Laboratory Manual For General Chemistry
Laboratory Manual For General Chemistry
Laboratory Manual For General Chemistry
General Chemistry
Laboratory Manual
for
General Chemistry
Dale J. Brugh
Dephlogisticated
Dephlogisticated
Columbus, Ohio
dephlo.net
Edition 13.8.26
Copyright law provides the author of this work with pro-
tection. No part of this book (including figures) may be
reprinted, reproduced, or transmitted in any form without
the prior written consent of the author. No part of this work
may be used in any form other than the form in which it is
provided by the author.
Contents
Contents i
Feedback vii
Website ix
Safety xi
Acknowledgments xiii
I Laboratory How To 1
4 Writing an Abstract 23
i
ii Contents
II Laboratory Projects 55
10 Chemical Information 57
10.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
10.2 Safety Considerations . . . . . . . . . . . . . . . . . . . . . . . 59
10.3 Experimental Procedure . . . . . . . . . . . . . . . . . . . . . . 59
10.4 Before Exiting Lab . . . . . . . . . . . . . . . . . . . . . . . . 62
10.5 Post-Lab Assignments . . . . . . . . . . . . . . . . . . . . . . 62
Contents iii
11 Volumetric Glassware 63
11.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63
11.2 Safety Considerations . . . . . . . . . . . . . . . . . . . . . . . 64
11.3 Experimental Procedure . . . . . . . . . . . . . . . . . . . . . . 65
11.4 Before Leaving Lab . . . . . . . . . . . . . . . . . . . . . . . . 66
11.5 Post-Lab Assignments . . . . . . . . . . . . . . . . . . . . . . 67
Amusement 233
Colophon 235
Feedback
vii
Website
This laboratory manual has a companion website at which you can find pre-lab
assignments and other supporting information. A PDF version of this manual is
also available for download. Instructors can request a username and password to
gain access to instructor notes.
↵
http://lab.dephlogisticated.net/genchem
⌦
ix
Safety
This manual contains instructions for experiments that can be dangerous. Do not
attempt to carry out these experiments on your own; they should be carried out
under the supervision of a qualified laboratory instructor.
Every attempt has been made to eliminate errors, but some will inevitably
remain. Even in the absence of errors, laboratory conditions sometimes change at
the last minute, requiring changes in procedures. The procedures in this manual
are no substitute for careful planning and the advice of your laboratory instructor.
Always pay careful attention to announced changes in the laboratory procedure.
xi
Acknowledgments
xiii
Part I
Laboratory How To
Chapter 1
Staying Safe in Lab
All laboratories are dangerous places. There are things you can do, however, to ⌘ Safetey protocols are not just about
your safety. They are also about the
minimize the danger to yourself and to others during laboratory work. The goal safety of everybody else in lab.
is to leave every lab with no injuries. This is what this chapter is about: how to
be safe in the lab.
3
4 Staying Safe in Lab
Use Gloves
Your laboratory drawer will have a pair of yellow kitchen gloves. Feel free to use
these when working with corrosive or toxic chemicals. The gloves are a barrier
against injury. Use them.
Use an Apron
There is a drawer in every general chemistry laboratory with an apron. If you
feel uncomfortable working with a chemical, feel free to wear one. In some
cases, your instructor will recommend that you wear one.
Chemical Spills
If chemicals are spilled on your clothing or on your skin, wash the chemicals off
immediately under cold tap water and then notify your lab instructor so he/she
can determine if you need further medical attention.
1.5. Chemical Hazard Information 7
Cuts
If you are cut, notify your lab instructor immediately so he/she may see that your
wound is properly attended to.
Table 1.1
NFPA hazard rating descriptions for health hazards.
0 No unusual hazard
1 May be irritating
2 May be harmful if inhaled or absorbed
3 Corrosive or toxic. Avoid skin contact or inhalation
4 May be fatal on short exposure. Protective equipment required.
Table 1.2
NFPA hazard rating descriptions for flammability hazards.
