
5. Absolutely NO food or drinks are allowed in the laboratory. This prohibition applies
to the storage of food and the consumption of food, beverages, medicines, tobacco,
and chewing gum. Contact lenses and cosmetics are not to be applied while in the
laboratory. Infractions will result in expulsion from the laboratory. Because cell
phones or other personal electronic media can easily be damaged in the laboratory,
use of such devices is at the students own risk.
6. Learn the location and how to operate the nearest eyewash fountain, safety shower,
fire extinguisher, and fire alarm box. First aid for acid or base in the eyes is to wash
with copious amounts of water using the eyewash fountain for 15 minutes; then go
immediately to the Student Health Center for further treatment. First aid for acid or
base on skin or clothing is to wash thoroughly with water for 15 minutes. Use the
emergency shower if appropriate, removing contaminated clothing for thorough
washing. If the safety shower or eyewash is activated, the exposed person must be
accompanied to the Student Health Center for further evaluation.
7. All operations in which noxious or poisonous gases or vapors are used or produced


must be carried out in the fume hood.
8. Confine long hair while in the laboratory. Hair can catch on fire while using open
flames.
9. Mouth suction must never be used to fill pipets. Always use a bulb to fill pipets.
10. All accidents, injuries, explosions, or fires must be reported at once to the LI. In case
of serious injury, the LI or Lab Supervisor must call 911 for an ambulance. In cases
where the LI and Lab Supervisor decide the extent of an injury warrants
evaluation/treatment, the student must be accompanied to the Student Health Center.
Students are also encouraged to seek medical attention if the student deems it
necessary. The student must always be accompanied to the Student Health Center.
11. Horseplay and carelessness are not permitted and are cause for expulsion from the
laboratory. You are responsible for everyone's safety.
12. Keep your working area clean immediately clean up ALL spills or broken glassware.
Exercise appropriate care to protect yourself from skin contact with all substances in
the laboratory. Clean off your lab workbench before leaving the laboratory.
Skateboards, rollerblades, and other such personal equipment must be stored outside
of the laboratory. Personal electronics are only permitted when needed for the
laboratory.
13. Put all toxic or flammable waste into the appropriate waste container(s) provided in
your laboratory.
14. Containers of chemicals may not be taken out of the laboratory except to the
dispensary for refill/replacement or to exchange full waste jugs for empty ones. All
containers must be CAPPED before you take them into the hallway to the dispensary.
Never take uncapped glassware containing chemicals into the hallways or other
public areas.
15. Laboratory doors must remain closed except when individuals are actively entering or
exiting the lab. DO NOT prop the door open with chairs, stools, or any other objects.
16. The student must have at least ONE UNGLOVED HAND when outside the laboratory.
Only use the ungloved hand to open doors. Gloves are presumed to be contaminated
and must not come into contact with anything outside the laboratory except chemical
containers.
17. Specific permission from your LI is required before you may work in any laboratory
other than the one to which you have been assigned. Only laboratory rooms where the
same laboratory course is operating may be used for this purpose.
18. If you have a special health condition (asthma, pregnancy, etc.) or any personal health
concerns, consult your doctor before taking chemistry lab.
19. If you come to the laboratory with non-compliant goggles, shoes, or clothing, you
will not be allowed to work in the laboratory. In that context, note that THERE ARE NO
MAKE-UP LABORATORIES. Your course grade will be significantly lowered or you may
fail the course if you do not meet the dress code.
You must sign the Safety Acknowledgement sheet before you may work in the lab. If
you have questions about these rules and procedures, please ask your LI before
starting any laboratory work in this course.














EXPERIMENTS





1

Redox Titrations

INTRODUCTION

In this experiment you are going to use a pair of oxidation-reduction reactions to
determine the concentration of a bleach unknown. First, you are going to standardize a
freshly prepared solution of sodium thiosulfate (Na
2
S
2
O
3
). You will do this by reacting
iodate (IO
3
-
) with excess iodide (I
-
) in acidic solution to produce a known quantity of
iodine and water. The iodine produced will be titrated with a sodium thiosulfate solution.
The products of the reaction between iodine and thiosulfate are the iodide ion and the
tetrathionate ion (S
4
O
6
2-
). By using a known amount of iodate and stoichiometric
calculations you are able to calculate the exact concentration of the thiosulfate solution
you have prepared.

In the second part of the experiment you will use your standardized thiosulfate solution to
analyze a bleach unknown. Bleach contains sodium hypochlorite (NaClO) that reacts
with iodide to produce iodine, chloride ion, and water. The amount of iodine produced
can then be determined by titration with your standard sodium thiosulfate.

As prelaboratory preparation, you should read sections the Redox sections in your text.
Redox reactions are much more complicated than simple acid/base reactions. You should
balance all the reactions described in this experiment before coming to the laboratory.


2
Safety: Wear gloves when handling bleach. Wear your goggles.

PROCEDURE

Work in Pairs on this experiment.

Part I. Standardization of Sodium Thiosulfate Solution

Plan out a titration procedure for the standardization of a sodium thiosulfate solution.
The following chemicals will be provided for you in the lab:

Solid potassium iodate (Must be dried in oven)
Solid potassium iodide
3 M sulfuric acid
1 M sodium thiosulfate
3% ammonium molybdate solution (This is a catalyst.)
Starch solution (This is the indicator you will use)
Bleach unknown

Do not contaminate the chemicals. The solutions in the reagent bottles should be
colorless. If they are brown they have been contaminated and should be returned to the
dispensary. The most common source of contamination is due to leaving caps off the
chemical bottles and using the same disposable pipet for more than one chemical. Be
vigilant! Do not be the person in your lab room that causes these problems!

Below is a rough outline of the titration procedure; you should elaborate and provide
further details such as the amounts used of each reagent in your laboratory report. The
outline of the procedure also contains some important information that will assist you in
performing an effective titration.

1. Preparation of the potassium iodate solution.

You should dilute the sodium thiosulfate solution to approximately 0.05 M.
This will give you reasonable volumes for your titrations. Plan on making about
300 mL of the sodium thiosulfate solution.

2. Preparation of the iodine solution.

Prepare 250 mL solution of potassium iodate (approximately 0.01 M), and
transfer a measured amount of this solution into the titration flasks. Prepare the
solution in a 250 mL volumetric flask and share the solution between you.

Calculate the final molarity of the potassium iodate to three significant figures.
Be sure to use volumetric glassware to transfer this iodate solution into your
titration flask

This method will speed up your titrations in two ways. You will spend far less
time at the balance, and potassium iodate takes a few minutes to dissolve so you
only have to wait once instead of several times.

3

Since you know very precise information about your iodate solution, make
iodate your limiting reagent. If you do your reactions with about 20 mL of iodate
solution you will need about two grams of potassium iodide and a few milliliters
of the 3 M sulfuric acid. Use your 10.00 mL transfer pipet (twice) to measure
20.00 mL the potassium iodate. This mixture will turn brown.

In an acidic solution, iodate and iodide react to produce iodine. Sulfuric acid is
chosen for this reaction since the sulfate anion will not interfere with this
particular set of redox reactions.

Save time by carefully measuring only your limiting reagent. The excess reagents
can be measured out much more generally. On the other hand, do not waste
chemicals by adding large excesses of the other reagents.

Add enough deionized water to the titration flask so that you can easily see
color changes.

3. Titration of the iodine solution with the sodium thiosulfate.

Titrate the iodine solution with the sodium thiosulfate solution you have made.
Do not add the starch indicator until the titration is almost finished.

As you perform the titration, the solution color should go from brown to yellow.
Once the solution fades to a light yellow you should add the starch indicator. This
sharpens the endpoint.

In concentrated iodine solutions, the starch complex can tie up some of the
dissolved iodine molecules, effectively removing them from the titration and
affecting the accuracy of the results.

Do at least three trials. Perform the titration immediately upon mixing the
chemicals. Though it is tempting to use "assembly line" techniques and prepare
all of your flasks at once and then titrate them all, this can also adversely affect
your results. The iodine in the solution can clump together over time and become
more and more difficult to dissolve.

Report your average molarity of Na
2
S
2
O
3
standardized solution, and standard
deviation. The post-lab exercises will guide you through these calculations.


4
Part II. Analysis of your Bleach Unknown

Once you have standardized your sodium thiosulfate solution you can move on to the
analysis of your bleach unknown. Plan a titration procedure that will allow you to
determine the mass percentage of sodium hypochlorite in a bleach sample.

Your procedure should be fundamentally the same as for the standardization,
but hypochlorite will take the place of iodate in the reactions. The tips for the
standardization procedure also apply for your unknown analysis.

Plan to use a little less than a gram of bleach unknown in each of your titrations.
Record the mass of bleach used for each trial to a thousandth of a gram.

If you use single gram samples of bleach you will be able to use the same
amounts of the other reagents that you used in the standardization.

Add about 5 drops of the ammonium molybdate catalyst solution to the
hypochlorite-iodide reaction in order to speed it up.

Report the strength of the bleach as the effective mass percentage of the bleach
that is sodium hypochlorite, NaClO, for each titration and then report the average
mass percentage of sodium hypochlorite in the unknown bleach. Calculate a
standard deviation and a 90% confidence limit.

The post-laboratory exercise will guide you through each of the above
calculations and questions.


Clean-up: Rinse the buret and all glassware with deionized water. All solutions can be
disposed of down the drain. If time permits, now would be a good time to clean any
other dirty glassware in your locker. Be sure that all glassware is returned to the proper
place and that your laboratory bench has been rinsed with water using a sponge.


5
DATA ANALYSIS

The following series of questions pertains to Part I of the Redox Titration Experiment,
where you are to calculate the molarity of the sodium thiosulfate standard solution.
Below are the post-lab questions as they will appear in the online post-lab. Please
answer all these questions moving to the online portion of the post-lab.

Enter the precise mass in GRAMS of the potassium iodate used to prepare your primary
standard solution. Your mass precision should be reported to a thousandth of a gram.
(Use three significant figures.)

If one had weighed out precisely 0.500 g of KIO
3
for the primary standard solution and
dissolved it in enough deionized water to make a 250 mL solution, the molarity of that
solution would be 0.00935 M. Enter your calculated molarity of the primary standard
KIO
3
solution. Use three significant figures

Standardization of the sodium thiosulfate solution using the potassium iodate
primary standard solution. We must examine each of the three acceptable trials. First,
let's consider the analyte volume. You were instructed to pipet two 10.00 mL aliquots of
potassium iodate into an Erlenmeyer flask for each analyte sample to be titrated.
Therefore, your analyte volumes of the potassium iodate should be 20.00 mL. For each
trial, enter the precise volume in mL of potassium iodate solution used in the
standardization of sodium thiosulfate (e.g. 20.00 mL or 10.00 mL).

Standardization of the sodium thiosulfate solution using the potassium iodate
primary standard solution. Now, we will examine the volumes of titrant and sodium
thiosulfate used in each trial. Your titration volumes of the sodium thiosulfate solution
should be approximately 20 - 30 mL. For each trial, enter the precise volume in mL of
sodium thiosulfate solution used in the titration of your potassium iodate solution
(e.g. 20.34 mL).

Using the volumes of sodium thiosulfate solution you just entered and the molarity of the
potassium iodate primary standard solution, calculate the molarity of the sodium
thiosulfate secondary standard solution for each trial. Enter your calculated molarity of
the sodium thiosulfate solution for each of the trials. Be sure to enter your calculated
molarities in the corresponding order that you entered your sodium thiosulfate volumes
previously. The sodium thiosulfate volume you entered for entry #1 above should
correspond to the sodium thiosulfate molarity that you enter for entry #1 here. Use three
significant figures.

The molarity of the sodium thiosulfate solution is taken as the average of the three trials.
Please enter the average molarity using three significant figures.

Please enter the standard deviation of the sodium thiosulfate molarity.


6
The following series of questions pertains to Part II of the Redox Titration Experiment,
where you are to calculate the mass percent of sodium hypochlorite in your sample of
bleach.

For the reaction of hypochlorite anion with iodide anion, the iodide anion acts as the
reducing agent according to the oxidation half-reaction, 2 I
-
(aq) I
2
(aq) + 2e-. Which
of the following reduction half-reactions is correct to give the overall reaction of
hypochlorite anion with iodide anion? Three choices will be given.

For the reaction of thiosulfate anion with iodine, the thiosulfate anion acts as the
oxidizing agent according to the oxidation half-reaction, 2 S
2
O
3
2-
(aq) S
4
O
6
2-
(aq) + 2e-.
Which of the following reduction half-reactions is correct to give the overall reaction of
thiosulfate anion with iodine? Three choices will be given.

Notice that the effective analytical connection for analysis of hypochlorite anion by the
thiosulfate anion in this experiment is the sum of the two reactions: 1) hypochlorite anion
with iodide anion to form iodine, and 2) thiosulfate anion with the iodine formed in
reaction one. In your laboratory notebook sum these two reactions to find the
stoichiometric factor that relates moles of thiosulfate anion needed to react with each
mole of hypochlorite anion in the bleach sample. Then select the correct response.
three choices will be given.

For each of three acceptable trials, enter the mass of your bleach sample in GRAMS.
Your mass precision should be reported to a thousandth of a gram.

For each of the three acceptable trials, enter the precise volume in milliliters of sodium
thiosulfate solution used in the titration of your bleach samples (e.g. 20.34 mL). Be sure
to enter your trial volumes in the corresponding order that you entered your masses of
your bleach samples previously. The bleach sample mass you entered for entry #1 above
should correspond to the sodium thiosulfate volume you enter for entry #1 here.

Using the volumes of sodium thiosulfate solution you just entered, the mass of bleach
sample, and the average molarity of the sodium thiosulfate solution entered earlier,
calculate the mass percent of NaClO for each bleach sample. Enter the calculated mass
percent of NaClO in each of the three acceptable trials. Be sure to enter your mass
percent values in the corresponding order that you entered your masses of your bleach
samples and volumes of your sodium thiosulfate previously. The bleach sample mass
you entered for entry #1 and the volume of sodium thiosulfate you entered above should
correspond to the mass percent of NaClO you enter for entry #1 here. Use three
significant figures.

Using your three trial values, calculate the average mass percent of NaClO. Enter the
average mass percent of NaClO in the bleach sample. (Use three significant figures)

Please enter the standard deviation of the average mass percent of NaClO in your bleach
sample.

7

Please enter the calculated 90% confidence limit for the average mass percent of the
NaClO in your bleach samples.

We will now determine the percent error in your analysis of the percent mass of NaClO
in your bleach sample. In order for us to identify which unknown sample you analyzed,
you will need to enter your laboratory room number, locker series and locker number.
These numbers are the hyphenated numbers embossed on your locker. For example, if the
hyphenated numbers read, 1068-6-24, your room number is 1068, your locker series is 6,
and your locker number is 24.

Concluding Remarks: Briefly discuss interpretations of your observations and results.
Include in your discussion, any conclusions drawn from the results and any sources of
error in the experiment.


8


9
Nomenclature of Transition Metal Complexes


Cobalt Complex
Cl
Co NH
2
Cl
H
2
N
H
2
N
NH
2


One of the most interesting aspects of transition metal chemistry is the formation of
coordination compounds, which are often referred to as transition metal complexes. You
will be studying some of these transition metal complexes in Chemistry 2C. Because of
their unique structure, transition metals have their own system of nomenclature.

There is an on-line prelaboratory presentation that reviews the rules of transition metal
complex nomenclature. Please review this presentation and then take the Nomenclature
quiz. You will find the Nomenclature quiz listed on the Main Menu of the Chemistry 2C
Presentation Website. The Nomenclature quiz is not like a pre-lab quiz. The quiz
consists of 10 randomly selected multiple-choice questions worth a total of 20 laboratory
points. You may begin and leave the quiz at any time without penalty. However, you
cannot go back to the previous question.

See your course syllabus, TA, or your course instructor for the due date of the
Nomenclature quiz.

10

11
Electrochemical Cells


INTRODUCTION

The use of electrochemical cells to convert the Gibbs energy stored in the constituent
half-reactions into electrical work is of enormous industrial as well as fundamental
significance. We have all used batteries and these are simply galvanic cells similar to
those you will construct in this experiment. In the laboratory, a typical electrochemical
(or galvanic) cell has the following general construction:




Figure 1: A Schematic of a Galvanic Cell

In Figure 1, there are two electrode-compartments, each of which contains an electrode
and the constituents of the half-reaction. In many instances, the electrode is actually one
of the chemical components of the half-reaction. For example, the copper electrode is
involved directly in the half reaction, Cu
2+
+ 2e
-
Cu. In other cases, however, the
electrode does not participate in the chemistry of the half-reaction, but merely provides
an inert conducting surface on which the electron exchange occurs. For example, when
the half reaction Fe
3+

+ e
-
Fe
2+
is studied, a Pt or C electrode rather than an iron
electrode is used. This is because on an iron wire, both Fe
3+
+ 3 e
-
Fe(s)

and Fe
2+
+ 2
e
-
Fe(s) could occur, rather than the Fe
3+

/ Fe
2+
reaction that is of interest.

The two electrode compartment must be separated by a barrier that permits ions to
migrate inside the cell, but does not allow the contents of the chambers to mix. A glass
tube that is filled with a gel saturated with a strong electrolyte such as KNO
3
is often
used. In this case, the K
+

and NO
3
-
ions create a "salt bridge" for the electrochemical cell.
Electrochemical cells have both a magnitude for the measured voltage and a polarity. An
electrode that is positive, relatively speaking, must be deficient in electrons, and hence a
reduction must be taking place at that electrode. Conversely, an electrode that appears
negative has a surplus of electrons. Hence, electrons are being released into it by an

12
oxidative half-reaction. By definition, oxidation occurs at an anode. Hence, the (-) pole
of an electrochemical cell is necessarily its anode, and the (+) pole is its cathode (where
the reduction occurs).

The directions for this experiment exploit the fact that electrochemical cells can be
described very efficiently by using conventional "cell diagrams." A possible diagram for
a galvanic cell that employs the net ionic reaction,

2 Ag
+
(aq) + Cu(s) Cu
2+
(aq) + 2 Ag(s)
is
Cu(s) | Cu(NO
3
)
2
(aq) (0.1M) || AgNO
3
(aq) (0.1M) | Ag(s)

The corresponding measured conventional cell voltage is roughly +0.4 V.

The cell diagram contains the information necessary to construct the electrochemical cell.
The cell diagram has a "right hand" electrode (here a piece of silver wire) and a "left
hand" electrode (here a piece of copper wire). A single vertical line means that the two
species flanking it have different phases. In this case, the two phases are the solid wires
and the liquid solutions whose concentrations are specified inside the parentheses. The
double vertical line implies some type of chemically inert salt bridge connecting the two
compartments in question.

The algebraic sign of a cell containing a spontaneous reaction is always a positive
voltage. A negative voltage reading is possible in this experiment even though all the
reactions are spontaneous. If a negative voltage is measured, then the cell diagram is
written in reverse of the spontaneous direction of the cell. A correct cell diagram of a
spontaneous redox reaction has the anode written on the left of the double vertical line
and the cathode written to the right.

In this experiment you will construct and measure the voltage of electrochemical cells
that involve the half-reactions (in alphabetical order): Cu
2+
+ 2e
-
Cu, Fe
3+

+ e
-
Fe
2+
,
Pb
2+

+ 2 e
-
Pb, Zn
2+
+ 2 e
-
Zn. From your results you will be able to determine the
relative positions of these half-reactions in a Table of Standard Potentials. You will also
confirm that the potentials of half-reactions are concentration dependent. As you know,
in order to calculate the voltages of non-standard cells (not 1 M and 1 atm), you need to
use the Nernst equation. A useful form of the Nernst equation is equation 21.18 in
section 21-4 on page 839 in your textbook. Read Chapter 21 in your Petrucci textbook,
8th ed., as pre-laboratory preparation before beginning this experiment.

There is one last but important note. This experiment is quite easy and short in terms of
the actual collection of data. However, the write-up is difficult and requires a good
understanding of electrochemistry. Students in the past have found it very helpful to take
the time to do each step slowly and try to understand what is happening. They also said
that it is critical to begin the write-up while in the laboratory in order to repeat steps that
have become confusing or to get assistance from the TA or fellow students. You are
strongly encouraged to follow this advice!


13
Preparation for Next Lab

Each student needs to dry a sample of solid calcium carbonate for the EDTA laboratory.
1. Each student must half fill one vial with pure calcium carbonate.
2. Place the uncapped vial in a beaker. Write your name on the white frosted area of
the beaker with a graphite pencil and place it in the oven. Do not use paper
labels on your vial or beaker. Cover the beaker with a watch glass.
3. Dry the sample in the oven for 1.5 hours. Do not adjust the temperature on the
oven. The temperature on the oven has been preset and will heat to the correct
temperature when the door remains closed.
4. After removing your sample from the oven, let it cool until it is warm but safe to
handle.
5. After the sample has cooled carefully, place the beaker containing the uncapped
vial in the desiccator until needed. Be careful not to touch the vial with your
fingers.

Make sure that you label the vial!






14
Safety, Clean-up and Special instructions:
1. Wear your Goggles and gloves throughout this experiment.
2. Dispose of all solutions on your spot plate by holding it vertically above the
mouth of the funnel in the neck of the metal waste disposal container and
rinsing it with a brisk stream from your wash bottle. The metal waste containers
are in the fumehoods. Wash the spot plate more thoroughly under the deionized
water faucet and dry it for later use.
3. Excess solutions containing lead and copper need to be disposed of in the metal
waste containers while the excess solutions containing only iron may go down
the drain with copious amounts of water.
4. Treat the voltmeters with care and respect, as they are expensive.

PROCEDURE

You will work in pairs on this experiment. The actual data analyses and the written
reports must be done entirely independently of your lab partner or other students. Make
sure that you avoid unauthorized collaboration and plagiarism. All suspected violations
of the Code of Academic Conduct will be referred to Student Judicial Affairs.

Part I. Constructing a Table of Standard Reduction Potentials

In this part of the experiment, you will be measuring the voltages of the several galvanic
cells diagrammed below. In other words, you will be using the "V" scales of the meters
(which you will find at the front of the laboratory.) Note that the meter display has both
an algebraic sign and a magnitude. Throughout this experiment you should clip the
"red" wire coming out of the meter to the "right hand" electrode of the cell in question. If
the meter shows a "plus" voltage, reduction takes place at that electrode. If the displayed
voltage is negative, oxidation is what really occurs at the "right hand" electrode of the
cell as diagrammed.

In most cases the cell electrolytes for Part I of the experiment will be 0.1 M stock
solutions of the nitrate salts of the various cations. For the cell containing a mixture that
is 0.1 M in both Fe
2+
and Fe
3+
, you should mix together 1 mL volumes of the 0.2 M stock
solutions of the respective sulfate or nitrate salts in a clean test tube.

Note that the Fe
2+
stock solution contains sulfuric acid and some iron nails. This is to
insure that any ferric ion that might get produced by air oxidation gets re-reduced to the
2+ oxidation state. Because oxygen does attack Fe
2+
, you should measure the voltages of
cells containing the ferrous ion as soon as possible after the solution in question has been
prepared. These cell voltages will probably change over time.

The electrode "compartments" are simply the wells in a "spot plate." A well will hold
about 1 mL of solution and they can be filled very easily using disposable polyethylene
pipets. The "salt bridge" is nothing more than a well containing 0.1 M sodium nitrate
solution which gets connected to two or more other wells with short (ca. 3 cm) lengths of
cotton string that you have pre-saturated in a watch glass containing 0.1 M NaNO
3

solution. You cannot connect the anode and cathode wells directly with the NaNO
3

saturated string. You must connect both the anode and the cathode to the well containing
the 0.1 M NaNO
3
solution with the string.


15
Use the plastic blue tongs that are available in the laboratory to manipulate the strings.
The strings can actually function as siphons so you should always fill all the desired wells
in the spot plate first and then put the conducting strings in place.

Assemble and measure the voltages of the following conventional cells:

Cell #1
Zn(s) | Zn(NO
3
)
2
(aq) (0.10M) || Cu(NO
3
)
2
(aq) (0.10M) | Cu(s)
Cell #2
Pb(s) | Pb(NO
3
)
2
(aq) (0.10M) || Cu(NO
3
)
2
(aq) (0.10M) | Cu(s)

Cell #3
C(graphite) | FeSO
4
(aq)

(0.10M), Fe(NO
3
)
3
(aq) (0.10M) || Cu(NO
3
)
2
(aq) (0.10M) | Cu(s)


Part II. The Concentration Dependence of Half Cell Potentials

Assemble and measure the voltages of the following conventional cells:

Cell #4
Cu(s) | Cu(NO
3
)
2
(aq) (0.010M) || Cu(NO
3
)
2
(aq) (0.10M) | Cu(s)
Cell #5
C(graphite) | FeSO
4
(aq)

(0.01M), Fe(NO
3
)
3
(aq) (0.10M) || Cu(NO
3
)
2
(aq) (0.10M) | Cu(s)

Cell #6
C(graphite) | FeSO
4
(aq)

(0.10M), Fe(NO
3
)
3
(aq) (0.010M) || Cu(NO
3
)
2
(aq) (0.10M) | Cu(s)

In Cell #5, the "left hand" compartment electrolyte solutions are prepared in the first by
diluting the 0.20 M stock solution by a factor of 10. This involves adding 1 mL of the
0.20 M stock solution to 9 mL of deionized water. Then, second, by mixing the ferric
sulfate solution with the diluted ferric nitrate solution in equal volume.

In Cell #6, the "left hand" compartment electrolyte solutions are prepared by mixing
0.2M ferric nitrate solution with the ferric sulfate solution in equal volume.

Clean-up: Dispose of the excess diluted copper solution in the waste container. The
iron solutions can be washed down the drain.



16
Part III. Estimating the Solubility Product of Lead(II) Sulfate

For this part of the experiment prepare a 0.050 M Pb(NO
3
)
2
solution by diluting the stock
0.1 M Pb(NO
3
)
2
solution by a factor of 2 in one test tube. In another test tube mix equal
volumes of 0.10 M Pb(NO
3
)
2
and 3.0 M ammonium sulfate. Allow about two minutes for
the complete precipitation of PbSO
4
. Assemble and measure the voltage of the cell:

Cell #7
Pb(s) | PbSO
4
(s), NH
4
+
(3.0 M), SO
4
2-
(1.50 M), NO
3
-
(0.10 M), Pb
2+
(? M) || Pb(NO
3
)
2
(0.050 M) | Pb(s)

(This is experimentally very easy to do: fill one well of your spot plate with the diluted
lead nitrate solution, fill an adjacent one with a slurry of the contents of the test tube
containing the precipitated lead sulfate, connect them with salt bridge strings to a well
full of the sodium nitrate solution, attach two Pb electrodes to the wires from the meter,
and measure the cell voltage.)

Clean-up. Dispose of all the lead-containing solutions in the proper waste container
found in the fumehood.


17
DATA ANALYSIS

Part I.
For every conventional galvanic cell diagram there is a corresponding (chemical) cell
reaction, as illustrated by the example in the Introduction section of this experiment.
According to the Nernst equation the conventional cell voltage of such a cell can be
written in general as
E
cell
= (E
cathode
- E
anode
)- [0.0257 / n] ln Q

where E
cathode
is the standard reduction potential of the cathode half cell reaction and
E
anode
is the standard reduction potential of the anode half cell reaction. Q is the reaction
quotient, for the overall cell reaction, using the concentrations given in the cell diagram.
Note that at equilibrium when Q = K then E
cell
is equal to zero.

For the cell discussed in the introduction this equation becomes:

E
cell
= (E
Ag+/Ag
- E
Cu++/Cu
) - 0.0129 ln[ (0.10M) / (0.10M)
2
]

= (0.799-0.337) - 0.0297

= + 0.432 V

The numerical values of the standard reduction potentials used in this example were
taken from a table in the Appendix of your textbook.

In part I you measured the voltages of three cells, each containing a different metal,
against a common Cu(II)/Cu reference electrode. The standard reduction potential of the
Cu(II)/Cu(s) redox couple is known to be 0.34V. This value is used as the "known"
standard reduction potential in the following calculations.

For each of the three cells whose voltages you measured in Part I of this experiment write
the corresponding redox reaction in the spontaneous direction and calculate the value of
the standard cell potential, (E
cathode
- E
anode
) using your measured cell potentials and the
Nernst equation. Using the standard cell potential you just calculated and the known
value of the standard reduction potential of the Cu(II)/Cu(s) redox couple, determine the
standard reduction potential of each of the noncopper metal half cells. You should also
compare your findings with the accepted values.

------------------------------------------------------------------------------------------------------------

Part I Analysis. The following series of questions and calculations will lead you through
the calculation of the standard reduction potentials of the half-cells, Zn
2+
/Zn(s),
Pb
2+
/Pb(s), and Fe
3+
/Fe
2+
.

Part I Analysis. Given the Nernst equation, E
cell
= (E
o
cathode
- E
o
anode
) - [0.0257/n]lnQ, and
the equation, E
o
cell
= E
o
cathode
- E
o
anode
, substitute E
o
cell
into the Nernst equation and solve
for E
o
cell
. Which of the following would be the correct expression for E
o
cell
? Three
choices will be given.

18

Part I Analysis. For the cell, Zn(s) | Zn(NO
3
)
2
(0.10M) || Cu(NO
3
)
2
(0.10M) | Cu(s) which
of the following is the correct spontaneous overall cell reaction: Three choices will be
given.

Part I Analysis. Please enter the value of E
cell
you measured in volts for the spontaneous
cell reaction for Zn(s) | Zn(NO
3
)
2
(0.10M) || Cu(NO
3
)
2
(0.10M) | Cu(s).

Part I Analysis. For the cell, Zn(s) | Zn(NO
3
)
2
(0.10M) || Cu(NO
3
)
2
(0.10M) | Cu(s) which
of the following is the correct expression for Q, the reaction quotient in the Nernst
equation, for the spontaneous overall cell reaction: Three choices will be given

Part I Analysis. Using your cell concentrations and the reaction quotient expression,
calculate and enter the value of Q for the Nernst equation for this cell Zn(s) |
Zn(NO
3
)
2
(0.10M) || Cu(NO
3
)
2
(0.10M) | Cu(s) .

Part I Analysis. Please enter the value of lnQ that appears in the Nernst equation for this
cell, Zn(s) | Zn(NO
3
)
2
(0.10M) || Cu(NO
3
)
2
(0.10M) | Cu(s) .

Part I Analysis. For the cell, Zn(s) | Zn(NO
3
)
2
(0.10M) || Cu(NO
3
)
2
(0.10M) | Cu(s), put all
the terms together that enter into the equation for E
o
cell
and enter the value you calculate
for it.

Part I Analysis. Please enter the accepted value from the table in your text for the
standard electrode potential, E
o
, for the half-cell reaction for copper: Cu
2+
(aq) + 2e-
Cu(s) in volts. You will use this value as a reference to calculate the standard electrode
potentials for the other half-reactions involved in the cells you measured.

Part I Analysis. Using the equation E
o
cell
= E
o
cathode
- E
o
anode
, and the reference value of E
o

for Cu(II)/Cu(s) for the role that copper plays in this overall cell reaction, determine the
value of the standard potential for the half-reaction Zn
2+
(aq) + 2e- Zn(s) and enter it
here.

Part I Analysis. For cell Pb(s) | Pb(NO
3
)
2
(0.10M) || Cu(NO
3
)
2
(0.10M) | Cu(s), which of
the following is the correct spontaneous overall cell reaction: Three choices will be given

Part I Analysis. Please enter the value of E
cell
you measured in volts for the spontaneous
cell reaction for cell Pb(s) | Pb(NO
3
)
2
(0.10M) || Cu(NO
3
)
2
(0.10M) | Cu(s).

Part I Analysis. For the cell, Pb(s) | Pb(NO
3
)
2
(0.10M) || Cu(NO
3
)
2
(0.10M) | Cu(s) which
of the following is the correct expression for Q, the reaction quotient in the Nernst
equation, for the spontaneous overall cell reaction: Three choices will be given

Part I Analysis. Using your cell concentrations and the reaction quotient expression,
calculate and enter the value of Q for the Nernst equation for this cell, Pb(s) |
Pb(NO
3
)
2
(0.10M) || Cu(NO
3
)
2
(0.10M) | Cu(s).

19

Part I Analysis. Please enter the value of lnQ that appears in the Nernst equation for this
cell, Pb(s) | Pb(NO
3
)
2
(0.10M) || Cu(NO
3
)
2
(0.10M) | Cu(s)

Part I Analysis. For the cell, Pb(s) | Pb(NO
3
)
2
(0.10M) || Cu(NO
3
)
2
(0.10M) | Cu(s), put all
the terms together that enter into the equation for E
o
cell
and enter the value you calculate
for it.

Part I Analysis. Using the equation E
o
cell
= E
o
cathode
- E
o
anode
, and the reference value of E
o

for Cu(II)/Cu(s) for the role that copper plays in this overall cell reaction, determine the
value of the standard potential for the half-reaction Pb
2+
(aq) + 2e- Pb(s) and enter it
here.

Part I Analysis. For cell C(gr) | Fe(NO
3
)
3
(0.10M), FeSO
4
(0.10M) || Cu(NO
3
)
2
(0.10M) |
Cu(s), which of the following is the correct spontaneous overall cell reaction: Three
choices will be given

Part I Analysis. Please enter the value of E
cell
you measured in volts for the spontaneous
cell reaction for cell C(gr) | Fe(NO
3
)
3
(0.10M), FeSO
4
(0.10M) || Cu(NO
3
)
2
(0.10M) | Cu(s).

Part I Analysis. For the cell, C(gr) | Fe(NO
3
)
3
(0.10M), FeSO
4
(0.10M) ||
Cu(NO
3
)
2
(0.10M) | Cu(s), which of the following is the correct expression for Q, the
reaction quotient in the Nernst equation, for the spontaneous overall cell reaction: Three
choices will be given

Part I Analysis. Using your cell concentrations and the reaction quotient expression,
calculate and enter the value of Q for the Nernst equation for this cell C(gr) |
Fe(NO
3
)
3
(0.10M), FeSO
4
(0.10M) || Cu(NO
3
)
2
(0.10M) | Cu(s).

Part I Analysis. Please enter the value of lnQ that appears in the Nernst equation for this
cell, C(gr) | Fe(NO
3
)
3
(0.10M), FeSO
4
(0.10M) || Cu(NO
3
)
2
(0.10M) | Cu(s).

Part I Analysis. For the cell, C(gr) | Fe(NO
3
)
3
(0.10M), FeSO
4
(0.10M) ||
Cu(NO
3
)
2
(0.10M) | Cu(s), put all the terms together that enter into the equation for E
o
cell

and enter the value you calculate for it.

Part I Analysis. Using the equation E
o
cell
= E
o
cathode
- E
o
anode
, and the reference value of E
o

for Cu(II)/Cu(s) for the role that copper plays in this overall cell reaction, determine the
value of the standard potential for the half-reaction Fe
3+
(aq) + e- Fe
2+
(aq) and enter it
here.


20
Part II.
1. Write the chemical reaction in the spontaneous direction for the copper concentration
cells--the first cell you examined in Part II of the experiment. Calculate the
theoretical value of the potentials for these copper concentration cells using the
Nernst equation. Compare the measured and theoretical values for these cell
potentials. Your agreement will be only semi-quantitative.

2. Altogether, you have measured the voltages of three cells with different relative
concentrations of Fe
2+
and Fe
3+
ions against a common Cu
2+
/Cu reference electrode.
If you write out the Nernst equation for these three cells expanding the logarithmic
terms you will find that in each case the cell voltage can be written as a sum of four
terms. [Hint: ln (a b / c) = (ln a) + (ln b) (ln c)] Three of them are invariant and
include the E
o
's of the iron and copper half reactions along with the term that takes
the log of the copper ion concentration into account. The fourth term, however,
varies in value and involves only the log of the ratio of the iron species
concentrations, and must therefore be responsible for the voltage changes you
observed in the laboratory. Calculate the theoretical cell voltage DIFFERENCES for
the three concentration cells involving the copper and iron and compare your
experimental results with these predictions. Again you should expect only semi-
quantitative agreement. In separate calculations, find the cell voltage difference
between cell #3 in Part I and each of the iron containing cells of Part II.

------------------------------------------------------------------------------------------------------------

Part II Analysis. Using the facts that a spontaneous cell reaction gives a positive
measured voltage when the red lead of the voltmeter is connected to the cathode, and that
reduction takes place at the cathode while oxidation takes place at the anode, which of the
following is the spontaneous reaction for the copper concentration cell you measured in
Part II of the electrochemistry experiment? Three choices will be given

Part II Analysis. Because the standard potentials are the same for both the anode and the
cathode reactions for a concentration cell, the Nernst equation for a concentration cell
becomes simply Ecell = -(0.0257/n)lnQ, where Q is to be calculated for the spontaneous
cell reaction. What is the value of Q for the copper concentration cell?

Part II Analysis. E
cell
= -(0.0257/n)lnQ Now, using your value for Q calculate E
cell
from the Nernst equation for the copper concentration cell, and enter it here.

For Part II of the electrochemistry experiment, you measured the potential of some
concentration cells. The laboratory manual asked you to construct the cells

a) Cu(s)Cu(NO
3
)
2
(0.010M) || Cu(NO
3
)
2
(0.10M)|Cu(s)
b) C(graphite) | FeSO
4
(0.010M), Fe(NO
3
)
3
(0.10M) || Cu(NO
3
)
2
(0.10M) | Cu(s)
c) C(graphite) | FeSO
4
(0.010M), Fe(NO
3
)
3
(0.10M) || Cu(NO
3
)
2
(0.10M) | Cu(s)


21
When the red lead for the voltmeter was connected to the right-hand electrode of the cells
as diagrammed above, which of these cells showed a positive algebraic sign for the
measured voltage?

Part II Analysis. When a measured cell voltage is negative, the electrode to which the red
lead is attached is actually the anode rather than the cathode. The anode is the electrode
at which oxidation takes place, so it is surrendering electrons to the external circuit. For
the two cells involving the iron and copper species, the Cu(II)/Cu(s) couple is the anode.
Which of the following half-cell reactions is taking place at the Cu electrode in the anode
compartment of these two cells? Three choices will be given

Part II Analysis. You will now calculate the theoretical cell voltage differences for the
three concentration cells involving the copper and iron, cells #3, #5, and #6, and compare
your experimental results with these predictions.

Part II Analysis. For the overall cell reaction in cells #3, #5, & #6,
Cu(s) + 2Fe
3+
(aq) 2Fe
2+
(aq) + Cu
2+
(aq), which of the following is the correct
expression for Q, the reaction quotient in the Nernst equation: Three choices will be
given

Part II Analysis. The Nernst equation for the cell potential of cells #3, #5, & #6, is
E
cell
= E
o
cell
- (0.0257/2)ln((Q
previous question
). What is the expression, then, for the cell
voltage difference between cells #5 and #3, Ecell#5 - Ecell#3? Three choices will be
given

Using the ion concentration values in cells #3 & #5 in the expression obtained from the
previous question, calculate the theoretical cell voltage difference between cells #5 and
#3.

Using the ion concentration values in cells #3 & #6 and the expression for
E
cell
#6 - E
cell
#3, calculate the theoretical cell voltage difference between cells #6 and #3.

Part III.

In this experiment what you have really done is prepare a concentration cell with
drastically different concentrations of the Pb
2+
ion in the two halves of the cell. Use the
Nernst equation and the measured cell voltage to estimate the Pb
2+
ion concentration in
the compartment containing the lead sulfate slurry. The solubility product of lead sulfate
can then be estimated by multiplying this result by the concentration of the sulfate ion in
that compartment. Your result should be within about a factor of ten of the tabulated
value for this constant.

------------------------------------------------------------------------------------------------------------

Part III Analysis. You will now calculate the solubility product for PbSO
4
by using your
measured potential for cell #7 in Part III of the laboratory.

22

Part III Analysis. Please enter the value of E
cell
you measured in volts for the
spontaneous cell reaction for cell Pb(s) | PbSO
4
(s), NH
4
+
(3.0M), SO
4
2-
(1.50M), NO
3
-

(0.10M), Pb
2+
(? M) || Pb(NO
3
)
2
(0.050 M) | Pb(s).

Part III Analysis. Because the standard potentials are the same for both the anode and the
cathode reactions for a concentration cell, the Nernst equation for a concentration cell
becomes simply E
cell
= -(0.0257/n)lnQ, where Q is the expression for the spontaneous cell
reaction. For the concentration cell, Pb(s) | PbSO
4
(s), NH
4
+ (3.0M), SO
4
2-
(1.50M), NO
3
-

(0.10M), Pb
2+
(? M) || Pb(NO
3
)
2
(0.050 M) | Pb(s) which of the following is the correct
expression for Q for the spontaneous overall cell reaction, Pb
2+
(0.050M) Pb
2+
(?): Four
choices will be given

Part III Analysis. For the concentration cell, Pb(s) | PbSO
4
(s), NH
4
+ (3.0M), SO
4
2-
(1.50M), NO
3
-
(0.10M), Pb
2+
(? M) || Pb(NO
3
)
2
(0.050 M) | Pb(s), E
cell
= -
(0.0257/2)lnQ
previous question
, what is the expression for x in terms of E
cell
? 4 choices will
be given.

Part III Analysis. Using your measured cell potential for Pb(s) | PbSO
4
(s), NH
4
+ (3.0M),
SO
4
2-
(1.50M), NO
3
-
(0.10M), Pb
2+
(? M) || Pb(NO
3
)
2
(0.050 M) | Pb(s) in your expression
for x, calculate the molarity of Pb
2+
in the anode compartment.

Part III Analysis. Which of the following is the correct solubility product expression,
K
sp
, for PbSO
4
? Five choices will be given

Part III Analysis. Using the expression, K
sp
= [Pb
2+
][SO
4
2-
], the concentration of sulfate
in the anode compartment, and determined value Pb
2+
concentration in the anode
compartment, calculate K
sp
. Please enter your molarity in decimal form only. Do not use
scientific notation.