0 Not combustible
1 Combustible if heated
2 Combustible liquid flash point of 100ı F to 200ı F
3 Flammable liquid flash point below 100ı F
4 Flammable gas or extremely flammable liquid
Table 1.3
NFPA hazard rating descriptions for instability hazards.
simple asphyxiant (SA), and unusual reactivity with water (W). The symbols for
these special hazards and their meanings are listed in Table 1.4.
Example NFPA hazard diamonds for chemicals you may encounter in the
general chemistry laboratory are shown in Figure 1.4.
It is important to remember that the NFPA system was developed for the
purpose of communicating information to fire fighters and other emergency
responders. Because of this, there is an emphasis on the material hazards in the
Table 1.4
NFPA special hazards symbols and meaning.
3 3 1 0
2 0 1 0 1 0 3 1
Figure 1.4
NFPA hazard diamonds for four chemicals you will encounter in the general
chemistry laboratory.
Oxidizing Highly
Toxic (T) Harmful (Xn) Corrosive (C)
Agent (O) Flammable (F)
Figure 1.5
European Union hazard labels with their meaning and code.
the first places you might seek this information is the material safety data sheet
(MSDS) for that substance.
Material safety data sheets are a common way to catalog the hazards and
safe handling procedures for a material. They are provided by the manufacturer
of a substance, and their exact format varies from supplier to supplier. Despite
this, they typically contain common information. An MSDS normally can be
expected to contain information regarding the composition of the substance,
hazard identifications (including NFPA ratings), first aid measures, fire-fighting
measures, spill handling measures, handling and storage recommendations,
⌘ You can normally obtain physical personal protection requirements, physical and chemical properties, toxicity
data such as boiling points and melting
points from the substance’s MSDS. (including signs of exposure), ecological impact, and disposal recommendations.
The Department of Chemistry saves all manufacturer-supplied MSDS for all
chemicals it buys because the U.S. Occupational Safety and Health Administra-
tion requires that all employees have access to this information. Our collections
of MSDS can be found under the counter in the stockroom. You are welcome
to examine the MSDS for any substance used in the general chemistry lab by
visiting the stockroom. You can find MSDS sheets from other sources, but
generally a fee is required for access. Every employer is required by law to
provide MSDS to their employees for free.
⌘ http://www.acros.com You can obtain MSDS sheets directly from the manufacturer of some chemi-
http://www.sigmaaldrich.com
cals, such as ACROS and Sigma/Aldrich. If you look up a chemical in Wikipedia,
you will often find a link for the MSDS sheet for that substance.
B D E
F A: Gloves
C B: Metal Spatula
C: Glass Stiring Rod
A D: Pipette Bulb
G K E: Watch Glass
F: Litmus Paper
G: Water Bottle
H: Cleaning Cloth
H
L J: Test Tube Tongs
J K: Test Tubes
N
L: Tongs
M: Split Rubber Stopper
P N: Graduated Cylinder
Q P: Beaker
Q: Erlenmeyer Flask
R R: Volumetric Flask
S S: Conical Funnel
M T: Thermometer
T
Figure 2.1
Illustrations of items typically found in a laboratory drawer.
13
14 Checking In and Checking Out of Lab
Each semester we like to make sure your drawer is stocked with the proper
type and quantity of clean and unbroken equipment. Therefore, we ask that you
inventory the contents of your drawer at the start and at the end of each semester
according to the following procedure.
1. Obtain Drawer Inventory: Before you can inventory the contents of your
drawer, you will need a list of what should be in the drawer. This is called
the drawer inventory. If a drawer inventory is not at your bench, ask your
instructor for one.
3. Remove All Equipment From Your Drawer: Remove your drawer from
its slot, and place it on your bench. Remove the contents and place them on
⌘ New sheets of paper for the bottom your bench. If the paper at the bottom of the drawer is dirty, dispose of it and
of your drawer, if needed, should be
available in the front of the lab. replace it with a new sheet of paper.
4. Clean All Equipment: Wash all glassware with soap and water, rinse with
deionized (DI) water, and dry thoroughly. Remove all labels. Make sure that
all other equipment is clean as well.