23
EDTA Titrations

INTRODUCTION

In these times of environmental awareness and concern, it is very important that you
become experienced with water analysis. As you know, Davis is not known for the
exceptional quality of its water. In fact, lets face it, the water here tastes pretty bad!
What is in it? That would be a good question to try to answer if we had lots of time and
if we wanted to spend it doing an experiment in qualitative analysis. However, for now
we want to learn more about quantitative analysis. It is well known that ground water
commonly contains a large amount of two metal ions, calcium and magnesium. The term
"hard water" refers to the presence of these two metals. These metals give the water a
rather harsh taste and will also cause the white deposits often observed on faucets or as
"lime" deposits in bathtubs. These white deposits are generally metal carbonates. In
addition, these two metal ions will precipitate soaps, leaving the unsightly bathtub scum
that you may have observed. Perhaps you have had the experience of living or visiting a
residence where the water has been "softened". Softening refers to a process whereby the
water is passed through a column in which the calcium and magnesium ions are removed.
This makes the water feel "softer" when taking a bath or shower, because the soap
precipitates do not form.

In this experiment, you will determine the amount of calcium carbonate present in an
unknown solid sample the stockroom has prepared. To do this you will use a hexadentate
ligand called ethylenediaminetetraacetic acid (EDTA). This ligand, due to its six donor
atoms and to its size and shape, has the exceptional ability to complex or chelate with a
variety of metal ions. The equilibrium constant for the formation of each metal/EDTA
complex is different, and the kinetic rate at which each metal complexing agent forms is
different as well. Thus, the ligand can be used to complex one metal ion in the presence
of another. For example, calcium-EDTA is given as an antidote for mercury ion
poisoning. Once the EDTA is ingested, it will selectively bind to the free mercury ions,
effectively removing them and not allowing them to bind to enzymes and cytochromes.
Thus the poison is removed and passes innocuously through the physiological system.
For our analysis, we will use disodium EDTA to bind to calcium and magnesium ion as is
shown below:

2 OH
-
+ Ca
2+
+ H
2
EDTA
2-
CaEDTA
2-
+ 2 H
2
O K

= 5.0 x 10
10


2 OH
-
+ Mg
2+
+ H
2
EDTA
2-
MgEDTA
2-
+ 2 H
2
O K

= 5.0 x 10
8


However, we need something to indicate when the reaction is complete. We need an
indicator. The indicator will need to be another ligand and it must have a different color
when it is free than when bound to a metal ion. One such ligand is Calmagite that binds
to alkaline earth metals producing a color change as follows:

M
2+
+ In
2-
(blue) MIn (red or pink)

K = ~ 7 x 10
-9


24

The reaction of EDTA with metals (K~10
8
) is greater than that of Calmagite (K~10
-9
).
Thus, if a small amount of indicator is added to a solution of magnesium and calcium, a
red or pink colored complex will result. If EDTA is then added via a buret, the color will
change when the metal is stripped from the Calmagite and binds to the EDTA; the
solution will turn blue. If we have carefully measured the amount of EDTA that we have
added, then we can determine the total amount of calcium and/or magnesium in the
sample.

It is important that you appreciate that EDTA has acid/base properties. It has four acid
constants, as is shown below (Note: Y = EDTA
4-
)

H
4
Y H
+
+ H
3
Y
-

K
a1
= 1.0 x 10
-2

H
3
Y
-

H
+

+ H
2
Y
2-
K
a2
= 2.2 x 10
-3

H
2
Y
2-

H
+
+ HY
3-
K
a3
= 6.9 x 10
-7

HY
3-
H
+

+ Y
4-
K
a4
= 5.5 x 10
-11


For this reason, analyses must be done at a constant pH and one that will enable the
ligand to bind successfully with the metal. These determinations will be conducted at
pH 10 via the addition of a NH
4
OH/NH
4
Cl (pK
a
= 9.24) buffer.




25

PROCEDURE

Work in Pairs on this experiment.

Pre-Laboratory Preparation

During the laboratory period before beginning this experiment (Electrochemical Cells)
you were instructed to dry a sample of pure calcium carbonate and an unknown sample.

Part I. Preparation and Standardization of an EDTA Solution

1. Prepare approximately 500 mL of a 0.03 M Na
2
EDTA

solution by filling the 1 L
bottle with approximately 300 mL of deionized water. Add the necessary mass of
solid Na
2
EDTA2H
2
O. Stir to dissolve. Since solid EDTA dissolves slowly, go on to
weigh your CaCO
3
samples for the standardization. After your solid Na
2
EDTA2H
2
O
has dissolved, take your solution to the fumehood and add about 20 mL of the pH
10 buffer.


NOTES:
(1) Do not use the buffer solution found on the shelves in the lab. Add
the 10 M ammonia buffer found in the fumehood.

(2) Only add the 10 M ammonia buffer to your solution in the fumehood.

2. Mix well and add another 180 mL of deionized water to make approximately 500 mL
of solution

3. Standardize the EDTA solution by using dry calcium carbonate. Here are some tips
to make your titration smooth and successful.

In preparing for the lab, you should have calculated the approximant mass of the
primary standard, CaCO
3
, necessary for the titration. Weigh your three samples of
your primary standard by difference being careful not to touch the vial containing the
calcium carbonate with your fingers. Use a small piece of folded paper wrapped
around the vial to handle the sample. Find the initial mass of vial; dispense the solid
in a 250 mL Erlenmeyer flask; and reweigh the vial. Record the precise masses in
your notebook. Calcium carbonate is insoluble in water. To dissolve the sample, add
about 20 mL of deionized water to it and then slowly add 6 M HCl drop-wise. You
Safety:
1. The pH 10 buffer is 10 M ammonia. Keep it under the fume hood as much as
possible and avoid breathing its vapors.
2. Wear your goggles!

26
will observe the evolution of CO
2
gas as the carbonate reacts with the HCl. It will
take approximately 6-15 drops of HCl to neutralize the sample and dissolve it. Do
not over acidify.

Question A: Write the balanced chemical equation for the standardization of EDTA
solution.

It is absolutely essential that the pH of the calcium carbonate solution remain at 10
throughout the titration. To ensure that the pH remains at 10, in the fumehood add an
additional 5 mL of the ammonia buffer (found in the fumehood) and another 30 mL
of water to the calcium carbonate solution. Check the pH of the solution using
Alkacid paper. You may also want to check the pH of the solution a couple of times
during the titration.

NOTES:
(1) Be sure to use only the ammonia buffer located in the fumehood. Do
not use any other buffers that may be found elsewhere in the
laboratory.

(2) Only add the ammonia buffer to your solution in the fumehood.

Five to six drops of Calmagite indicator is sufficient to show the color change at the
endpoint. In addition, one can sharpen the endpoint by adding about 1 mL of the
solution labeled Na
2
MgEDTA. The magnesium ion is approximately 40 times more
strongly bound to the indicator Calmagite than is the calcium ion. In addition, the
calcium ion is approximately 200 times more tightly bound to the ligand EDTA. Thus
when EDTA is added to the solution it will preferentially bond to the calcium ion.
When the calcium ion has completely reacted, the EDTA will then pull the magnesium
ion away from the indicator and the solution will then change color. Note that adding
one mL of this solution does not affect the stoichiometry of the titration as the solution
contains an equal molar amount of magnesium and EDTA. Be sure to titrate all the
way to the blue color endpoint and not stop titrating when the solution is the purple
color. Keep the flask of your first trial titration to use as a reference color for
subsequent trials. Be sure you have three acceptable trials before moving on to Part II.
To determine if a trial is acceptable, calculate the molarity of the EDTA solution based
on your volumes and mass of CaCO
3
for each trial and then perform the Q-test. For
more details regarding the Q-test calculation, see the introductory section of your
laboratory manual.

Question B: Write the balanced chemical equation for the reaction between the
EDTA solution and the indicator, MgIn(aq).

Perform the analysis with three samples. Calculate the molarity of the EDTA solution for
each sample. Calculate an average molarity and the standard deviation. The post-lab
exercises will guide you through these calculations.


27
Part II. Determination of Calcium in an Unknown

1. Clean three 125 mL, 250 or 300 mL Erlenmeyer flasks. It is very important that the
flasks be extremely clean and well rinsed with deionized water. Accurately weigh
three samples of your dry unknown into the three Erlenmeyer flasks. The unknown
samples should weigh between 0.150 - 0.180 grams.

2. Titrate the unknown samples using the same procedure that you used for the
standardization of your EDTA solution. Be sure you have three acceptable trials
before cleaning up. To determine if a trial is acceptable, calculate the percent mass
CaCO
3
in the sample for each trial based on your volumes of EDTA and mass of
CaCO
3
for each trial and then perform the Q test. Report the average percent by mass
of CaCO
3
in your unknown along with both a relative and standard deviation, and a
90% confidence limit. The post-lab exercises will guide you through these
calculations.

Clean-up: Rinse all glassware with deionized water. Return all chemicals and
equipment to the proper location. All solutions may go down the drain with copious
amounts of water. Rinse the bench with your sponge and water.


In order for the on-line program to identify the unknown that you were assigned to
analyze, you will need to know the hyphenated number embossed on your locker in your
laboratory room. For example, in room 1068 SLB one of the locker's hyphenated number
reads, 1068-6-24.

Your lockers hyphenated number is - _________ - _________- _________

28
DATA ANALYSIS

In the standardization of the sodium EDTA solution using the solid calcium carbonate
primary standard, we must examine each of three acceptable trials. Enter the precise mass
in GRAMS of the dry primary standard, calcium carbonate, used for each of three
acceptable trials in the standardization titration. Your mass precision should be reported
to a thousandth of a gram.

In the standardization of the sodium EDTA solution using the solid calcium carbonate
primary standard, your titration volumes of the sodium EDTA solution should be
approximately 20 - 30 mL. For each of the 3 acceptable trials used in the titration of your
calcium carbonate samples, enter the precise volume in milliliters of EDTA solution (e.g.
20.34 mL). Be sure to enter your volumes in the corresponding order that you entered
your masses of calcium carbonate previously. For instance, the mass of calcium
carbonate you entered for entry #1 above should correspond to the volume of EDTA
solution that you enter for entry #1 here.

Using the volumes of sodium EDTA solution you just entered and the corresponding
calcium carbonate masses entered earlier, calculate the molarity of the sodium EDTA
solution for each trial. Enter your calculated molarity of the EDTA solution for each trial.
Be sure to enter your calculated molarities in the corresponding order that you entered
your EDTA volumes previously. For instance, the EDTA volume you entered for entry
#1 above should correspond to the molarity that you enter for entry #1 here.

The molarity of the EDTA solution is taken as the average of the three trials. Please enter
the average molarity.

Please enter the standard deviation of the EDTA molarity.

The following series of questions pertains to Part II of the EDTA Titration Experiment,
where you are to calculate the percent mass of calcium carbonate in your dry unknown
sample.

In the titration of the dry unknown sample with the secondary standard solution, sodium
EDTA, we must examine each of three acceptable trials. Enter the mass of your dry
unknown sample in GRAMS, for each your three acceptable trials. Your mass precision
should be reported to a thousandth of a gram.

In the titration of the dry unknown sample with the secondary standard solution, sodium
EDTA, your titration volumes of the sodium EDTA solution should be approximately 20-
30 mL. For each of the three acceptable trials, enter the precise volume in milliliters of
EDTA solution used in the titration of your dry unknown samples (e.g. 20.34 mL). Be
sure to enter your trial volumes in the corresponding order that you entered your masses
of the samples previously. For instance, the dry unknown sample mass you entered for
entry #1 above should correspond to the EDTA volume you enter for entry #1 here


29
Using the volumes of EDTA solution you just entered and the corresponding dry
unknown sample masses entered earlier, calculate the percent mass of calcium carbonate
in the unknown sample mixture. Enter the calculated percent mass of calcium carbonate
in the dry unknown sample for each of the three acceptable trials. Be sure to enter your
mass percentages to the correct number of significant digits and in the corresponding
order that you entered your masses of your dry unknown samples and volumes of your
EDTA previously. The dry unknown sample mass you entered for entry #1 above should
correspond to the percent mass of calcium carbonate you enter for entry #1 here.

The percent mass of calcium carbonate in the dry unknown sample is taken as the
average of the three trials. Enter the average mass percent of calcium carbonate in the dry
unknown samples.

Please enter the standard deviation of the average mass percent of calcium carbonate in
your dry unknown samples.

Please enter the calculated 90% confidence limit for the average percent mass of the
calcium carbonate in your dry unknown samples.

Please enter your room number, locker series and locker number which is the hyphenated
numbers embossed on your locker. For example, if the hyphenated numbers read, 1068-
6-24, your room number is 1068.


30

31
Introduction to Inorganic
Qualitative Analysis


INTRODUCTION

In this experiment you will be introduced in an abbreviated way to systematic methods
that chemists have traditionally used to identify the cationic constituents of a mixture. In
most such schemes, including this one, a sequence of precipitating agents is used to
separate the original mixture into smaller groups, each of which may contain more than
one constituent. Each of the smaller groups is then examined further.

The elements that you will be focusing on are eight of the twelve metallic constituents of
the third long row of the periodic table: K, Ca, Cr, Mn, Fe, Co, and Zn. You will first
encounter them as 0.05 M aqueous solutions of nitrate salts. During the course of the
experiment some of these elements may change their oxidation states one or more times.

The scheme you will be using does not include the Cu
2+
ion because it behaves rather
unpredictably when subjected to the reagents used here to effect the separation of a
mixture of these cations. In more elaborate analytical schemes the copper gets removed
early on by precipitating it as the sulfide from a 0.3 M acid solution saturated with
hydrogen sulfide. The sulfide ion concentration in such a solution is so incredibly low
that only CuS (K
sp
~ 10
-35
) precipitates at that point.

The first part of the experiment comprises a series of diagnostic tests in which you will
determine experimentally how six of the eight salts respond to the various treatments that
will comprise the overall analytical scheme. These tests may all be performed in a
single laboratory period if you have thoroughly studied the experiment before you
come to lab so that you know exactly what you will be doing and in what order.


32
Safety: Gloves must be worn at all times. Some of the reagents used in this experiment
can cause burns or other skin damage.

PROCEDURE

Work in Pairs on this experiment.

Part I. Qualitative Analysis Analysis of a Known Solution

Setup
1. All glassware must be kept scrupulously clean. Each reagent/test solution should
have its own dropper.
2. Start a hot water bath in a 400mL beaker (1/3-full of water).
3. Set aside another beaker to serve as a waste container.
4. Make a 3% H
2
O
2
solution. (Dilute the 30% H
2
O
2
stock solution by a factor of 10
using deionized H
2
O.) Store this solution in a clean test tube and supply with a
plastic pipet.
5. Obtain about 5mL of each of the following: 6M NaOH and 6M HNO
3
. Store
these in clean test tubes and supply each with a plastic pipet.

Making the Known Solution
1. To make your known solution, combine 1 mL of each of the following metal
nitrate solutions in a round-bottom test tube: Ca
2+
, Co
2+
, Cr
3+
, Fe
3+
, K
+
, Mn
2+
,
Zn
2+

2. Be sure and note the colors of each individual solution in your Lab Notebook.

I nitial Separation of the Cr
3+
, Fe
3+
, K
+
, Mn
2+
, Zn
2+
I ons
1. First transfer 1 mL of your cation solution to a clean centrifuge tube.
a. Add 10 drops of 6M NaOH (shake after every 2 drops).
b. Add 5 drops of 3% H
2
O
2
. Shake tube and place in hot water bath for 3
minutes.
c. If a precipitate is present, do the following:
i. Centrifuge the sample.
ii. Check for complete precipitation (ppt) by adding a few more drops
of 6M NaOH and watching for the additional formation of ppt on
the top of the solution.
iii. When ppt is complete, decant the supernatant liquid and SAVE
this for Step 5.
2. To the ppt from the previous step,
a. Add 10 drops of 6M HNO
3
.
b. Stir the solution well and place the tube in the hot water bath for 3
minutes.
c. Centrifuge (if necessary) and remove supernatant liquid. SAVE this for
Step 4.


33
Confirmation Tests for the Mn
2+
and Co
2+
I ons
3. To the ppt from step 2,
a. Add about 5 drops of 3% H
2
O
2
(or until the ppt dissolves).
b. Place in a hot water bath (using a hot plate) for about 3 minutes (or until
bubbling stops).
c. Place a small amount of this solution in a spot plate well.
i. Add a small sprinkle of NaBiO
3
.
ii. Stir. If a reaction is observed, then the Mn
2+
cation has been
confirmed.
d. To the remaining solution in the tube,
i. Add equal volumes of 0.2 g KNO
2(s)
and 4 M KC
2
H
3
O
2
(aq)
ii. Seal the tube with parafilm and shake vigorously. If a reaction is
observed, then the Co
2+
cation has been confirmed. If NO reaction
was observed, dont panic! You will be prompted to try another
test for Co
2+
later.

Confirmation Tests for the Fe
3+
I on (and Alternative Test for Co
2+
)
4. To the tube containing the liquid from Step 2
a. Add 6M NaOH until a ppt is visible.
b. Then add 1 drop of 6 M HNO
3
until the ppt disappears again. It may be
necessary to add more than 1 drop. Your solution is now neutralized.
c. Place a small amount of this solution in 2 wells of a spot plate.
i. To the first well, add 2 drops of KSCN. If a reaction is observed,
then the Fe
3+
cation has been confirmed.
d. If the confirmation test for Co
2+
in Step 3d for did not show a reaction,
then
i. To the remaining neutralized solution in your tube, add equal
volumes of 0.2g KNO
2
(s) and 4M KC
2
H
3
O
2
(aq).
ii. Seal the tube with parafilm and shake vigorously. If a reaction is
observed, then the Co
2+
cation has been confirmed.

Confirmation Tests for Cr
3+
and Zn
2+
ions.
5. To the liquid from Step 1,
a. Add 1 drop of the thymolphthalein indicator.
b. Add glacial acetic acid dropwise (while shaking gently) until you see
some sort of color change.
c. Place a small amount of this solution a spot plate well.
i. Add a few drops of 0.1M Pb(NO
3
)
2
to the well. If a reaction is
observed, then the Cr
3+
cation has been confirmed.
ii. To the remaining solution in the tube, add 3 drops of dithizone in
chloroform. If a reaction is observed, then the Zn
2+
cation has
been confirmed.
d. Cleanup.
i. Rinse the tube containing dithizone (using acetone) into the
Dithizone Waste Container.
ii. Any remaining waste can be transferred to your waste beaker.

34

Confirmation Tests for Ca
2+
and K
+
ions.
6. Place a small amount of the original solution in two wells of a spot plate.
a. In one well, add 2 drops of sodium tetraphenylborate. If a reaction is
observed, then the K
+
cation has been confirmed.
b. In the other well, add 5 drops of a small amount of 0.2M K
2
C
2
O
4
(aq). If a
reaction is observed, then the Ca
2+
cation has been confirmed.

Cleanup
Make sure all waste gets transferred to the appropriate waste containers in the fumehood:
Cation Waste or Dithizone/chloroform/acetone Waste Container. Rinse the spot plate
with acetone into the dithizone/chloroform/acetone waste container. If the waste
container is full, take the full bottle to the dispensary and replace it with an empty one.

DATA ANALYSIS

Part I. Qualitative Analysis Due before beginning Part II. To be completed on-
line.

After completing Part I, please complete the on-line post-laboratory exercises for
week 1. The questions you will answer on line are shown below as questions 1 7. If
you have completed the on-line exercises for Part 1 of this laboratory, your TA will
provide you with a blank "flow chart."

Record the correct answers here while you do the on-line exercise and bring these
answers to lab class with you.

Question 1. An unknown solution could contain any or all of the following cation: K
+
,
Ca
2+
, Cr
3+
, Mn
2+
, Fe
3+
, Co
2+
, Zn
2+
. A 1 mL portion of the unknown is treated with 2 mL
of 6 M NaOH, added a few drops at a time with shaking. Immediately thereafter 10
drops of 3% hydrogen peroxide are added dropwise with shaking, and the centrifuge tube
is then heated for a few minutes in a water bath until bubbling ceases.

The resulting conglomerate is then centrifuged and the supernatant liquid is decanted off
and saved. (Although you have not demonstrated these facts for yourself, Ca
2+
will be
precipitated as the hydroxide at this stage and K
+
will remain in the decanted liquid.)

At this stage of the experiment the elements that could be found in the decanted liquid
are:


_____ ______ ______ _______ _______ _______ _______ _______ _______

35
The elements that could be found in the remaining precipitate are:


_____ ______ ______ _______ _______ _______ _______ _______ ________


Question 2. The precipitate from Question 1 is washed twice, first with a 1 mL portion
of 1 M NaOH (you will make your own) and then with 1 mL of deionized water.
Centrifuge the tube after each washing and discard the two supernatant liquids. Now
treat the precipitate with 1 mL of 6 M HNO
3
and heat the centrifuge tube briefly in a
water bath. The centrifuge tube is then centrifuged, and the supernatant liquid is
decanted and saved. (The Ca(OH)
2
produced in Question 1 is acid soluble.)

At this stage of the experiment the elements that could be found in the decanted liquid
are:

_____ ______ ______ _______ _______ _______ _______ _______ ________

The elements that could be found in the remaining precipitate are:


_____ ______ ______ _______ _______ _______ _______ _______ ________


Question 3. The precipitate from Question 2 is treated with 1 mL of 6 M HNO
3
followed
immediately by the drop-wise addition of 3% hydrogen peroxide until the precipitate
fully dissolves. The centrifuge tube is heated in a water bath until bubbling ceases.

At this stage of the experiment the elements that could be found in the resulting liquid
are:

_____ ______ ______ _______ _______ _______ _______ _______

The elements that could be found in the remaining precipitate are:


_____ ______ ______ _______ _______ _______ _______ _______


Question 4. The decantate from Question 1 is neutralized with acetic acid and divided
into the appropriate number of portions. How many portions? What should you do with
each of them? What would be the observation if each treatment led to a positive
(confirmatory) result?

Question 5. The final decantate from Question 2 is divided into the appropriate number
of wells of a spot plate and tested as in Part I of this experiment. How many wells?

36
What reagents would be required for each spot-test, and what would be the observation if
each spot-test led to a positive (confirmatory) result?

Question 6. The liquid from Question 3 is divided into the appropriate number of
portions and again spot tested. What reagents would be required and what would be the
observation if each spot-test led to a positive (confirmatory) result?

Question 7. The original unknown solution is tested separately for the presence of
potassium and calcium. How will you perform these tests?

37
PROCEDURE

Part II. Qualitative Analysis Analysis of an Unknown Mixture

1. Obtain an unknown cation solution from your TA. The unknown solution
contains 5 cations.
2. Note the initial color of your unknown solution. How does this compare to the
colors of the original known solutions? What cations are likely to be present in
your unknown?
3. Record your Unknown # (based on locker #) in your Lab Notebook.
4. Follow the same steps as Part I until you have confirmed all 5 unknown cations.
5. Perform the Final Confirmation for your unknown (see below).

Final Confirmation Steps
1. Once you have determined the 5 cations present in your solution, mix up a
theoretical unknown solution containing 1mL of each of the known cations that
you think are present in your unknown solution.
a. Place 1 mL of this solution in a centrifuge tube.
b. Place 1mL of your original unknown solution in a second centrifuge tube.
2. Compare the color of the 2 solutions from Step 1-2 of Part II.
a. Are they the same?
3. Run several of the tests described in Part I side-by-side and compare.
a. Do they behave the same way?
b. Are the ppt colors exactly the same?
c. If so, then you have confirmed the cations in your unknown solution.


Complete your post-laboratory exercises for Part II! You will be asked for your
unknown # (based on locker #) and all the confirmed cations in that unknown.

38

39
Synthesis of a Transition Metal
Coordination Complex
trans-[Co(en)
2
Cl
2
]Cl

INTRODUCTION

In this experiment you will prepare a coordination compound of Cobalt(III) with the
bidentate ligand ethylenediamine (en; NH
2
CH
2
CH
2
NH
2
). Coordination compounds are
also called complexes, and if they are ions they are called complex ions. A complex ion
contains a central metal to which Lewis bases (ligands) have been attached or
coordinated. The purpose of this experiment is to provide an introduction to the field of
transition metal coordination chemistry and have you synthesize a coordination
compound. This synthesis will allow you to experience some of the common procedures
used to prepare and isolate inorganic compounds. The complex you will synthesize is
trans-[Co(en)
2
Cl
2
]Cl, a green-colored cobalt transition metal complex, which will be
used to study spectrophotometry and kinetics in the experiments which follow.

The principal oxidation states of cobalt are the +2 and +3 states. The aqueous
[Co(H
2
O)
6
]
3+
ion is very unstable because it is a powerful oxidizing agent and is readily
reduced by water to [Co(H
2
O)
6
]
2+
:

4 [Co(H
2
O)
6
]
3+
+2 H
2
O 4 [Co(H
2
O)
6
]
2+
+ O
2
+ 4 H
+


However, the +3 oxidation state is stabilized by replacing the coordinated water
molecules with less labile ligands such as NH
3
, NO, CN
-
, and NH
2
CH
2
CH
2
NH
2
(en). A
labile complex exchanges its ligands rapidly. Lability is associated with the d-electron
configuration of the central metal. In general, ligands coordinated to a Co
3+
ion do not
dissociate from the Co
3+
ion rapidly, and as a consequence, they are not easily replaced
by other ligands. Thus, Co
3+
complexes can endure many laboratory manipulations, and
as we shall see, some of them can be prepared in structural forms whose stable existence
depends on the durability of the bonds to the cobalt atoms.

Trans isomer
Cl
Co NH
2
Cl
H
2
N
H
2
N
NH
2
Cis isomer
Co
NH
2
Cl
Cl H
2
N
H
2
N
NH
2

Figure 1. The trans- and cis- isomers of [Co(en)
2
Cl
2
]Cl.


40
In this assignment, you will prepare a complex ion with a net +1 charge in which two
molecules of ethylenediamine (en) and two chloride ions are bonded to a central Co
3+
ion.
Each of the two ethylenediamine molecules is attached to the Co
3+
ion via the lone pairs
on the basic nitrogen atoms at each end of ethylenediamine. Thus, six atoms (four
nitrogen atoms and two chlorine atoms) are directly bonded to the cobalt atom and form
the corners of an imaginary octahedron (eight-faced solid) with the cobalt atom at the
center (see Figure 1). Notice that there are two possible structures for the complex. In
one structure (the cis- isomer), the two chlorine atoms occupy adjacent corners of the
octahedron. In the other structure (the trans- isomer), the two chlorine atoms occupy
opposite corners of the octahedron. These structurally different complexes have different
physical and chemical properties. For example, the cis complex is dark purple in color,
while the trans complex looks green. In this experiment, you will prepare the chloride salt
of the trans complex. The trans complex you prepare here will be used later in
spectrophotometry and kinetics studies of its acid hydrolysis. Hereafter, we use the
symbol en for the ethylenediamine molecule/ligand. It is very crucial that you measure
all reagents and carry out all procedures exactly as described. Otherwise, you will
synthesize an unintended complex or obtain a mixture of products.

Please read the appropriate chapter in your textbook, as pre-laboratory preparation for
this experiment.

Preparation for Next Lab: You will need to retain the product for use in the
Spectrophotometry and Kinetics experiments that follow.



41
Safety:
1. Place all waste solutions/precipitates into the proper waste container.
2. Wear gloves when using ethylenediamine, 30% & 10% hydrogen peroxide, and 12 M
hydrochloric acid; these three chemicals can cause severe burns.
3. Never attempt to smell any solution, as the odors can be irritating in high
concentrations.
4. Avoid standing between your product and the fumehood as a solution is heating.
5. Wear your goggles!

PROCEDURE

You will work in pairs on this experiment. The actual data analyses and the written reports
must be done entirely independently of your lab partner or other students. Make sure that you
avoid unauthorized collaboration and plagiarism. All suspected violations of the Code of
Academic Conduct will be referred to Student Judicial Affairs.

Synthesis of trans-[Co(en)
2
Cl
2
]Cl

1. You will need the following chemicals for this synthesis:
a) CoCl
2

.
6H
2
O(s)
b) 3 M ethylenediamine (en)
c) 10 % H
2
O
2

d) 12 M HCl (in the fumehood)
e) Ethanol

2. Prepare a hot water bath by placing about 125-175 mL of deionized water in a 250
mL beaker and begin heating the water with a hot plate immediately upon entering
the laboratory.

3. Accurately weigh 2.4 grams of CoCl
2
.
6H
2
O(s) and place it in a 50 mL Erlenmeyer
flask. Add 8 mL of deionized water to dissolve. Do the next step in the fumehood.
After the entire solid has dissolved add 8 mL of the ligand ethylenediamine (C
2
N
2
H
8
)
to the cobalt solution. Carefully make observations regarding any color or
temperature changes and record these in your notebook.

Question A: Explain why the color changes occur during this reaction.

Question B: Write a balanced chemical equation for this process. The product is
Co(en)
2
Cl
2
.

4. Return to the laboratory bench with your cobalt solution and make 12 mL of a 10%
H
2
O
2
solution from a 30% H
2
O
2
stock solution. Slowly add 8 mL of the 10% H
2
O
2
to
the cobalt solution. Let the flask sit for 5 minutes at room temperature with
occasional swirling and note any color or temperature changes. Transfer the solution
to your small casserole. Rinse the flask with 8 mL of deionized water and add this
rinse solution to the solution in the casserole.


42
Question C: Explain why the color changes during this process.

Question D: An excess of H
2
O
2
has been used in this step since cobalt(II) is oxidized
in the presence of the decomposing hydrogen peroxide. In the reduction half reaction
of H
2
O
2
in a basic solution hydroxide ions are formed, 2e
-
+ H
2
O
2
(aq) 2OH
-
(aq).
Write a balanced ionic equation for the redox reaction occurring in step 4.

As a side note: The decomposition of hydrogen peroxide takes place as self-reaction
involving both oxidation and reduction processes. Therefore, a by-product reaction
occurring here is 2 H
2
O
2
(aq) 2 H
2
O(l) + 2O
2
(g). This reaction is catalyzed by
the presence of transition metal ions.

5. Place the small casserole over the 250 mL beaker that is partially filled with the
boiling water (use a hot plate to boil water). Be careful to avoid breathing the vapors
that may rise out of the casserole. Next, quickly but carefully, add 12 mL of
concentrated HCl and note any color changes. Continue heating the casserole on top
of the beaker for about 50 minutes. During the 50 minutes the volume of the cobalt
solution should be reduced to one quarter of the original volume (you may want to
use another casserole with the targeted volume of water for comparison). As the
volume of solution in the casserole is reduced, a crust of crystals (like a thin slurry)
will begin to form on the surface of the liquid. Do not allow the solution to
completely evaporate from the casserole. Thus, you may have to add a few mL of
deionized water to avoid this, but only add a minimum. You may also need to add
small amounts of water to the beaker in order to maintain this volume of water while
boiling.

Question E: Write a balanced chemical equation for this process. The product is
[Co(en)
2
Cl
2
]Cl.

6. Carefully remove the casserole and place it in an ice bath. Let the casserole cool for 5
minutes and then add 4 mL of 95% ethanol to force more of the water soluble product
to crystallize. It is important here that you allow the casserole to cool before rinsing
your product with the 95% ethanol. Allow 5 more minutes for the product to fully
crystallize.

7. While the crystals are forming in step 6, set up the vacuum filtration apparatus as
shown in Figure 3. This apparatus consists of a 125 mL filter flask, a black #3
neoprene adapter, and a plastic filtering funnel with a white fritted glass filter inside.
Clamp the filter flask securely to the support rods. Wet the tip of the thick rubber
tubing and connect it to the flask from vacuum supply in the lab. Obtain a small circle
of filter paper from the front of the room. Always use filter paper when filtering
through a funnel. The filter paper is thin. Be sure you only have one sheet of filter
paper. Place the filter paper against the fritted glass inside the funnel. Begin by
turning on the vacuum. Seat the filter paper to the fritted glass by squirting a little
deionized water on the filter paper. If everything is working properly, the paper

43
should be pulled down against the fritted glass and the small spray of deionized water
should be pulled through into the flask.

Figure 3: Filtering Apparatus

8. Once the product has crystallized, remove the casserole from the ice bath and, using a
rubber policeman, carefully transfer both the solid and the solution to the funnel.
After the aqueous solution has been pulled through the filter, carefully disconnect the
filtration apparatus and turn off the vacuum. Dispose the aqueous solution into the
metal ion waste container. Assemble the filtration apparatus again and rinse the
crystals twice with 4 mL portions of 95% ethanol. You may use the ethanol to help
transfer any product that remains in the casserole. Do not use water since the product
is water soluble. Continue to pull air through the crystals to dry the crystalline
product. The solution remaining in the Erlenmeyer flask may be washed down the
drain with copious amounts of water.

9. Clean an evaporating dish. Carefully transfer the damp product onto the dish. Place
the evaporating dish over the boiling water bath for 5 minutes to finish the drying.

10. Weigh a clean, dry plastic snap-cap vial. Transfer the dry product to the vial and
weigh. Calculate the mass of the product and the percent yield. Label for the vial
indicating molecular formula, the mass, the date, and the names of both you and your
partner. Hand in your labeled vial to your TA before you leave. Your TA will retain
your product for use in the Spectrophotometry and Kinetics experiments that follow.
The post-laboratory exercises will guide you through the above calculations and
questions.


Clean Up: Remove the used circle of filter paper from your funnel and dispose of it in a
crock pot. Rinse the filter flask, filter, and neoprene adapter thoroughly with deionized
water and return these to the front of the room. Do not place this community equipment
in your locker.

Vacuum

44
DATA ANALYSIS

The following series of questions involve the chemistry in the synthesis of trans-
[Co(en)
2
Cl
2
]Cl.

Which of the following reasons correctly explains the color changes that take place when
ethylenediamine (C
2
N
2
H
8
) is added to the solution of cobalt(II) chloride? Three choices
will be given

Which of the following balanced chemical equations correctly represents the chemical
reaction that takes place when ethylenediamine (C
2
N
2
H
8
) is added to the solution of
cobalt(II) chloride to form dichlorobis(ethylenediamine)cobalt(II)? Three choices will be
given.

Which of the following reasons correctly explains the color changes that take place when
8 mL of the 10% H
2
O
2
is added to the solution of dichlorobis(ethylenediamine)cobalt(II)?
Four choices will be given.

An excess of H
2
O
2
has been used in this step since cobalt(II) is oxidized in the presence
of the decomposing hydrogen peroxide. In the reduction half reaction of H
2
O
2
in a basic
solution hydroxide ions are formed, 2e- + H
2
O
2
(aq) 2OH
-
(aq). Which of the
following is the correct balanced ionic equation for the redox reaction occurring when the
hydrogen peroxide is added to dichlorobis(ethylenediamine)cobalt(II) solution? Three
choices will be given.

Which of the following is the correct balanced equation for the reaction that takes place
when concentrated hydrochloric acid is added to dichlorobis(ethylenediamine)cobalt(III)
hydroxide solution? Three choices will be given.

The following few questions will lead you through the calculation of the percent yield of
product.

You were instructed to use approximately 2.4 grams of cobalt(II) chloride hexahydrate to
begin the synthesis. What is the precise mass in grams of starting material, cobalt(II)
chloride hexahydrate, that you used? Your mass precision should be reported to a
thousandth of a gram.

What is the molar mass of Co[H
2
O]
6
Cl
2
Five choices will be given.

How many moles of Co[H
2
O]
6
Cl
2
were available of the starting material?

The theoretical yield (in grams) of product is obtained by assuming that every mole of
Co[H
2
O]
6
Cl
2
available as the starting material is converted to product trans-
[Co(en)
2
Cl
2
]Cl
2
. What value in grams is your theoretical yield of product?

What is the mass in grams of product, trans-[Co(en)
2
Cl
2
]Cl, that you collected? Your
mass precision should be to a thousandth of a gram.

45

Based on your calculated theoretical yield and your reported mass of product, calculate
the percent yield of product, trans-[Co(en)
2
Cl
2
]Cl? Report your percent yield to a tenth of
a percent, i.e. 45.3%.

Concluding Remarks: Briefly discuss interpretations of your observations and results.
Include in your discussion, any conclusions drawn from the results and any sources of
error in the experiment.


46

47
A Spectroscopy Study
Spectrophotometric Analysis of trans-Co[(en)
2
Cl
2
]Cl
and the Aquation Product, [Co(en)
2
(H
2
O)Cl]Cl
2


INTRODUCTION

In the spectrophotometric portion of this experiment you will analyze trans-
[Co(en)
2
Cl
2
]Cl that you previously prepared and its acid catalyzed hydrolysis product,
[Co(en)
2
(H
2
O)Cl]Cl
2
.

You will compare the visible absorption spectra of the two cobalt complexes in aqueous
solution, examine how their separate absorptions depend on the concentrations of the
cobalt complex solutions, and use the combined absorptions to determine the
concentrations of the two cobalt complexes in an aqueous mixture.

A Brief Introduction to Spectrophotometry

The use of spectral data to identify and quantify substances is fundamental to chemical
analysis. You are already familiar with the absorption spectra that are produced when
atoms of an element absorb photons of electromagnetic radiation of certain wavelengths
and cause an electronic transition from lower to higher energy states. You learned in
Chemistry 2A that each element has a characteristic absorption spectrum.

Many substances absorb photons in the visible light region of electromagnetic radiation
spectrum while reflecting other photons in the visible light region. As a result of the
reflected photons, a particular substance appears a certain color. Visible light, therefore,
may be used to study colored substances. This is referred to as spectrophotometry. For
example, a blade of grass is green, because its chlorophyll absorbs red and blue
wavelengths strongly and green less strongly, so most of the green is reflected, as shown
by Figure 1 below.

The height and shape of the curve make up a characteristic absorption spectrum for a
substance and can be used for identification purposes. The curve varies in height because
chlorophyll absorbs incoming wavelengths to different extents. The absorption spectra
is of chlorophyll a and chlorophyll b is shown below. There is high absorption of red and
blue frequency photons, hv.


48
Figure 1. The absorption spectra of chlorophyll a and chlorophyll b.










A spectrophotometer (or spectrometer, for short) is used to measure absorption spectra
and is a combination of a light source that emits a continuous band of radiation, a
monochromator (usually a reflection grating with associated optics) to select a narrow
range of wavelengths, and a photoelectric detector to measure the light intensity, as
indicated in Figure 2.


Figure 2: Schematic Representation of a Spectrophotometer.

In addition to identifying a substance, an absorption spectrum can be used to determine
its concentration because the absorbance, the amount of light of a given wavelength
absorbed by a substance, is proportional to the number of molecules present in the
sample. This relationship is called the Beer-Lambert Law or more simply Beers Law.
Consider monochromatic light of a given intensity incident on a sample, as shown in
Figure 2. If this light can be absorbed by the sample, then the transmitted light will have
a lower intensity than the incident light. The transmittance, T, is defined as the ratio of
the transmitted intensity, I, to the incident intensity, I
0
,




The percent, %T, is simply 100 T. The transmittance is decreased if either the
concentration, C, of absorbing substance is increased or the path length, , of the sample
is increased, since both increase the number of absorbing species in the path of the light.

Sample
||
Light
Source Wavelength
Selector
0
I
I
T =
Green
Blue
Yellow
Red

49
A related quantity is the absorbance, A, which is given by



%T is read directly from the spectrometer. However, the absorbance is particularly
important since it, and not the transmittance, is directly proportional to the concentration
of the absorbing substance and the path length. This proportionality constitutes Beers
Law, and is commonly written as

A = c C.

The concentration, C, is expressed in moles per liter (M) and the path length, , is
generally expressed in cm. The quantity c is called the molar absorptivity and has units
of M
-1
cm
-1
. Note that the quantity cC is dimensionless, as are both the absorbance, A,
and the transmittance, T. The molar absorptivity is characteristic of the substance. It
tells us how much light the substance absorbs at a particular wavelength. A graphical
plot of either the absorbance at constant path length or the molar absorptivity versus
wavelength is called the absorption spectrum of the substance.
Beer's Law forms the basis for the analytical use of spectroscopy to determine concentra-
tions. As indicated by the equation of Beers Law shown above, a plot of the absorbance
at a given wavelength for a particular species versus the concentration of the species
yields a straight line with a slope equal to c and an intercept of zero. Since the path
length of the cell used for the absorbance measurements is typically known, the molar
absorptivity of the species at a chosen wavelength is readily determined from such a
Beer's Law plot. The concentration of the species in an unknown sample can then be
determined by measuring the absorbance of the sample at the same wavelength in any
cell of known path length.
The wavelength for such an analysis should be chosen so that small changes in
wavelength do not yield large changes in absorbance. Namely, the chosen wavelength
should be in a relatively flat portion of the absorption spectrum. Typically, a wavelength
associated with a maximum in the spectrum is chosen, since at a maximum, the slope of
the spectrum is zero or horizontal and simultaneously good sensitivity is obtained in the
analysis (significant absorbance for a given concentration).
One should always establish, before its analytical use, that Beer's Law is followed by a
species over the concentration range of interest, since deviations from Beer's law often
occur at high concentrations. Typically, these deviations can be traced to changes in the
absorbing species or the bulk solution with concentration. For example, in concentrated
solutions the solute molecules are closer together on average and interact with each other,
changing their energy levels and spectroscopic properties from a dilute solution. The
species of interest also may exist in equilibrium with other species that have different
molar absorptivities. In such cases, a graph of absorbance versus concentration will
appear to deviate from a straight line at high concentrations.
( ) %T log 2
100
%T
log - T log - A
10 10
= = =

50
If two species are present, and neither affects the light absorbing properties of the other,
then the observed total absorbance is simply the sum of the absorbances of the individual
species. When this is true, the individual concentrations can be determined from
spectrophotometric measurements. Because interactions often do arise, sometimes when
least expected, the absorption spectra of the species should be investigated when they are
separate and when they are simultaneously present to determine whether the absorbances
are indeed additive before any analytical spectrophotometric measurements.