⌘ Do not return broken or chipped 6. Inventory Equipment: Return the cleaned and undamaged equipment to
glassware to your drawer. your drawer one item at a time. As you return each item, place a check mark
⌘ If you do not know what an item next to that item on the drawer inventory. If you find any extra equipment
looks like, refer to Figure 2.1 for that is not on the list, set it aside and do not put it back in your drawer.
assistance.
7. Check Gloves: Check the provided kitchen gloves for fit and condition. If
they fit and are undamaged, check them off on the drawer inventory. If they
are damaged or do not fit, you will need to get them replaced.
8. Make List of Needed Equipment: All the unchecked items on the drawer
inventory are the items you need to replace.
10. Label Gloves and Goggles: Using a magic marker, put your name on your
goggles and gloves. You can now leave them in your drawer.
11. Sign Drawer Inventory: When you are satisfied that your drawer has every
item on the drawer inventory and that all of the equipment is undamaged,
sign and date the drawer inventory.
12. Have Instructor Check Drawer: Have your instructor check your drawer
and your drawer inventory form. You should make sure your instructor signs
the drawer inventory.
13. Return Drawer Inventory to Your Instructor: Return the signed drawer
inventory to the front desk in the lab.
1. Obtain Drawer Inventory: Your drawer inventory from the beginning of the
semester should be at your bench. If it is not, obtain it from your instructor.
2. Remove All Equipment From Your Drawer: Remove your drawer from
its slot, and place it on your bench. Remove the contents and place them on
your bench. If the paper at the bottom of the drawer is dirty, dispose of it and ⌘ New sheets of paper for the bottom
of your drawer, if needed, should be
replace it with a new sheet of paper. available in the front of the lab.
3. Clean All Equipment: Wash all glassware with soap and water, rinse with
deionized (DI) water, and dry thoroughly. Remove all labels. Make sure that
all other equipment is clean as well.
4. Check for Damaged Glassware: Examine all glassware in your drawer. If
you find any glassware that is chipped, broken, or otherwise unusable, dispose ⌘ If you have any question about
whether a piece of equipment is usable
of it in the broken glassware receptacle. or not, ask your instructor.
9. Have Instructor Check Drawer: Have your instructor check your drawer
and your drawer inventory form. You should make sure your instructor signs
the drawer inventory.
10. Return Drawer Inventory to Your Instructor: Return the signed drawer
inventory to the front desk in the lab.
11. Disposer of Gloves: Throw your kitchen gloves in the trash. They are
contaminated with chemicals and should not be removed from the lab and
used for any other purpose.
12. Take Personal Items With You: Take your goggles and any other personal
items with you as you leave lab.
Chapter 3
Keeping a Laboratory Notebook
Your laboratory notebook is a permanent record of the scientific work you ⌘ Detailed instructions for keeping a
laboratory notebook will vary by
have done and the results you have obtained. It should be accurate and utterly instructor and employer, but the basic
concepts remain the same.
honest. It should be kept in a manner consistent with conventional practice
in chemistry and the specific practices of the organization in which you are
doing your scientific work. This chapter provides some guidelines for keeping a
laboratory notebook in general chemistry at Ohio Wesleyan University.
17
18 Keeping a Laboratory Notebook
gives the reader assurance that nothing has been added or deleted after the
original work was done and recorded. This notebook should be dedicated for
use as a general chemistry laboratory notebook. It should not be used for lecture
notes or for other laboratory courses.
1. Always write in the notebook in permanent blue or black ink. Never use
pencil or erasable ink. Never use any color of ink other than black or blue.
2. Never rip or cut out pages from your laboratory notebook. The notebook is a
record of all things you have done, including the ugly things and the mistakes.
⌘ The fact that you have been asked 2. Number each side of each page of your laboratory notebook in blue or black
to number both sides of each page
means you should use both sides of ink, starting with the number 1 on the very first sheet of paper in the notebook.
each sheet.