51
Operation of GENESYS
TM
20 Spectrophotometer

Spectrophotometers all contain some kind of light source (visible instruments often use
just a tungsten bulb); various mechanical and optical elements which are used to create a
directed and collimated beam; a wavelength selector of some sort (often either a
diffraction grating or a prism); an enclosed cell compartment to hold the absorbing
sample; a radiation detector (often a photocell or more commonly now a photodiode);
and some kind of readout device (e.g. a needle deflection on a meter).

It is important that you understand the operation of the GENESYS
TM
20 before you begin
this laboratory. The GENESYS
TM
20 is an expensive and sensitive instrument and must
be operated carefully and intelligently.

The light source in a GENESYS
TM
20 is an ordinary tungsten lamp whose radiation
extends over the entire visible range. The light from the lamp passes through an entrance
slit and is dispersed by a diffraction grating. The grating can be rotated so that a small
band of selected wavelengths from the dispersed beam passes through an exit slit, and
then through the cell (cuvette) containing the sample. The cuvettes used with a
GENESYS
TM
20 have a path length (internal diameter) of 1.00 cm. The light transmitted
through the sample strikes a solid-state silicon detector that generates an electrical signal
proportional to the radiant power (light intensity). The signal from the detector drives a
meter that can be calibrated to read transmittance or absorbance.

The calibration procedure entails setting 0 Absorbance at a given wavelength with a
cuvette containing a reference or blank solution. The blank solution is missing the
component of interest, but is otherwise as identical as possible to the solution to be
analyzed for the component of interest. Typically, the blank solution is just the solvent.
This is required since the output of the lamp and the sensitivity of the detector varies with
wavelength. The electronics of the instrument automatically sets 100% absorbance. An
identical cuvette containing the solution of interest is then inserted into the spectrometer,
and the absorbance is read from a meter on the instrument. Both the calibration and the
reading must be done at the same wavelength. The reading for the solution then
represents the absorbance at the chosen wavelength due to the component of interest.
The calibration has accounted for any absorption (or reflection or scattering) of light by
the cuvette and other species in the reference solution.

GENESYS
TM
20 Spectrophotometer


1. On / Off switch
2. LCD display
3. Sample compartment hood
4. Keyboard
5. ----
6. Lamp compartment door


52
The power switch is located on the bottom left in the back of the instrument. When you
turn on your GENESYS 20 spectrophotometer, it performs its power-on sequence.
This sequence includes checking the software revision, initializing the filter wheel and
the monochromator. The power-up sequence takes about two minutes to complete.
Allow the instrument to warm up for 10 minutes before using it.

Keyboard Layout of GENESYS 20 spectrophotometer
























53
Absorbance and %Transmittance Measurements

Be sure the cell holder is empty before turning on the instrument.


1. Press A/T/C to select the absorbance or % transmittance
mode. The current mode appears on the display.



2. Press nm or nm to select the wavelength.
Note: Holding either key will cause the wavelength to
change more quickly.



3. Insert your blank into the cell holder and close the
sample door.
NOTE: Position the cell so the light (indicated by the
arrow in drawing) passes through the clear walls.




4. Press 0 ABS/100%T to set the blank to 0 A or 100%T.





5. Remove your blank and insert your sample into the cell
holder. The sample measurement appears on the LCD
display.



54
Error Messages

This section lists the messages generated to alert you of errors or other abnormal
conditions. The instrument recognizes two types of errors. With the first type, the
instrument is still functional; with the second, the instrument is not functional until the
condition is resolved.

1. Flashing Data Display: The sample has an absorbance or a transmittance value below
or above the photometric range of the instrument. The display flashes until the
condition is resolved.

2. Sample too dark: The instrument has been asked to zero a sample with a high
absorbance at a low energy point. The instrument beeps three times to announce the
message, the message remains on the display for two seconds, then the normal
display returns.

3. Sample too bright: The instrument has been asked to zero a sample while the door of
the sample compartment is open. The instrument beeps three times to announce the
message, the message remains on the display for two seconds, then the normal
display returns.


Determining the Blank Cuvette

1. Obtain a pair of cuvettes. One will be used for the blank solution and the other will
be used for the standard and unknown samples.

2. Fill both cuvettes with the solvent and wipe the outside with a Kimwipe to make sure
it is clean and dry (no fingerprints). Be sure to always add enough solution to reach to
within 1/8 of the triangular mark on the cuvette. This will insure that all incident
radiation passes through the solution. It is also critical that the triangular mark on
the cuvette be facing you when inserted in the sample holder for all measurements.

3. Insert one filled cuvette into the sample holder that is located under the hood to the
left. Close the hood.

4. Calibrate to 0 absorbance by pressing the 0 ABS/100%T key. Remove the cuvette,
insert the other cuvette, and read the absorbance for this second cuvette. If the
reading is less than 0 absorbance, then this second cuvette will be used as the blank
cuvette; if the reading is greater than 0 absorbance, then the first cuvette will be used
as the blank cuvette.


55
Calibrating the Instrument

The calibration procedure must be performed for absorbance measurements taken at each
different wavelength.

1. Select the desired wavelength by pressing the up or down wavelength selector
arrow keys of the key pad of the instrument.

2. Insert the blank cuvette containing the blank reference solution (which is acidic
solvent for this experiment) into the sample holder and close the hood.

3. Calibrate to 0 absorbance by pressing the 0 ABS/100%T key.

4. Remove the blank cuvette. Do not re-adjust any dials at this point. You are now
ready to insert the other cuvette containing the sample of choice for a measurement at
this particular wavelength.

5. Repeat steps 1-4 for all measurements that take place at different wavelengths.


Question A: Why do we allow electronic instruments to warm-up before use?

Question B: Why is it important not to have fingerprints on the cuvette?

Question C: Why is it important to align the cuvette in the sample holder the same way
each time?

56
The Experiment

In the present exercise you will experimentally determine the wavelengths of the visible
absorption maxima of two non-interacting compounds and measure the molar
absorptivity for both of them at these two different wavelengths. Then, you will measure
the absorption of an unknown mixture of two compounds in order to determine the
concentration of each species.

The two compounds referred to above are the green chloro complex synthesized in the
last experiment and a red aquo derivative, which you will make from the solution of the
green complex.

In acidic solutions with low free chloride ion concentrations, one of the chloride ions in
the trans-[Co(en)
2
Cl
2
]
+
complex ion can be replaced by a water molecule to give an
equilibrium mixture of the cis and trans isomers of the aquo complex,
[Co(en)
2
(H
2
O)Cl]
2+
. This reaction is accompanied by a color change from green to red:









H
+

trans-[Co(en)
2
Cl
2
]Cl + H
2
O cis- & trans- [Co(en)
2
(H
2
O)Cl]Cl
2

chloro complex (green color) aquo complex (red color)
Throughout this experiment, the green-colored trans-[Co(en)
2
Cl
2
]Cl will be referred to
as the chloro complex, while the red-colored mixture of the cis and trans isomers of the
hydrolysis product, [Co(en)
2
(H
2
O)Cl]Cl
2
, will be simply referred to as the aquo
complex.

In the first part of this experiment you will determine the wavelength of maximum
absorbance (
max
) for the two complexes. Then, you will prepare four solutions of each
complex of known concentrations. You will then measure the absorbance of each
solution using a GENESYS
TM
20 spectrophotometer at the wavelength corresponding to
the maximum absorbance for the chloro complex and will graph the data, with
concentration on the x-axis and absorbance on the y-axis, to form a Beer's Law plot. By
finding the slope and knowing the path length of your cuvette cell, you will be able to
calculate the molar absorptivity coefficient at that wavelength for that complex. You will
repeat this for the second wavelength that corresponds to the maximum absorbance
position for the aquo complex. These measurements (i.e. at both wavelengths) will be
Co
Cl
Cl
N
H
2
H
2
N
N
H
2
H
2
N
Co
Cl
OH
2
N
H
2
H
2
N
NH
2
H
2
N
Co
NH
2
OH
2
Cl
H
2
N
N
H
2
NH
2


57
carried out for solutions of chloro and aquo complexes. In the final portion of this
experiment, you will analyze solutions that contain a mixture of the two complexes. You
will determine the concentrations of both complexes in the mixture using your
spectrophotometric measurements.

400 500 600 700 800
Wavelength / nm
Green Cplx
Red Cplx


Figure 4. Absorption Spectra of Cobalt(III) Ethylenediamine Complexes

A
b
s
o
r
b
a
n
c
e

58
Safety: Treat the GENESYS
TM
20 spectrophotometers with great care as they are expensive
and delicate instruments. Wear your goggles.

PROCEDURE

You will work in pairs on this experiment. The actual data analyses and the written reports
must be done entirely independently of your lab partner or other students. Make sure that you
avoid unauthorized collaboration and plagiarism. All suspected violations of the Code of
Academic Conduct will be referred to Student Judicial Affairs.

Part I. Solution Preparation and Aquation of the Chloro Complex.

1. Prepare the solvent to be used in the spectrophotometric part of this experiment by
adding 6 mL of 3 M sulfuric acid to 75 mL of water.

2. Use a 50 mL buret to dispense a measured 35 0.2 mL of this solvent into a clean 50
mL Erlenmeyer flask. Place this 50 mL flask to above the liquid level in a 250 mL
beaker containing an ice bath made roughly of equal parts of water and ice.

3. Accurately weigh ca. 200 4 mg sample of the green chloro complex and transfer it
carefully to the flask of cooled, acidic solvent. Remove the flask from the cooling
bath, swirl it several times to insure that the solid has completely dissolved and the
solution is homogeneous, and then quickly fill another 50 mL buret (or a 25 mL
buret) with this cold solution. Return the flask containing the rest of the green
solution to the ice bath.

4. Dispense a measured 17.5 0.2 mL portion of the cold green solution into another
clean Erlenmeyer flask and then quickly return the green solution remaining in the
buret to the still-cooling flask from which it originally came. At this point you should
have two essentially identical 17.5 mL samples of the green solution in two different
flasks--one of them in an ice bath and the other one out on the bench top warming to
room temperature.

5. Put the "warmer" flask into a beaker that contains boiling water for about 10 minutes,
which should cause the green starting material to be converted entirely to the red aquo
product. Cool the flask containing the red solution to room temperature. If you wish
you can use an ice bath to speed up the cooling.


59
Part II. Spectral Assignments.

Overview: Figure 4 contains the absorption spectra of the red and green complexes. You
will need to determine the true absorption maxima of the two complexes. The instrument
you will use to make this determination is the manually operated GENESYS
TM
20
spectrophotometer.

1. You should start with the red solution. The red solution is stable so it is clearly the
one to use to familiarize yourself with the instrument and experimental procedure.

2. Your red stock solution is a little too concentrated to give good results. Therefore,
you will want to use a disposable pipet to put about 2 mL of it in a test tube and then
dilute that with about 2 mL of the acidic solvent dispensed from the 50 mL buret.

3. Obtain a pair of cuvettes. One will be used for the blank solution and the other will
be used for the standard and unknown samples. Determine which cuvette will be used
for the blank solution by following the procedures given above under the section,
Determining the Blank Cuvette.

4. Fill the cuvette selected for the blank to within 1/8 of the triangular mark on the
cuvette with the acidic solvent dispensed from the 50 mL buret.

5. Rinse the other cuvette with a small portion of the diluted red solution (aquo product)
and then fill it to within 1/8 of the triangular mark on the cuvette with this solution.

6. From the scanned spectra given in Figure 4 shown above, estimate the wavelength of
the absorption maximum of the red colored complex.

7. Select a wavelength that is about 10 nm lower than the estimated absorption
maximum determined in step 6. Calibrate the instrument following the procedure
given above under the section, Calibrating the Instrument. Once you have establish
0 absorbance using your blank solution, insert the sample cuvette and read the
absorbance. Record your measurement.

8. Remove the sample cuvette, increase the wavelength by two nanometers (nm), and
recalibrate the instrument using the blank cuvette. Re-insert the sample cuvette and
read the absorbance. Record your measurement.

9. Repeat step 8 until you have taken absorbance measurements every two nanometers
from 10 nm below your estimate to 10 nm above your estimate. This can be done
fairly quickly if you team up, with one person recalibrating, measuring, and calling
out the resulting absorbances and the other one recording the data. Switch roles half
way through the process so each partner has an opportunity to perform both tasks.

10. Empty the sample cuvette. Rinse it with deionized water, and carefully blot it dry
using a Kimwipe.

60

11. Repeat steps 2 and 5-10 above for the green solution (chloro complex) instead of the
red and thereby find the true wavelength of the green complex absorption maximum.
You need to work efficiently because at room temperature the green solution changes
slowly with time. For step 2, mix 2 mL of the cold stock solution with 2 mL of
solvent at room temperature and use the resulting solution immediately unless water
condenses on the outside of the test tube in which you did the mixing. If that
happens, hold the test tube tightly in your hand until it warms up to above the dew
point. The absorbance measurement will be greatly affected if condensation occurs
on the outside of the cuvette. For step 7, be sure to use the estimated wavelength of
maximum absorption for the green solution.

12. Review your absorbance readings for the two complexes. Determine the wavelength
where maximum absorbance occurred for each colored complex. Record these
wavelengths for use in Part III.








61
Part III. Collecting the Data Needed to Construct Beer's Law Plots.

Overview: In this part of the experiment you will prepare eight solutions with known
concentrations--four each of both the red and green solutes--and measure their
absorbances at the wavelengths of the two absorption maxima you determined in Part II
above; i.e., you will make a total of sixteen spectroscopic measurements.

1. Fill one 50 mL buret with the cold, green chloro solution and another one with the
solution of its red aquation product. Evenly splitting up the workload within the
partnership, dispense four measured 3.0 0.2 mL portions of each of these solutions
into separate clean test tubes. This entails numerous buret readings, but in order to
maintain a reasonable degree of precision here you really do have to make them all.
As always, immediately store the "green" tubes in the ice/water bath.

2. To the four "red" test tubes in turn use the 50 mL buret to add measured volumes of
the acidic solvent as follows: 2.0 0.2; 3.0 0.2; 4.0 0.2 and 5.0 0.2 mL. (You
should now have four tubes containing accurately measured total volumes of about 5,
6, 7, and 8 mL.)

3. With the proper technique measure the absorbance of each of these solutions at the
wavelengths you determined above for the absorption maxima of both the red and the
green complexes (for a total of 8 readings).

4. One test tube at a time, repeat steps 2 and 3 with the four samples of the green
complex. As before, you can use the diluted samples immediately unless water vapor
condenses on the outside of the test tube after mixing--in which case warm it up with
your hand.

5. When you are finished with Part III, you should have collected a total of 16 different
absorbance readings here; 8 for the red solutions and 8 for the green solutions.

Part IV. Collecting Data for the Analysis of a Mixture of the Two Complexes.

Your TA will give you a solution that contains a mixture of the red and green complexes
prepared by allowing a solution of the chloro complex to partially convert to the aquo
product. Measure the absorbance of the mixture at the wavelength of maximum
absorbance found for green solution in Part I and measure the absorbance of the mixture
at the wavelength of maximum absorbance found for the red solution in Part I. (You
should have a total of 2 readings.)

Clean-up: The contents of the test tubes must be discarded to the waste container
labeled Cobalt waste.





62

DATA ANALYSIS

Part III. Making the Beer's Law Plots.

Overview and a Modest Theoretical Excursion: In this part of the experiment you will
manipulate the data collected in Part III to obtain the values of effective molar
absorptivity, symbolized by c*, for both the red and the green complexes at the two
wavelengths of interest here.

Beer's Law in the form in which you have seen it previously, A = cC, strictly applies
only to a slender beam of monochromatic light passing through a cell with flat, parallel
windows. In the present experiment the light beam is not small and the cell is not a
rectangular parallelepiped, so the path length, , cannot be defined.

Operationally, the detector outputs a signal that is the average of the exit intensity over
the cross section of the cylindrical cuvette. If necessary one could measure what might
be called an "effective path length" for each cuvette by measuring the absorbance of a
solution of some absorber whose true molar absorptivity has already been measured, but
we do not have to do this here. Instead, we can combine the molecular property c and
the effective path length of the cell being used for all the measurements into a new
constant, c*, whose magnitude is valid only for the particular system (absorber and
cuvette) under study. Beer's Law then takes the simpler form A = c*C. (Note that the
way it is defined here c* must have dimensions M
-1
because absorbance is
dimensionless.)

We shall henceforth distinguish the four different c* values by two-letter identifying
subscripts: namely, GG, GR, RG and RR. The meanings of these combinations are as
follows:

GG = Green solution examined at the wavelength of the Green absorption
maximum
GR = Green solution examined at the wavelength of the Red absorption
maximum
RG = Red solution examined at the wavelength of the Green absorption
maximum
RR = Red solution examined at the wavelength of the Red absorption maximum.

According to the modified form of Beer's Law introduced above, one can determine the
numerical value of c* ( = c ) for some solute at a given wavelength by determining the
slope of a plot of absorbance vs. concentration.


63
You may find it useful to use a spreadsheet program to do the following calculations.

1. Calculate the molar concentrations of the eight solutions you studied.

2. Calculate the 16 absorbances and use them along with the concentrations calculated in
Step 1 to prepare four graphs of absorbance vs. concentration. Each of your plots
should occupy most of an 8.5"x11" sheet of graph paper. From these plots determine
the four pertinent values of c*. (You must plot the data even if you have a hand
calculator that will do linear regression for you. Many scientists have been blindsided
by doing computer fits to data that really did not obey the fitting equation. If your
plots are nicely linear then you can certainly get the slope the easy way.)

Part IV. Spectrophotometric Analysis of a Mixture of the Two Complexes.

Theory: The absorbance of a mixture of absorbing species that do not interact with each
other in any way is simply the sum of the absorbances of the individual species. This
means that in a solution that contains both the red and the green complexes in significant
amounts the absorbance at
max
of the green form will be given by the equation

A
G
= c*
GG
[C
G
] + c*
RG
[C
R
]

and the absorbance at
max
of the red form will be given by

A
R
= c*
GR
[C
G
] + c*
RR
[C
R
]

where [C
x
] is the molar concentration of X = R, G.

It follows from this that if the four c* values are all known, the individual concentrations
in a mixture of the two species can be obtained by measuring its absorbance at the two
maximal wavelengths and solving the pair of simultaneous equations given just above.
(Students who know some linear algebra will recognize that these equations can be
compacted into the matrix equation.)

Calculate the concentrations of the green chloro complex and the red aquo complex
in the mixture.



64
The following series of questions pertains to the analysis of the data in Parts III and IV.
Your data and resulting calculations will be verified as you proceed through the exercise.
You should have worked through the analysis of Parts III and IV in your notebook before
beginning; otherwise, you may need an hour or so to complete this exercise. You may
leave the exercise at any point and continue it later.

Why do we allow electronic instruments to warm-up before use?

Why is it important not to have fingerprints on the cuvette?

Why is it important to align the cuvette in the sample holder the same way each time?

In part I step 3, you were instructed to weigh approximately 200 mg of the green chloro
complex. Please enter the precise mass in milligrams of the green chloro complex used
to prepare the solution.

In part I step 2, you were instructed to dissolve the green chloro complex into
approximately 35 mL of acidic solvent. Please enter the precise volume in milliliters of
the acidic solvent used to prepare the solution (e.g. 35.02). Your precision should be to a
hundredth of a milliliter.

If you weighed out 203 mg of the green chloro complex and dissolved it in 35.14 mL of
acidic solvent, the molarity of your stock solution would be 0.0202 M. Using your
precise value of mass and volume that you entered above, please enter your calculated
value for the concentration of the original green chloro complex stock solution in moles
per liter.

Please enter the value of the wavelength in nanometers of the maximum absorbance for
the GREEN solution.

Please enter the value of the wavelength in nanometers of the maximum absorbance for
the RED solution.

The original red stock solution has the same concentration as the green stock solution
since one mole of the red aquo complex forms for each mole of the green chloro complex
that is converted. Therefore, the concentrations of the two sets of four diluted solutions,
the red and green, are equal for each respective concentration. Enter the four calculated
values of the concentration of the solutions you prepared. Enter them in decreasing order
(highest to lowest) of concentration in units of moles per liter.
(The order of entry is very important here.)

Next, we will collect your data for the absorbance of each of your diluted samples for
both the green and red solutions that is used subsequently to verify your Beer's law plots.
We will refer to your Beer's law data using the shorthand suggested in your laboratory
manual. GG, GR will be the measurements of the green solution at the maxima of the
green and red complexes respectively and RG, RR will be the measurements on the red

65
solution at the maxima of the green and red complexes respectively. It is important to
correspond the absorbance readings with the correct diluted sample. To do this you will
need to enter, first, the absorbance that corresponds to the diluted sample of entry #1
above; second, the absorbance corresponding to diluted sample of entry #2; etc... This
means that your absorbance values will be in decreasing order. Please check for this
carefully as it will affect the slope calculations.

First, let's collect the data needed for the determination of the GG effective
extinction coefficient. The absorbance values should have a value between 0 and 1.
Please enter the 4 values of the GG absorbance measurement in corresponding order of
solution concentration (high concentration to low concentration; values of absorbance
will be running in the same sense, high absorbance to low absorbance and expressed to
three significant digits).

Plot the values of GG Absorbance versus Concentration on a spreadsheet or a
programmable calculator, and carefully determine the slope of the best straight line fit
through the data. The slope values for GG, GR, RG, and RR must be accurately
determined because they will enable you to solve for the unknown concentration of your
mixture of the two cobalt complexes. Enter the value of the slope of A vs. C. This is your
effective extinction coefficient for GG.

******
Now let's collect the data needed for the determination of the GR effective extinction
coefficient. The absorbance values should have a value between 0 and 1. Please enter
the four values of the GR absorbance measurement in corresponding order of solution
concentration (high concentration to low concentration; values of absorbance will be
running in the same sense, high absorbance to low absorbance and expressed to three
significant digits).

Plot the values of GR Absorbance versus concentration on a spreadsheet or a
programmable calculator, and carefully determine the slope of the best straight line fit
through the data. The slope values for GG, GR, RG, and RR must be accurately
determined because they will enable you to solve for the unknown concentration of your
mixture of the two cobalt complexes. Enter the value of the slope of A vs. C. This is your
effective extinction coefficient for GR.

******
Now let's collect the data needed for the determination of the RG effective extinction
coefficient. The absorbance values should have a value between 0 and 1. Please enter
the four values of the RG absorbance measurement in corresponding order of solution
concentration (high concentration to low concentration; values of absorbance will be
running in the same sense, high absorbance to low absorbance and expressed to three
significant digits).

Plot the values of RG Absorbance versus concentration on a spreadsheet or a
programmable calculator, and carefully determine the slope of the best straight line fit

66
through the data. The slope values for GG, GR, RG, and RR must be accurately
determined because they will enable you to solve for the unknown concentration of your
mixture of the two cobalt complexes. Enter the value of the slope of A vs.C. This is your
effective extinction coefficient for RG.

******
Now let's collect the data needed for the determination of the RR effective extinction
coefficient. The absorbance values should have a value between 0 and 1. Please enter the
four values of the RR absorbance measurement in corresponding order of solution
concentration (high concentration to low concentration; values of absorbance will be
running in the same sense, high absorbance to low absorbance and expressed to three
significant digits).

Plot the values of RR Absorbance versus concentration on a spreadsheet or a
programmable calculator, and carefully determine the slope of the best straight line fit
through the data. The slope values for GG, GR, RG, and RR must be accurately
determined because they will enable you to solve for the unknown concentration of your
mixture of the two cobalt complexes. Enter the value of the slope of A vs.C. This is your
effective extinction coefficient for RR.

We are now ready to complete the analysis of Part IV data. Using the values of the
effective extinction coefficients you determined from your slopes and the values of the
absorption you obtained for the mixture at the spectral maxima for the green and red
solutions, solve the 2x2 simultaneous linear equations for the concentrations of the green
and red complexes in the mixture. When you have an answer for these concentrations,
we will use the same data and verify your result.

The absorbance values should have a value between 0 and 1. Please enter the absorbance
you measured for the mixture of cobalt complexes at the wavelength of absorption
maximum for the GREEN complex.

The absorbance values should have a value between 0 and 1. Please enter the absorbance
you measured for the mixture of cobalt complexes at the wavelength of absorption
maximum for the RED complex.

Please enter the values you calculated for the concentrations of the green and red
complexes in the mixture. (Use three significant figures.)

67
A Kinetics Study
Kinetics Studies of trans-Co[(en)
2
Cl
2
]Cl
and the Aquation Product, [Co(en)
2
(H
2
O)Cl]Cl
2


INTRODUCTION

In this segment of the experiment, you will be studying kinetics based on the same acid
catalyzed hydrolysis reaction of the green chloro complex you previously prepared.
Recall, in acidic solutions with low free chloride ion concentrations, one of the chloride
ions in the trans-[Co(en)
2
Cl
2
]
+
complex ion can be replaced by a water molecule to give
an equilibrium mixture of the cis and trans isomers of the aquo complex,
[Co(en)
2
(H
2
O)Cl]
2+
. This reaction is accompanied by a color change from green to red:

H
+
trans-[Co(en)
2
Cl
2
]Cl + H
2
O cis- & trans- [Co(en)
2
(H
2
O)Cl]Cl
2

chloro complex (green color) aquo complex (red color)
You will take advantage of a color change in this reaction to determine both the order of
reaction, and the activation energy required to initiate the hydrolysis.

In this segment of the experiment, you will be studying kinetics based on an acid
catalyzed hydrolysis reaction of the green chloro complex you previously prepared. In
particular, you will determine both the order of reaction, and the activation energy
required to initiate the hydrolysis.

As you have previously studied, the rates of chemical reactions can usually be expressed
as algebraic functions of the concentrations of the reacting species. In many cases, the
rate of reaction is proportional to the product of the concentrations of the reactants, each
raised to a power called the order of the reaction with respect to that reactant:

Rate = k[A]
a
[B]
b


where the exponents a and b are referred to as the orders with respect to the reactants A
and B; and k is the rate constant. In most cases, the orders, a and b, are zero, one, or two.
Read the appropriate chapter in your textbook, as pre-laboratory preparation before
beginning this experiment.

The first two parts of this exercise will be to determine the order for the hydrolysis
reaction with respect to the [Co(en)
2
Cl
2
]
+
ion. For one of the two parts, you will be given
data that was collected previously for the decrease in [Co(en)
2
Cl
2
]
+
ion over time, from
which you can deduce the order of the reaction. Specifically, by finding the best function
of chloro complex concentration that gives the best linear correlation, we can determine
the order of the reaction.

68
For the other part, you will use a complementary method for determining the order of
reaction. You can examine half-lives using the following rationale for Part I. At a
particular acid concentration, you may assume that the hydrolysis rate can be expressed
by the relation:
Rate = k[Co(en)
2
Cl
2
+
]
n


where n = 0, 1, or 2, and here the square brackets indicate molar concentrations. To find
the order of this reaction we will measure the dependence of the initial concentration, C
0
,
of the [Co(en)
2
Cl
2
]
+
ion on the time required for the reaction to proceed half-way to
completion. It can be shown that for zero, first, and second order reactions, this time
(denoted t
1/2
), is expressed as follows:








In general, the half-life is proportional to (C
0
)
1-n
. We will use these relations to determine
the order of the reaction in Part I. Because the rate constant can be readily calculated
from t
1/2
as shown above (they are inversely proportional), a determination of t
1/2
will
yield the rate constant.

Question A: What would you expect for the ratio of the half-lives, t
1/2
(0.05 M) / t
1/2

(0.01 M), if the reaction were (a) zero order, (b) first order, or (c) second order?

The last part of the assignment is the determination of the activation energy of the
reaction. The rate constant for a reaction is related to the energy of activation, E
a
, by the
Arrhenius equation:
k = Ae
-Ea/RT


where A is a constant characteristic of the reaction, R is the gas constant, and T is the
absolute temperature in Kelvin. By taking the logarithm of both sides, we obtain:




Thus, if you determine the rate constant for the aquation of the chloro complex at several
different temperatures, you can make a plot of (ln k) vs. (1/T). A straight line drawn
through the points should have a slope of E
a
/R, and so a determination of the slope
permits a calculation of E
a
.

PROCEDURE

0, for
2
C
o
2 / 1
= = n
k
t
1, for
2 ln
2 / 1
= = n
k
t
2. for
C
1
o
2 / 1
= = n
k
t
A
T R
E
k
a
ln
1
ln + |
.
|

\
|
=

69
You will work in pairs on this experiment. The actual data analyses and the written
reports must be done entirely independently of your lab partner or other students. Make
sure that you avoid unauthorized collaboration and plagiarism. All suspected violations
of the Code of Academic Conduct will be referred to Student Judicial Affairs.

Part I. Determining Order of the Reaction (by using t
1/2
)

1. Prepare 60 mL of 0.5 M sulfuric acid solution by mixing 10 mL 3 M H
2
SO
4
with 50
mL deionized water.

2. Prepare a stock acidic solution of the green chloro complex, about 0.050 M in
trans-[Co(en)
2
Cl
2
]Cl, by dissolving about 170 mg of the compound measured
precisely in 12 mL 0.5 M sulfuric acid solution in a 100 mL beaker. Store this
solution in an ice-water bath.

3. In order to get correct color matches, it is important to use the same size test tubes for
all tests in Parts I and II. Using a disposable pipet, transfer exactly 1.5 mL of the
stock 0.050 M green chloro solution to one test tube and 3.0 mL to each of two other
test tubes. Store the 3.0 mL solutions in an ice-water bath.

4. Prepare a similar but more dilute green chloro solution, about 0.010 M in the green
chloro complex, by dissolving about 33 mg of trans-[Co(en)
2
Cl
2
]Cl in 12 mL of the
0.5 M sulfuric acid solution. Again, transfer one 1.5 mL and two 3.0 mL portions of
the 0.01 M solution to separate test tubes. Store the two 3.0 mL solutions in an ice-
bath.

5. Heat the two test tubes containing 1.5 mL of solution in a beaker of boiling water
using a hot plate for 5 to 10 minutes. This treatment will effect complete conversion
to the red aquo complex. Cool these two test tubes to room temperature, and to each
solution add 1.5 mL from the two stock solutions you prepared containing the
corresponding concentration of the original complex. Store both test tubes in ice-
water bath.

70
Table I.

Test Tube # Contents Brief Procedure
1 1.5 mL 0.05 M trans-[Co(en)
2
Cl
2
]Cl boilturns red; + 1.5 mL 0.05 M trans-
[Co(en)
2
Cl
2
]Cl 3 mL grayish t
1/2
comparison standard for 0.05 M runs
2 3.0 mL 0.05 M trans-[Co(en)
2
Cl
2
]Cl 0.05 M run #1
3 3.0 mL 0.05 M trans-[Co(en)
2
Cl
2
]Cl 0.05 M run #2
4 1.5 mL 0.01 M trans-[Co(en)
2
Cl
2
]Cl boilturns red; + 1.5 mL 0.01 M trans-
[Co(en)
2
Cl
2
]Cl 3 mL grayish t
1/2
comparison standard for 0.01 M runs
5 3.0 mL 0.01 M trans-[Co(en)
2
Cl
2
]Cl 0.01 M run #1
6 3.0 mL 0.01 M trans-[Co(en)
2
Cl
2
]Cl 0.01 M run #2

6. You now should have six test tubes, each containing 3 mL of solution (see Table I).
There are two sets of three tubes; the concentration in one set of solutions is about
five times that of the other set. Two members of each set contain a green solution of
essentially pure trans-[Co(en)
2
Cl
2
]Cl. The third tube of each set contains a grayish-
pink solution, half of which has been converted to the aquo complex. Keep these two
grayish-pink standards in an ice bath so that further conversion from chloro to aquo is
minimized.

7. Adjust the temperature of a 250 mL beaker containing 150 mL water to within at least
2C of 55C. Take two test tubes of the essentially pure green chloro complex--one
from the 0.05 M set, and one from the 0.01 M set (i.e. Test Tube #2 and 5). Place the
two tubes into the beaker of hot water, noting the time to the nearest second. At the
beginning, agitate the two test tubes in the hot water bath so that temperature
equilibrium is rapidly attained (be careful not to break the thermometer). Maintain
the bath temperature constant to 0.5 by adjustment of the hot plate or, if necessary,
by addition of small amounts of cold water. Record the exact temperature of the bath.
Record the times at which the color of each solution matches the grayish-pink color
of the corresponding half-reacted solution (i.e. Tubes #1 and 4). For best comparison,
briefly lift the test tube out of the hot water bath and use a white paper background.

8. Repeat the experiment with the next two test tubes for trial #2. Average the results
for each concentration from the two runs and determine the associated errors.

9. Save the test tube containing the 0.05 M reference half-reacted complex (i.e. test tube
#1) for Part II.

71
Part II. Determination of the Activation Energy

1. You have already determined t
1/2
for a temperature near 55C in Part I. However, the
measurement was not held truly constant at 55C for the entire duration of the
reaction time since the test tube was originally at room temperature and thus required
some time to equilibrate to 55C in the water bath. For this section, in an effort to get
a more accurate t
1/2
determination, you will add solid directly to pre-equilibrated
water in test tubes already at the prescribed water bath temperatures.

2. Prepare six clean test tubes each filled with 3 mL portions of the 0.5 M sulfuric acid
solution you made for Part I.

3. Weigh into a boat 40 mg of trans-[Co(en)
2
Cl
2
]Cl for reference. Place the reference at
your workstation along side your bulk supply of green complex. As each trial is
performed scoop out roughly 40 mg by gauging it visually against your reference.
Why is the precise mass not important?

4. Since you will be working in pairs for this experiment, one student should collect data
at 80, 75, and 55C while the other student should collect at 80, 65, and 45C,
each according to the following procedure. Both students measure t
1/2
at 80C since
the reaction is very fast at that temperature and the results may vary.

Adjust the water bath to the desired temperature with the test tube already in the
water bath. After the test tube containing the 0.5 M sulfuric acid has completely
equilibrated (5-10 min.), quickly dump a previously weighed portion of trans-
[Co(en)
2
Cl
2
]Cl into the test tube and swirl while holding it inside the water bath to
insure complete dissolution of the solid. Compare the color with that of the half-
reacted reference test tube referred to in Step 9 of Part I to determine the t
1/2
at that
temperature. Time how long it takes mixture to reach the desired "gray" color.

5. Each pair of students should exchange data so that both of you have t
1/2
at five
temperatures. For t
1/2
at 80C use the average value of data you and your partner
collected.


Clean-up: The cobalt solutions in the test tubes must be discarded in the waste
container labeled cobalt complex solution waste found in the fumehood. Any solid
green cobalt complex will be collected in the container labeled Cobalt complex solid
waste.


72
Part I.
Question B: From your measured half-lives, you should be able to state the dependence
of the half-life on the concentration of trans-[Co(en)
2
Cl
2
]
+
.

Question C: Determine the order of your reaction and discuss any potential sources of
error.

Part II
Question D: For each of the five temperatures, calculate the rate constant and then plot
ln k as a function of 1/T. What is the energy of activation for the reaction?

Question E: What is the value of the rate constant at 25 C?



Question F: As stated in the introduction, a plot of ln k as a function of 1/T yields a
straight line with slope -E
a
/R. Show that a plot of ln t
1/2
versus 1/T would have a slope
of +E
a
/R given that for reactions of order zero, one, or two; and t
1/2
is inversely
proportional to k. Does the proportionality constant affect the slope?

Question G: For many reactions near room temperature, the rate approximately doubles
for a 10 C rise in temperature. What is the corresponding activation energy?


Supplementary Activities (9 points).
Determining Order of the Reaction (by tracking the reaction over time)

1. On-line you will find a set of data collected on a solution of the green chloro
complex that was monitored over time during the course of its conversion to the
aquo complex. Use these data of Time vs. Concentration of green complex and
the integral forms of the rate laws to determine the order of the reaction. Hint:
You will need to plot [A]
t
vs. time, ln[A]
t
vs. time, and [A]
t
-1
vs. time. Plot all 3
graphs and determine which one yields a straight line. Use Excel.

2. On-line you will find a set of experimental concentration data for two different
reactions, A & B. In each case, use these data of Time vs. Concentration for each
reaction and the integral forms of the rate laws to determine the order of the
reaction.

Turn in your 9 correctly labeled graphs into your TA.

73
DATA ANALYSIS

Which of the following values would you expect for the ratio of half-lives for a reaction
with starting concentrations of 0.05M and 0.01M, t
1/2
(0.05M) / t
1/2
(0.01M), if a reaction
is known to be zero order? 5 choices given.

Which of the following values would you expect for the ratio of half-lives for a reaction
with starting concentrations of 0.05M and 0.01M, t
1/2
(0.05M) / t
1/2
(0.01M), if a reaction
is known to be first order? 5 choices given.

Which of the following values would you expect for the ratio of half-lives for a reaction
with starting concentrations of 0.05M and 0.01M, t
1/2
(0.05M) / t
1/2
(0.01M), if a reaction
is known to be second order? 5 choices given.

What value do you calculate for the ratio t
1/2
(0.05M) / t
1/2
(0.01M) from your
experimentally measured half-lives at 55
o
C?

Given your experimentally measured ratio of half-lives for the two different
concentrations, select the concentration dependence that best describes your experimental
ratio. 3 choices given.

Based on the ratio of half-lives for the two different concentrations that you determined,
and comparing the experimental ratio with the theoretical ratios for kinetic orders 0, 1,
and 2, which order does this reaction exhibit? 3 choices given.

The following series of questions pertains to the analysis of the data in Part II of the
Kinetics Experiment. The activation energy of the reaction will be determined based on
your data. Your data and resulting calculations will be verified as you proceed through
the exercise.

In part II of the experiment you and your partner measured the half-life of the reaction at
5 different temperatures. You should have constructed a table with column headings
T(C), T(K), 1/T, t
1/2
, k = ln(2)/t
1/2
, ln(k) and rows for each of the five temperatures for
which your team determined the half-lives. If you have not completed such a table, either
extend your existing table to include all these columns, or create the entire table now.
You may leave the exercise at any point and continue it later if necessary. Please enter
the 5 precise temperatures in degrees Celsius at which you measured the half-life of the
reaction (e.g. 81.5). Enter them in increasing order (lowest to highest).

Convert each of the temperatures you entered above to Kelvin and find the reciprocal.
Enter the reciprocal Kelvin temperatures in the corresponding order with the above
Celsius temperatures. Your reciprocal Kelvin temperatures will be entered in decreasing
order (highest to lowest). Use four significant figures. (e.g. 0.003143).

Please enter the 5 measured half-lives in units of seconds in corresponding ordered with
the above Celsius temperatures. (e.g. 35.5). The first half-life entered here should
correspond to the first (lowest) Celsius temperature entered above.

74

Calculate the rate constant of each of the half-lives, t
1/2
, you entered above. Enter the rate
constants in the corresponding order with the of the half-lives. Report your rate constant
values using at least 3 nonzero digits. (e.g. 0.00439).

Calculate the natural logarithm of each of the rate constants, k, you entered above. Enter
the natural logarithm values in the corresponding order with the of the rate constants.
Report your natural logarithm values using at least three digits. (e.g. -7.89).

Plot the values of ln(k) vs.1/T on a spreadsheet or a programmable calculator. Carefully,
determine the slope of the best straight line fit through the data using a regression (least
squares fitting) formula provided by your calculator or spreadsheet. The slope value
should be accurately determined to enable you to calculate a reasonable value for the
activation energy of the reaction. Remember that the best fit line of the points on this
graph should not be forced to go through the origin, (0,0), since the y-intercept in not
necessarily zero. Enter the value of the slope of ln(k) vs.1/T.

The activation energy of the reaction may be calculated using the previously determined
slope. Please enter the value you calculate for the activation energy in kJ/mol using the
value you obtained for the slope of ln(k) vs. 1/T.

Use one of your experimentally determined values of k, the activation energy you
determined, and the Arrhenius equation to calculate the value of the rate constant at 25
C. Alternatively, you can simply extrapolate the straight line plot of ln(k) vs. 1/T in
your notebook to 1/298 , read off the value of ln(k), and find the inverse of ln k.
k(25 C) = _______________

By showing the algebra for combining the Arrhenius equation with the expression for the
half-life of a reaction of order zero, one or two, you should convince yourself that a plot
of ln(t
1/2
) vs.1/T will have a slope of +E
a
/ R as long as the half-life is inversely related to
the rate constant. Use this information to answer the following question. Does the
proportionality constant between half-life and inverse rate constant affect the slope of a
plot of ln(t
1/2
) vs. 1/T? 2 choices given.

For many reactions near room temperature, the rate and the rate constant approximately
doubles for a 10
o
C rise in temperature. What is the value of activation energy in kJ/mol
for such a reaction?

Listed below are some data that was collected on a solution of the green chloro complex
as a function of time during its conversion to the aquo complex. Copy these data into
your notebook or cut and paste these values into a spreadsheet program. Use this data
and the integrated forms of the rate laws to determine the order of the reaction. You must
plot all three graphs to determine which yields a straight line. The plot that gives a clear
straight line identifies the order of the reaction. Report the order of the reaction and turn
in your graphs to your TA at the beginning of the next laboratory period. Each graph is
worth 1 point.

75
Determination of Vitamin C Content
Via a Redox Titration

INTRODUCTION

Vitamin C has received much publicity in the late 20th century as a promising antioxidant
and a potential cure for the common cold according to the controversial hypothesis by the
Nobel Laureate Linus Pauling. A more widely accepted role of Vitamin C is as a cure for
one of the most suffered nutritional deficiencies, scurvy, which was especially
threatening for sailors on long voyages in the 18th century. Vitamin C is chemically
known as L-ascorbic acid, and human beings do not possess the biochemical metabolic
pathways to produce it in the body. We must therefore consume Vitamin C (current daily
recommendation is 60 mg) from various foods. It is found in many fresh fruits and
vegetables such as sweet peppers, spinach, and citrus juices.