Use one of the outside corners for numbering such as the bottom left and
right.
3. Leave pages 1 and 2 blank. On page 3, make a title page by printing the
course title and your name. If you have done things correctly, this page should
be on the right side of the notebook.
4. Leave page 4 blank. On page 5, write “Table of Contents” at the top. This is
where you will list the title of each experiment you perform and the the page
number on which each experiment begins.
5. Leave pages 6 through 8 blank for the entries you will make in the table of
contents.
things correctly, this will be a page on the right side of your laboratory notebook.
Work for every project should begin on a new odd numbered page.
The following list describes in more detail what you should put in your
laboratory notebook when starting a new project with pre-lab work. Note that if
there is no pre-lab assignment for a particular experiment, you can just move on
to the next section.
1. Write the title of the experiment at the top of the starting page.
2. Under this title, write a subtitle for the type of work you are doing. For
instance, if you are doing pre-lab work, write “Pre-Lab Assignment” under
the experiment title.
3. Write the date next to the title in the ISO standard dating format: 2012-09-15
(Year-Month-Day). This should be the date that you are doing the work, the
actual date at the moment you are writing the date. Be completely honest.
4. Do your pre-lab work. Since the pre-lab work is primarily for your benefit,
you can organize this material almost any way you want. It must be clear,
however, what you were doing and that you made an earnest effort to complete
the work asked of you. Much like the rest of the notebook, it should be clear
to other readers what you were doing.
5. When you finish pre-lab work for a day, draw a line across the page to
indicate where you stopped. If you continue pre-lab work another day, write
the current date just below the line you drew and keep doing the work. This
will make it clear what work you did on each day.
1. Write the title of the experiment immediately under the line at the bottom of
your pre-lab work.
3. Write the date next to the title in ISO standard dating format.
4. If you are working with partners, include their names near the title.
These are just organizational details. The real content of the notebook
comes next. From the moment you walk into lab until the moment you leave,
everything you do gets described in your laboratory notebook. This section gives
an overview of the things to be included in your laboratory notebook during an
experiment and recommendations for their inclusion. Exact instructions cannot
be written for this part. Every experiment is different, and you will have to learn
to use your judgment about what is important to include and what is not.
20 Keeping a Laboratory Notebook
Even experienced chemists sometimes do not have a feel for the relevant in-
formation to record in the laboratory notebook. Such an understanding develops
with time, and it is our job as instructors to help you develop that understanding.
Procedures
During your experimental work, you should include a detailed description of
the procedures you carry out such that your instructor or another student can
repeat the experiment from your notebook alone. In some cases, you may want
to include diagrams of equipment set-ups because this may be the most effective
way to describe what you did or the equipment you used.
These procedures should be written in your own words as you carry out
the steps. You should not copy the procedure from the laboratory manual nor
should you just reference the laboratory manual. What the manual says to do
and what you did may be different, and the laboratory notebook always needs to
be a record of what you actually did.
Your procedures should be recorded in the past tense. For instance, “added
50.0 mL of DI water to the flask” is appropriate but “add 50.0 mL of DI water to
the flask” is not appropriate. The former is a record of what you did. The latter
is an instruction.
Spectra
⌘ Spectra are included with a single If you use an instrument to collect a spectrum, you should include that spectrum
fold and a single piece of tape.
3.7. What to Include After the Experiment 21
Calculations
Include in your notebook all calculations you must perform. This means that you
should actually do the calculations in your notebook. Remember, the notebook
is a record of all laboratory work, including calculations. If you just include the
answers to calculations, I will assume you plagiarized the result.
Graphs
If you are asked to prepare a graph, it should be included in your laboratory
notebook in the same manner as you include spectra. The graphs included in
your notebook must be labeled on the outside such that it is clear what can be
found on the inside. Do not tape your graphs shut, and do not tape them along
the fold. If you have multiple related graphs to include, you can include several
of them on the same blank page in your notebook by taping them to slightly
different positions on the page such that the graphs are stacked.