In this experiment, you will determine the Vitamin C content in various Vitamin C tablets
readily available to the consumer at neighborhood drug stores. This determination will
utilize the fact that L-ascorbic acid is readily oxidized to L-dehydroascorbic acid
according to the following oxidation half-reaction (which has an oxidation cell potential
of 0.127 V at pH = 5):







You will use another organic molecule, N-bromosuccinimide (NBS), as the oxidizing
agent. The pertinent reduction half reaction is:



76



The "indicator" in the "redox" titration you will be doing is actually generated in place by
a second redox reaction after all of the ascorbic acid in the sample of interest has been
consumed. The titration flask initially contains some added KI and starch solution. The
first small excess of NBS oxidizes some iodide ions to molecular iodine, which then
reacts with more I
-
to produce the triiodide ion, I
3
-
. The polymeric amylose (starch)
molecules wrap themselves around the triiodide ions and form a blue colored aggregate
to signal the endpoint.

Ascorbic acid solutions are susceptible to air oxidation, which can be inhibited in various
ways, including acidification. The air oxidation of ascorbic acid is catalyzed by metal
ions increasing the rate of degradation of ascorbic acid significantly. Oxalic acid forms
complexes with most metal ions and prevents their functioning as an oxidation catalyst.
Oxalic acid is commonly employed to increase the longevity of ascorbic acid. The last
segment of this experiment will test these factors involved in the degradation of ascorbic
acid.

Please read the appropriate chapter in your textbook, as pre-laboratory preparation for this
experiment.



77
Safety: Place all waste solutions/precipitates into the proper waste container. Wear your
goggles!

PROCEDURE

You will work in pairs on this experiment. The actual data analyses and the written
reports must be done entirely independently of your lab partner or other students. Make
sure that you avoid unauthorized collaboration and plagiarism. All suspected violations
of the Code of Academic Conduct will be referred to Student Judicial Affairs.

Part I. Preparation of solutions

You will be grouped by your TA in order to prepare the following solutions in a timely
manner.

Titrant Solution. Prepare about 500 mL of an NBS titrant solution by dissolving
approximately 100 mg of NBS in a 1 L bottle that is about half-full of deionized
water.

Primary Standard. Accurately weigh ca. 100 mg of ascorbic acid and transfer it
quantitatively to your 250 mL volumetric flask. Add ca. 2 g of oxalic acid to the
flask, partially fill it with deionized water and swirl until the solids have dissolved.
Continue gradually adding water and swirling the flask to keep the contents well
mixed, and finally add water from a disposable pipet to bring the liquid level to the
mark. Do a final mixing by inverting and swirling the flask at least 30 times. Keep
the volumetric flask sealed as much as possible to minimize the opportunity for air
oxidation to occur.

Analytical Sample. Follow a similar procedure as above but use an accurately
weighed ca. 100 mg sample of a commercial Vitamin C tablet in place of the ascorbic
acid. You will first have to crush the Vitamin C tablet in a folded sheet of paper
using your small iron ring as the hammer, making a fairly fine powder. Further grind
the crushed tablet using the pointed end of a centrifuge tube as a pestle and a small
beaker as a mortar into a very fine powder. These tablets sometimes contain binders,
which will not completely dissolve.

Solution with Metal I ons. Accurately weigh ca. 100 mg of ascorbic acid and transfer
it quantitatively to a clean 250 mL volumetric flask. Partially fill the volumetric flask
with deionized water and swirl until the solids have dissolved. Continue gradually
adding water and swirling the flask to keep the contents well mixed, and finally add
water from a disposable pipet to bring the liquid level to the mark. Do a final mixing
by inverting and swirling the flask at least 30 times. Divide the solution
approximately in half into two 250 mL beakers. To one beaker add 1 g of oxalic acid
and stir with a glass rod until the oxalic acid has dissolved. Label each of the beakers
so that the one containing oxalic acid can be distinguished from the one without. Add
1 mL of 0.05 M ferric nitrate solution to each of the beakers and set them aside.

78
Part II. Titrations

Do these titrations one at a time--in other words, do not let ascorbic acid solutions sit
around exposed to the atmosphere for very long.

Assaying your NBS solution: With a volumetric pipet take a 10 mL aliquot of the
"partnership's" standard ascorbic acid solution and add it to a 125 mL Erlenmeyer
flask that already contains 20 mL of water, 2/3 mL of 6 M acetic acid, 5 mL of 4% KI
solution and 1 mL of starch indicator solution. You may approximate the 2/3 mL of 6
M acetic acid here by delivering between 0.5 and 0.75 mL of 6 M acetic acid, using a
disposable pipet.

As you approach the end point you should see the blue color form where the drop
enters but go away again when the flask is swirled. Repeat this titration at least two
more times.

Analyzing commercial Vitamin C: Perform the above titration procedure at least
three times using the" solution of the commercial Vitamin C tablet and thereby
obtaining the data needed to compute the ascorbic acid content of this product.

Part III. Investigation of degradative factors on ascorbic acid.

Effect of Metal Ions

Titrate a 10.00 mL aliquot of the ascorbic acid solution containing metal ions as well as
titrate a 10.00 mL aliquot of the ascorbic acid solution containing metal ions plus the
oxalic acid following the procedures given in Part II under Assaying your NBS solution.
Repeat these titrations to obtain more accurate results by using another 10.00 mL aliquot
if there is time.

Clean-Up: All solutions may be poured down the drain with copious amounts of water.



79
DATA ANALYSIS

When you use the half reaction method to balance the redox reaction between one mole
of NBS and ascorbic acid to give L-dehydroascorbic acid and succinimide, how many
moles of electrons are transferred?

How many moles of NBS are consumed for every one mole of ascorbic acid reacted?

In the presence of excess iodide ions, the iodine formed by reaction of iodide with NBS
will react further to form triiodide ions. What does the triiodide combine with to form the
blue color of the endpoint?

You were instructed to use approximately 100 mg of ascorbic acid to prepare your
primary standard solution. What is the precise mass in milligrams of the ascorbic acid
used to prepare your primary standard solution?

If one had weighed out precisely 100 mg of ascorbic acid for the primary standard
solution and dissolved it in enough deionized water to make a 250 mL solution, the
molarity of that solution would be 0.00227 M. What is your calculated molarity of the
ascorbic acid primary standard solution based on the precise number of milligrams of
ascorbic acid you weighed out and entered above?

In the standardization of the NBS solution, using the ascorbic acid primary standard
solution, we must examine each of the three acceptable trials. Your titration volumes of
the NBS solution should be approximately 20 - 30 mL. For each trial, what is the precise
volume in mL of NBS solution used in the titration of your ascorbic acid solution (e.g.
20.34 mL)?

Using the volumes of NBS solution you just entered and the molarity of the ascorbic acid
primary standard solution, calculate the molarity of the NBS secondary standard solution
for each trial. What is your calculated molarity of the NBS solution for each trial?

The molarity of the NBS solution is taken as the average of the three trials. What is the
average?

What is the standard deviation of the average molarity of the NBS solution?

You were instructed to use approximately 100 mg of the Vitamin C to prepare your
analytical sample solution. What is the value for the precise mass in mg of the Vitamin C
tablet that was dissolved in your analytical sample solution?

In the analysis of the ascorbic acid content in a Vitamin C tablet, we must examine each
of the three acceptable trials. Your titration volumes of the NBS solution should be
approximately 10-20 mL. For each trial, what is the precise volume in milliliters of NBS
used in the titration of the 10.00 mL Vitamin C sample(e.g. 10.45mL)?


80
Using the volumes of NBS solution you just entered and the average molarity of the NBS
standard solution, calculate the milligrams of ascorbic acid in the 10.00 mL Vitamin C
sample for each trial. What is your calculated milligrams of ascorbic acid in the 10.00
mL Vitamin C sample, for each trial?

Using the milligrams of ascorbic acid you entered above, the ratio of total sample volume
to aliquot volume, and the total milligrams of the Vitamin C tablet that you dissolved,
calculate the mass of ascorbic acid in the Vitamin C tablet for each trial. Do this by
scaling up to find the amount (mg) of ascorbic acid in your 250 mL flask. What is your
calculated mass of ascorbic acid in the Vitamin C tablet, for each trial?

What is the average for your determination of the mass of ascorbic acid in the Vitamin C
tablet?

What is the standard deviation of the mass of ascorbic acid in the Vitamin C tablet?

In the final part of the experiment, you were asked to examine the protective ability of
oxalic acid in preventing the oxidative degradation of Vitamin C by catalytic ferric ions.

At the beginning of the experiment you or one of your partners prepared two solutions
containing ascorbic acid and ferric ions. In one of these solutions oxalic acid was added
and the two solutions were set aside in open containers.

When you titrated a sample from each of these solutions, one containing oxalic acid and
one without oxalic acid, which solution required more NBS to reach the endpoint in the
titration?

How many trials did you complete for the analysis of the ascorbic acid/ferric ion solution
containing oxalic acid?

For each trial, what is the precise volume in mL of NBS solution used in the titration of
the ascorbic acid/ferric ion solution containing oxalic acid?

For each NBS volume you entered above, calculate the mass in mg of ascorbic acid
present in the 10.00 mL sample solution that DID contain oxalic acid.

How many trials did you complete for the analysis of the ascorbic acid/ferric ion solution
that DID NOT contain any oxalic acid?

For each trial, what is the precise volume in mL of NBS solution used in the titration of
the ascorbic acid/ferric ion solution that DID NOT contain any oxalic acid?

For each NBS volume you entered above calculate the mass in mg of ascorbic acid
present in the 10.00 mL sample solution that DID NOT contain oxalic acid.

What is the mg of ascorbic acid that was protected by the presence of the oxalic acid?

81

Is oxalic acid effective in inhibiting the catalytic effect of metal ions?

Which of the following redox reaction schemes may be responsible for the direct
degradation of ascorbic acid. Choices given.

Which of the following redox reaction schemes may be responsible for the catalytic
degradation of ascorbic acid. Choices given.

Which of the following transition metal structures involving oxalate ion (from the oxalic
acid) and iron would you expect to be responsible for the inhibition of catalytic
degradation of ascorbic acid? Choices given.

Vitamin C can be added to applesauce to inhibit it from becoming brown in color when
exposed to the air. Discuss how this protection occurs based on the reactions of Vitamin
C and its possible role as a sacrificial antioxidant.

Concluding Remarks: Briefly discuss interpretations of your observations and results.
Include in your discussion, any conclusions drawn from the results and any sources of
error in the experiment.































APPENDIX

A-1
A) General Experimental Guidelines
The laboratory is a critical component of your study of chemistry. Therefore, a student
must complete all of the assigned laboratory work, including all on- & off-line post-
laboratory exercises, in order to pass this course.

1. Pre-Laboratory Preparation
Many of the Chemistry 2 laboratory experiments are intricate and use chemicals
that could present a hazard if used improperly. Thus, students are required to
judiciously prepare for each experiment by carefully reading the experiment and
writing a Title, Purpose, Procedure (brief outline), and Data (outline) section
before arriving at the laboratory. A detailed description of each section is
described below under, "Writing a Laboratory Report". After preparing the
laboratory notebook, students will complete the on-line pre-laboratory
presentation and must pass the pre-laboratory quiz. Any student without this
preparation completed at the beginning of the laboratory period is deemed unsafe
and must leave the laboratory until the pre-laboratory write up is complete and the
supervising TA is convinced that you are prepared to begin the experiment.

2. Data Collection
All data must be recorded in ink directly into your laboratory notebook. At the
completion of the experiment, you must turn in a copy of your data sheet to your
TA beforeyou leave the laboratory.

3. Unknowns
Students will obtain all unknowns from the TA. Students must be explicit in their
request for an unknown; that is, they must know the name of the experiment and
unknown. If a student needs more unknown, they should notify the TA who will
then write a note of explanation that the student can take to the dispensary. The
note should contain the student's name, the student's locker number, the laboratory
section number, the TA's name, the experiment name, and the name of the
unknown.

4. Writing A Laboratory Report
Below is the suggested format that your report should follow. Portions of the
report should be written in your laboratory notebook and others will be submitted
on-line as part of the post laboratory exercises. Post laboratory exercises are due
one week after the completion of the laboratory.

Below is a general outline of a common format that is often used in science
laboratory courses. Discuss this format with your TA during the first laboratory
period so that you clearly understand what will be expected.

Title: The report should have a title that concisely describes the
experiment.

Purpose: A brief and concise statement that describes the goals of the
experiment and the methods employed. Any pertinent chemical reactions

A-2
are generally indicated. State the purpose of the experiment in the form of
a complete sentence. Do not start with the word "To."

Procedure: A brief and concise outline of each step of the experiment
should be included. If you are using a published procedure, you should
also cite the literature or laboratory manual. A drawing of the apparatus
may also be included.

Data and Observations: Report all measurements and observations that
are pertinent to the experiment. Be sure to note any problems or
unexpected occurrences. It is important that this section be as neat and as
organized as possible. The use of tables will often help in this regard. All
data must be recorded in ink directly into the notebook at the time it is
collected. A severe penalty will be imposed for pencil or transcribed data
entries. Do not erase mistakes. Simply draw a line through the error and
record the correction. Your notebook is subject to examination at any
time.

The following sections are to be submitted on-line as part of the post-laboratory
exercise:

Calculations: This section generally includes any complicated
calculations that are involved in the experiment. Again, it is important to
use foresight when organizing this section.

Questions: All assigned questions are answered in this section.

Results & Conclusions: Report the outcome of the experiment.

All reports must be written in non-erasable ink. A date should be indicated on
each report, especially in the Data section. You must prepare for each experiment
by writing the Title, Purpose, and Procedure beforecoming to the laboratory. If it
is not completed the student must finish it and the TA will deduct 30% of earned
points from the post-laboratory exercise for first time offenders (70% for repeat
offenders). Students will not be granted extra time to complete the laboratory. It
is also important to organize and prepare the format of the Data section before
coming to the laboratory so that you will only need to neatly record your data and
observations during the experiment. Each section should be clearly marked with
a proper heading. Your notebook should be organized and written in such a
manner that another chemist could read it and repeat the experiment in precisely
the same way. It is also important to complete the report as soon as possible after
the completion of the experiment as this is much more efficient than waiting until
the night before the experiment is due.

5. Statistical Treatment of Data
Every measurement made in the laboratory is subject to error. Although you
should try to minimize error, two types of errors will occur. Systematic or
Determinate Errors are those errors which are reproducible and which can be

A-3
corrected. Examples are errors due to a miscalibrated piece of glassware or a
balance that consistently weighs light. Random or Indeterminate Errors are due to
limitations of measurement that are beyond the experimenter's control. These
errors cannot be eliminated and lead to both positive and negative fluctuations in
successive measurements. Examples are a difference in readings by different
observers, or the fluctuations in equipment due to electrical noise.

You will be graded by your ability to obtain accurate results. Accuracy describes
how close your result is to the true value. Another related term is precision.
Precision describes how close your results from different trials are to each other.
Data of high precision indicates small random errors and leads experimenters to
have confidence in their results. Data that is highly accurate suggests that there is
little systematic error. A well-designed experiment (and a well-trained
experimenter) should yield data that is both precise and accurate.

In an effort to describe and quantify the random errors which will occur during
the course of the Chemistry 2 laboratory you will be asked to report an average, a
standard deviation, a 90% confidence limit, and a relative deviation. You may
also have to analyze multiple trials to decide whether or not a certain piece of data
should be discarded. The following sections describe these procedures.

Average and Standard Deviation
The average or mean, x, is defined by

x =
Ex
i
N


where each x
i
is one measurement and N is the number of trials or samples.


The standard deviation, o, measures how close values are clustered about the
mean. The standard deviation for small samples is defined by

o =
E (x
i
- x)
2
N - 1


The smaller the value of o the more closely packed the data is about the mean, or,
in other words, the measurements are more precise.

Confidence Limits
Confidence limits provide an indication of data precision. For example, a 90%
confidence limit of 2.0 indicates that there is a 90% probability that the true
average of an infinite collection of data is within 2.0 of the calculated average
of a limited collection. Clearly the more precise a set of data, the smaller the
confidence interval. Thus, a small confidence interval is always the goal of any
experiment. In General Chemistry you will be required to calculate the 90%
confidence interval for all experimental collections of data. The formula to do
this is:



A-4
Confidence Limit =
t o
N



where t varies with the number of observations. For the 90% confidence limits
you are asked to calculate, t = 6.314 when N = 2, t = 2.920 when N = 3, t = 2.353
when N = 4, t = 2.132 when N = 5, and t = 2.015 when N = 6. You should always
report your result as the average the 90%

confidence limit.

Relative Deviation
The relative average deviation, d, like the standard deviation, is useful to
determine how data are clustered about a mean. The advantage of a relative
deviation is that it incorporates the relative numerical magnitude of the average.

The relative average deviation, d, is calculated in the following way.
a) Calculate the average, x, with all data that are of high quality.
b) Calculate the deviation, |x
i
- x|, of each good piece of data.
c) Calculate the average of these deviations.
d) Divide that average of the deviations by the mean of the good data.

This number is generally expressed as parts per thousand (ppt). You can do this
by simply multiplying by 1000.

Please report the relative average deviation (ppt) in addition to the standard
deviation in all experiments.

Analysis of Poor Data: Q-test
Sometimes a single piece of data is inconsistent with other data. You need a
method to determine, or test, if the data in question is so poor that it should be
excluded from your calculations. Many tests have been developed for this
purpose. One of the most common is what is known as the Q test. To determine
if a data should be discarded by this test you first need to calculate the difference
of the data in question from the data closest in value (this is called the "gap").
Next, you calculate the magnitude of the total spread of the data by calculating the
difference between the data in question and the data furthest away in value (this is
called the "range"). You will then calculate the Q
Data
, given by

Q
Data
=
gap
range


and compare the value to that given in the table below. The values in the table
below are given for the 90% confidence level. If the Q
Data
is greater than the
Q
Critical
then the data can be discarded with 90% confidence (the value has a less
than 10% chance of being valid).



A-5
Number of Trials Q
Critical

3 0.94
4 0.76
5 0.64
6 0.56


While the Q test is very popular, it is not always useful for the small samples you
will have (you will generally only do triplicate trials).

Keep in mind that you also always have the right to discard a piece of data that
you are sure is of low quality. That is, when you are aware of a poor collection.
However, beware of discarding data that do not meet the Q test. You may be
discarding your most accurate determination!

B) On-line Pre- & Post-Laboratory Procedures
The Department of Chemistry is introducing on-line pre-& post-laboratory activities.
The purpose of the pre-laboratory presentations is to aid the student in preparing for the
laboratories. Each post-laboratory exercise is designed to guide you through the
calculations or concepts that apply.

Prior to doing any activities, all students are required to complete the Safety Quiz online
after watching the online safety videos. Prior to coming to the laboratory class, the pre-
laboratory exercises are to be viewed and the pre-lab quiz must be completed on-line.

Read your Laboratory Manual and complete your pre-laboratory write up before viewing
on-line pre-laboratory presentation.

Have laboratory notebook and calculator with you when viewing the on-line pre-
laboratory presentation or completing the post-laboratory exercises. Plan ahead. As
with any computer activity, the on-line activities may take time to complete. Do not wait
until the last minute to complete any of the required on-line activities.

1. Accessing the Website
Each time you access the On-Line Chemistry 2 Laboratory website you must do
so through SmartSite and/or the web address given by your instructor.

a. The Welcome Page tests whether the Flash plug-in is working. If you do
not have the correct Flash player installed. If you do not see the movie on
the Welcome page, then there is no guarantee that you will be able to view
all videos and slides.



A-6



b. Click on My Profile to enter your personal information.



2. Viewing the Pre-laboratory Presentations.
a. If you click on Pre-Laboratory Presentations, it will take you to the
Pre-Laboratory Presentation screen as seen below. There is a brief tutorial
in the Getting Started Presentation.


A-7


NOTE: If you run into difficulty with any of these steps, please contact
mwwebhelp@ucdavis.edu.

b. Sequentially view the slides by either clicking on Prev and Next
buttons, or view any slide in the presentation by selecting it in the Slide
Menu. Note you may review any slide at any time.







c. The entire text for each slide may be viewed by moving the slider
directly to the right of the text frame.

d. Audio is provided but not essential. All the information is conveyed in
the text and the main frame.

Slide Menu
Text Frame
Presentations
Menu

A-8
3. Taking the Pre-laboratory Quiz
After viewing the lab session, go back to the Chemistry 2 Laboratory Presentation
Home Page by clicking at the top of the page.

a. Click on pre-laboratory quizzes. Choose the appropriate laboratory quiz.
Each pre-lab quiz must be completed at least 1 hour prior to attending your
scheduled lab class. A passing score of 100% (correct answers to all three
questions) is required before you will be allowed to perform the laboratory
experiment. If you fail the quiz on the first attempt, you may take the quiz
a second time. Because the questions are chosen randomly, you may
receive different questions on your second attempt, so it is a good idea to
review the pre-lab session prior to your second attempt. You may also
view the laboratory session while you are taking the prelaboratory quiz. If
you fail to pass the quiz on a second attempt, review the laboratory material
again and be prepared to take another prelaboratory quiz at the beginning
of laboratory class given by your TA but you will not receive any points.

b. Pre-lab quizzes are timed quizzes. You have twenty minutes to take the
quiz. Furthermore, once you open a window to take a quiz, it will be
counted as one of your two attempts even if you do not hit the submit
button before closing the window. Only start the pre-lab quiz when you
are ready to take it.

c. In order to receive your 2 points for the prelaboratory quiz you must
complete it successfully at least 1 hour before your laboratory class is to
begin.



4. Completing the Post-Laboratory Exercises.
You will need to complete all the on-line post-laboratory exercises for each lab in
order to receive credit for the laboratory portion of the course.

In the post-laboratory exercises, you will be asked to enter your data and the
results from your calculations. For your data entries, the post-lab exercises are
designed to check that your data is sensible. For example, if you are asked to

A-9
weigh approximately 3 g of a substance, the program will check to see if your
data entry falls within a range such as 1 - 6 grams.

For your calculation entries, the program is designed to verify that your
calculation is correct based on your previously entered data. The program also
allows for rounding differences. For example, if the program is expecting the
entry, 0.234, based on your data, then a value in a range of 0.232 0.236 may be
accepted.

There are also multiple-choice questions and free response questions posed in the
post-lab exercises. An on-line text box will be provided for you to write any
concluding remarks discussing and explaining your experimental results.

a. Click on post-laboratory exercises. Choose the appropriate laboratory
exercise and follow the instructions. See below.








A-10
b. You will need to have your laboratory notebook and a calculator or
spreadsheet program to complete the exercises. You should keep a detailed
record of your data entries and the resulting calculations in your laboratory
notebook. You may need to reference this material when discussing a
calculation with a TA.

c. As you proceed through your post-lab exercise, a scroll down window
appears at the bottom of the screen. This summary is the post-lab data
summary, and it contains your accepted entries and the number of points
awarded for each question. You may refer to this summary to verify the
values you entered that are used in subsequent calculations.

d. When asked to collect data for multiple trials, you must have data for at
least 3 trials to complete the post-lab exercises. The single exception to
this is Part III of the Vitamin C laboratory. When entering data or
calculated values, do not include unit symbols.

e. In many cases, you will not be able to proceed to the next question until
you have correctly answered the previous question. Some hints are
provided for the first few incorrect responses. If you are unable to proceed
after repeated attempts to enter a correct response, please contact your TA.

f. Be careful and deliberate about your entries. Once you proceed to the
next question, you cannot go back and change your answer to a previous
question.

g. In contrast to the pre-lab quizzes, you may exit the post-laboratory
exercise at any time and re-enter as many times as you wish. Upon re-
entry, the program will begin with the same question that you were
answering when you exited. Points are not awarded until you click the
submit button.

Scoring Scheme
The first line of text on each question contains a terse notation describing
the scoring for that question. The notation used and an explanation of each
is provided below:

1. Data Entry No Scoring
Simply enter your experimental value. The program will verify that
your entry is within the expected range for the experiment, but no
awarding of points is involved.

2. Scoring Scheme: 21
These are typically questions that have only two alternative answers. If
you select the correct answer, you will receive two points. If you select
the incorrect answer, you will receive one point for completing the
question and you will be informed of the correct answer.


A-11
3. Scoring Scheme: 3-2-1-1
These are typically multiple-choice questions with three alternatives. If
you select the correct answer on the first try, you will receive three
points. The possible points earned are then reduced by one point on
each try and a hint is provided. You will receive a minimum of one
point if you answer correctly on the third or subsequent tries.

4. Scoring Scheme: 3-3-2-1
These are typically questions that require you to do calculations based
upon previously entered experimental data, but may also be multiple
choice questions with 4 or more alternatives. If you respond correctly
on either of the first two tries, you will receive three points. The
possible score is reduced by one point for each of the next two tries and
remains one point for a correct response on any subsequent try.

5. Free Response (1 or 2 points possible)
Some of the laboratories contain questions where you will write your
answer in a text box. The point value for each question will be
indicated. Your TA will read your responses and award you your
points accordingly. Your points for these questions will appear in your
on-line score sheet.

6. Analysis (1 to 5 points possible)
In some of the laboratories, you will analyze a sample of unknown
content. In the Redox and EDTA laboratories you will find a mass
percent and in the Qualitative Analysis laboratory you will be
identifying the metal ions present in a mixture. In these three
laboratories, you will be awarded 1 to 5 points for accuracy. In order
for the on-line program to identify which sample you were assigned to
analyze, you will need to enter your locker series number.

Due Date/ Late Submission of Post-lab Exercise.

The post-laboratory exercises must be completed by the next normally scheduled
laboratory meeting. The last post-laboratory exercise is due the last day of
instruction. Each post lab exercise has a date/time stamp to indicate the date and
time of completion. Late submission of your post lab exercise will be met with a
5-point deduction for every calendar day it is late.

NOTE: If you run into difficulty with any of your post-laboratory entries, please
contact your TA.


A-12

C) Late Reports & Make-Up Policy
1. Late Reports

Laboratory reports are due at the beginning of the period after the one allocated
for the completion of the experiment. The last report each quarter is due at the
time indicated by the TA. Late reports will be met with a 5-point deduction for
every calendar day the report is late.

2. Laboratory Make-Up Policy
Students must attend the laboratory class for the section in which they are
enrolled. If a student misses a laboratory class with an excused absence, it must
be made up before the end of the following week of laboratory. No further
opportunity for make-up will be provided to the student who fails to make up the
lab by the following week. No make ups for unexcused absences. I f a student
misses the last lab of the quarter, it must be made up immediately. Typically,
laboratory classes end one or two days before the end of the quarter. No
laboratory make-ups will be offered after one week from the scheduled date of
the lab. Excused absences include an extended illness or family emergency.
Bring proof to your TA or head TA immediately upon return. If you cannot
present this proof or have an unexcused absence, you may receive a failing grade
in the course.

3. Laboratory Make-up Procedure
You are required to complete all labs in order to pass the course and it is your
responsibility to make up any missed labs promptly. Failure to make up a lab
may result in a failing gradefor the course.

If you miss a lab, you must make it up by attending another scheduled laboratory
section. Consult the Class Schedule and Room Directory for a listing of rooms
and times. Go to the selected laboratory section and ask the teaching assistant if
you may be admitted to make up a lab. You must be on time for the start of the
lab period. If there is room in the class, the teaching assistant will allow you in
the lab, unlock your locker, and allow you to do the lab. Make sure to record the
teaching assistant's name, date, time and room number where you made up the
laboratory. Have the TA collect your data sheet and he or she will give it to your
regularly assigned teaching assistant. No laboratory report will be accepted
without a valid copy of the data sheet.

4. Plagiarism and Unauthorized Collaboration
Some of your experiments will be done with lab partners. You are encouraged to
discuss your data and its analysis and interpretation with your lab partner, other
students and the TAs. However, the actual data analyses and the written reports
must be done entirely independently of your lab partner or other students. Make
sure that you avoid unauthorized collaboration and plagiarism. All suspected
violations of the Code of Academic Conduct will be referred to Student Judicial
Affairs.

A-13
D) Common Laboratory Procedures
1. Using the Balance
A balance is used to measure the mass of an object. Each laboratory room
contains two electronic balances that are very easy to use. A diagram of a balance
is shown in Figure 1. To use the balance, turn it on by pushing the tare bar down.
The electronic readout should then be lit. Open one of the sliding doors and be
sure the balance pan and surrounding area is clean. You can clean it with a
balance brush or Kimwipe. Next shut the doors and press the tare bar to set the
balance at zero. Now simply place the object to be weighed on the balance and
measure the mass to 0.001 grams.








Figure 1: The Balance


Always use weighing paper when weighing solids to protect the balance. To do
this simply place the weighing paper on the balance pan and be sure it is not
touching the side. Press the tare bar on the right side and the balance will then
read 0.000 g. Now add the desired mass of solid and record the mass. Always
clean the balance carefully after use. At the end of the period,, turn off the
balance by raising the tare bar. Always use the balance with extreme care as it is
very expensive.

A-14
2. Handling Solids
Use a clean spatula to transfer solid from bottles. Never use a contaminated
spatula. Also, never return unused solid to the reagent bottle. Simply discard it.
To avoid waste, never remove more solid from a bottle than is necessary. Below
in Figure 2 is an illustration of how to properly weigh and transfer a solid using
weighing paper. In the Chemistry 2 laboratories we are presently using weighing
boats rather than weighing paper, however the techniques shown in the Figure are
still useful and should be carefully examined.









Figure 2: Solid Transfer




A-15
3. Handling Liquids
When transferring liquids from a reagent bottle, always remove the cap/stopper
and hold it in your hand. Never place the cap/stopper on the bench or
contamination could result. Pour the liquid slowly and carefully to avoid spillage.
You may find the use of a glass rod helpful, as is shown below in Figure 3.





Figure 3: Liquid Transfer


4. Capping a Flask
During many experiments you will have to cap a flask to protect the contents from
contamination. Figure 4 illustrates the proper method using Parafilm.




Figure 4: Capping a Flask


A-16
5. Measuring Liquid Volumes
Many glassware items have volume marks printed on them. Before using a piece
of glassware to make a volume measurement, you should take a moment to study
its calibrations to insure that you know how to read them properly. A beaker or
Erlenmeyer flask can be used for rather rough measurements. A graduated
cylinder of the appropriate size can be used for measurements of moderate
accuracy. A pipet is commonly used to transfer an accurately known volume of a
liquid from one container to another. However, the accuracy of such a transfer is
only as good as the technique of the operator will allow.

In making any volume measurement, the liquid level should always be the same
as your eye level. Erlenmeyer flasks and graduated cylinders are usually
filled/read by raising them to your eye rather than by squatting down to bring your
eye level to the bench top. The liquid level in a pipet is always lowered to the
mark while the mark is held steady at eye level.





Burets: With practice, the position of the
meniscus of a liquid in the 25 mL burets
used in the Chemistry 2 labs can be
estimated to within 0.02 mL. Figure 5
shows the use of a card with a dark strip on
it to sharpen the image of the meniscus.
You will find by experiment that if the top
of the strip is positioned slightly below the
level of the liquid in the buret, the bottom
of the meniscus will be very easy to see.



Figure 5: Reading the Meniscus


You should always use the following procedure when changing the solution in a
buret. First, empty the buret out the top and half-fill it with deionized water.
Open the stopcock and drain about 5 mL out of the tip. Over the sink, empty the
buret out the top by inverting it swiftly, and then repeat the water washing, this
time also opening the stopcock when the buret is inverted to allow most of the
water to drain back out of the tip. Wait about 30 seconds for drainage and then
close the stopcock. While it is still upside down, blot/wipe off the top of the buret
with a laboratory tissue. Then turn it upright, and using a clean beaker for the
transfer, add enough of the new solution to bring the liquid level up to about the
48 mL mark. Next, drain part of the liquid out of the tip into a waste receiver,
close the stopcock, and wipe off the tip with a laboratory tissue. Then, at the sink,
cradle the top of the buret between the thumb and index finger of one hand.
While holding it by the tip with your other hand, turn the buret horizontal. While
twirling the buret by the tip, slowly empty it through the top, being careful to wet
the entire interior wall with the new solution. Repeat this operation two more
times. Finally, fill the buret above the zero mark and drain the excess out the tip
until the meniscus is within the calibrated portion of the buret. Be sure that no air


A-17
bubbles are trapped in the tip. Do not attempt to bring the meniscus to 0.00. This
method is both time consuming and unwise, since the 0.00 line may not be in
precisely the right place.

Pipets: Students often experience some initial difficulty in using a pipet. The
following instructions, the illustrations in Figure 6 and some hands-on practice
using deionized water should help you to become proficient fairly quickly. In
what follows, we assume that the pipet has been pre-rinsed with the solution you
want to transfer following essentially the same procedure as that described above
for burets, except that you must use a bulb to suck the small doses of water or the
new liquid into the pipet rather than pouring them in from a beaker.




Figure 6: Using a Pipet

To begin a pipetting operation hold the pipet vertical and rest the pointed end on
the bottom of the container from which you want to transfer a sample. With your
least-dexterous hand, use a rubber bulb fitted with an Eppendorf tip to draw the
liquid a few centimeters above the mark on the pipet. If you keep the pipet
bottomed, you can then remove the bulb and quickly seal the pipet mouth with the
index finger of your "better" hand before the liquid level falls below the mark.
You might try conditioning your index fingertip first by rubbing it gently in the
palm of the other hand. If your finger is too wet, you can't create a small enough
crack (see below), and if it is too dry, you can't get a good seal.

Raise the over filled pipet vertically out of the vessel from which you are taking
the measured sample and quickly put a beaker or some other waste receiver under
it. Raise the mark on the pipet to your eye level, tilt the receiver slightly, and
touch the pointed tip of the pipet to a dry spot on its sidewall.

If you now slightly rock your index finger you can open and close a tiny crack at
the mouth of the pipet and thereby allow the liquid level in the pipet to fall exactly
to the mark on its shaft. (In this step some individuals have more success by
slowly rotating the pipet using the thumb and the other fingers on the hand

A-18
holding it.) Be patient because if you overshoot the mark you must begin the
whole process again.

Remove the accurately filled pipet from its container and while still tightly sealing
its top with your finger, quickly dry the lower portion of the shaft with a single
downward stroke of a laboratory tissue. Tilt the final receiver slightly and while
holding the pipet vertical, place its tip against the receiver wall so that when take
your finger off of the pipet mouth, liquid will flow smoothly down to the bottom
of the vessel. You want to avoid splashing as much as possible. Keep the tip of
the pipet in contact with the flask sidewall for at least 30 seconds after it looks
empty, and then remove it from the receiver.

The pipets in the Chemistry 2 laboratories are calibrated "to deliver" the specified
quantity of liquid rather than "to contain" it. What this really means is that you
should never blow the last drops out of them.

6. Filtration
You will often need to
separate a liquid from a
solid. At times you will
simply decant, that is,
you will carefully pour
out the liquid, leaving the
solid behind. At other
times you will need to
filter the solution. To do
this you will use filter
paper and a funnel. You
must first flute the paper
in order to accelerate the
process; this is shown in
Figure 7.

Figure 7: Fluting the Filter Paper


You will then set the paper in the funnel using your wash bottle. To do this
simply place the paper into the funnel and add a small amount of water to the
bottom of the filter. Slowly add water to the sides with a circular motion to avoid
air bubbles between the paper and the funnel. Once the paper has set, transfer the
solution to be filtered. If the solid has settled, decant the liquid through the filter
first in order to save time. Never overwhelm the filter; don't add the solution too
quickly and never come to within one centimeter of the top of the paper. Transfer
the solid using a wash bottle and rubber policeman, and then wash the solid as
directed by the experimental procedure.

7. Heating
You will use both a hot plate and a Bunsen burner to heat solids and solutions.
Always be careful to avoid burns and never heat a material too quickly or
explosive "bumping" can occur. When using a hot plate always begin at the
setting indicated in the manual. However, this setting may vary depending on the
hot plate so you will have to experiment. In using a Bunsen burner, always use a


A-19
tight blue flame as shown in Figure 8. Control the heat transfer by adjusting the
distance from the burner to the object. Note that the distances suggested in the
manual are measured from the hottest part of the flame to the object.




Figure 8: The Bunsen Burner


8. Barometric Readings and Unit Conversions
There are barometers placed in each laboratory room that give the barometric pressure
readings in inches of Hg. This measurement must be converted to mmHg. The
conversion factor is 1.00 inch = 25.4 mm.


A-20
9. pH Meter Operating Instructions














A-21
E) Maps




A-22

A-23

F) Dispensary Procedures
1. Dispensing Policies
The following outline concisely describes the various stockroom dispensary
procedures that will be used this quarter. Please read this over carefully, and
discuss any questions you may have with your TA.



a. Policies at Beginning of Quarter

Goggles You must use the approved goggles given to you in Chemistry
2A. If you have lost those goggles, it is your responsibility to replace them
before the lab starts.

Locker Supplies There will be a two-week grace period for filling out
dispensing room slips when checking out supplies from the dispensary for
your locker. Make sure that you have everything on your locker list by the
end of the second week of instruction.

b. Policies During the Quarter

Locker Supplies If a locker item is broken after the initial two-week
period, you must bring the broken item or a representative portion thereof
to the dispensary and fill out a dispensing slip for a replacement. If for
some reason you are not able to bring the broken item, you must fill out a
dispensing room slip and have your TA sign it before you may obtain a
replacement.

Equipment on Loan from the Dispensary All equipment that is on loan
from the dispensary must be returned to the dispensary at the end of each
laboratory period.

Refilling of Chemical and Supply Containers When replacing or refilling
general laboratory chemicals or supplies, be sure to bring the empty
containers to the dispensary. In the case of chemical containers, be sure to
return the tops or caps with the containers.

Waste Containers Full waste containers may be exchanged for empties
located below the fume hoods. Additional containers may also be obtained
from the dispensary.

c. Policies at the End of the Quarter

Surplus Stores Any item you may have in surplus should be placed in the
area set aside for surplus items in the laboratory (a box at the back of the
lab).

Filling Locker Requirements If your locker is short of any items when you
are checking your locker equipment against your locker list, obtain the

A-24
missing items from the surplus items in the laboratory. If the missing item
is not in the surplus area, obtain it from the dispensary.

Preparing Your Locker for Check-In Clean all equipment. Replace all
broken or missing items by checking them out from the stockroom. Return
all extra equipment to the extra glassware box in the lab. Have your TA
check the contents of the locker and if everything is present and clean then
they will lock the drawer.

A-25
2. Waste Labels

WASTE LABELS used in Chem 2 Classes:
Chem 2 Experiments
Cation Metal
Waste
Chemical Waste Composition:
Bismuth, Chromium,
Cobalts, Copper, Lead
Manganese, Silver, Zinc
WASTE
Label is WHITE and is used in all Chem 2 courses.

Chem 2C Experiment
Qualitative Analysis
Chemical Waste Composition:
Chloroform,
Dithizone,
Acetone
WASTE ONLY
Label is BLUE and is used only in Chem 2B


A-26


Chem 2B Experiment
Colligative Properties
Chemical Waste Composition:
Cyclohexane, Acetone,
p-Dibromobeneze,
p-Dichlorobenzene,
Naphthalene, Diphenyl,
Benzophenone,
WASTE ONLY
Label is YELLOW and is used only in Chem 2B


A-27
3. Locker Inventory
GLASSWARE PORCELAIN
1 100 ml Beaker 1 Small Casserole
1 150 ml Beaker 1 Large Casserole
1 250 ml Beaker 1 Evaporating Dish
1 400 ml Beaker 2 Crucible
1 800 ml Beaker 2 Crucible Cover
1 50 ml Erlenmeyer Flask
2 125 ml Erlenmeyer Flask PLASTIC WARE
2 250 or 300 ml Erlenmeyer Flask 1 250 ml Washing Bottle
2 500 ml Erlenmeyer Flask 1 25 ml Graduated Cylinder (may be glass)
1 100mm Watch Glass 1 Short Stem Funnel (may be glass)
2 Glass Stir Rod 2 1 L Bottle, square
10 Test Tubes (rounded end) 1 Desiccator
6 Centrifuge Tubes (pointed end) 1 Pipet bulb w/ Tip
2 Thermometer, non-mercury 1 Plastic Test Tube Rack
2 25 ml Volumetric Flask
1 250 ml Volumetric Flask OTHER
1 5 ml Volumetric Pipet 1 Centrifuge Tube Brush (pointed end)
1 10 ml Volumetric Pipet 1 Test Tube Brush (rounded end)
2 Match Books
METAL EQUIPMENT 1 Vial, Alkacid Test Paper
1 Beaker Tongs 1 Sponge
1 Crucible Tongs 2 Rubber Policeman
1 Scoopula 1 Wire Triangle, Pipe Stem Covered
1 Test Tube Clamp 1 Wire Gauze Square
COMMUNITY LOCKERS SHELVES
8" Extension Clamp 50 ml Buret
Clamp Holder AT LAB BENCH
Small Support Ring Bunsen Burner
Large Support Ring w/ Silicone Rubber Tubing
CHEMISTRY 2 LOCKER LIST
COMMUNITY SUPPLIES
Procedure for end of Quarter
Procedure for beginning of quarter
(1) Replace broken or missing items in your locker in the first two weeks. They may be checked out from the stockroom
(Room 1060). All excess equipment should be placed in the extra glassware box (red) in the lab room.
(2) One pair of SAFETY GOGGLES will be supplied to each Chem 2A student. They must be worn AT ALL TIMES
when in the laboratory, including during locker check out. Only safety goggles which have been approved by the
Chemistry Department are acceptable
Student Name ____________________________________________________ T.A. ____________
(print) (initial)
(1) Clean and dry all equipment.
(2) Replace all broken or missing items by checking them out from the stockroom. Return all extra equipment to the extra
glassware box in lab.
(3) Have your TA check your equipment and initial below.


A-28