For example, if the third post-lab question is “What color was your product?”
do not just write “3. Red” as your answer. Instead. Be more descriptive. Write
something such as “3. The product was red in color.” This will make your answer
independent of the manual. You do not need to re-write the questions in the
post-lab assignment.
23
24 Writing an Abstract
4.3 Content
⌘ An example abstract can be found If you were writing a complete journal article, the purpose of the abstract would
on the course website.
be to convey quickly to the reader the nature and scope of the information
presented in the paper. Therefore, the abstract must be brief. However, it must
also contain sufficient information for the reader to decide whether or not to
read the whole paper. This means it must contain the material that is core to the
experiment and the key results but nothing else.
The abstract should be contained entirely within one paragraph. In that one
paragraph you should do the following in the order given.
The abstract is not to be a list of bullet points. You must write a paragraph
in full English sentences. Be certain to use clear, concise, well-constructed
sentences. Make sure there are no misspelled words. Use proper grammar
throughout.
⌘ Yes, this is an arbitrary choice, and When writing the abstract, do not use first person, active voice. Instead, use
you could write just as effectively in first
person. However, here you must third person, passive voice. Since the experiment has been completed, use past
conform to the expected standard in
chemistry.
tense. For example, do not say “I heated the reaction mixture for 10 minutes.”
Instead, say “The reaction mixture was heated for 10 minutes.” This may seem
strange, but it is the custom in chemistry, and you are expected to follow this
custom.
1. Never begin a sentence with a numerical value. Always find another way to
begine the sentence.
2. All numbers less than 1 should either have a leading 0 inserted before the
decimal or be written in scientific notation.
3. Never begin a sentence with a chemical formula. You can begin a sentence
with a chemical name but not a formula.
5. Make sure each chemical formula is displayed with proper chemical symbols.
7. Never refer to the “week” in which part of a laboratory was conducted unless
the timing was important for the chemistry involved.
8. Never begin the abstract with the phrase, “In this lab.”
9. Never begin the abstract with the phrase, “The purpose of this lab. . . ”
27
28 Writing an Experimental Section
be so short, but in this course your experimental procedures are not terribly
complicated. As a consequence, you are limited to one page to encourage you
to sort through all the experimental details to fish out the important ones for
inclusion.
5.3 Content
An experimental section should contain all the relevant detail necessary for
another expert to reproduce your work. This does not mean that you should
reproduce the instructions from your laboratory manual. Instead, you should
find the most concise way to communicate what was done. This requires that
you understand the important variables in your work. For instance, was the
temperature of your solutions important in obtaining your results? If it was, you
should report the temperature of the solutions. If the temperature was immaterial
to your results, then you should not report it.
This can be confusing early in a scientific career because it may not always
be clear what is important and what is not. This is understandable, but you
are expected to make some effort to sort through your experiment to find the
important facts. This is part of the purpose of asking you to write an experimental
section.
In an experimental section, you should do the following.
⌘ Always use appropriate units. 2. State the identity and quantity of reagents used in the experiment.
As with all scientific writing, you should strive to be concise. However, just
because the experimental section is to be concise does not mean you do not
have to use full English sentences. You do! Be certain to use clear, concise,
well-constructed sentences. Make sure there are no misspelled words. Use
proper grammar throughout.
⌘ Yes, this is an arbitrary choice, and When writing the experimental section, do not use first person, active voice.
you could write just as effectively in first
person. However, here you must Instead, use third person, passive voice. Since the experiment has been com-
conform to the expected standard.
pleted, use past tense. For example, do not say “I heated the reaction mixture
for 10 minutes.” Instead, say “The reaction mixture was heated for 10 minutes.”
This may seem strange, but it is the custom in chemistry, and you are expected
to follow this custom.
5.3. Content 29
1. Never begin a sentence with a numerical value. Always find another way to
being the sentence.
2. All numbers less than 1 should either have a leading 0 inserted before the
decimal or be written in scientific notation.
3. Never begin a sentence with a chemical formula. You can begin a sentence
with a chemical name but not a formula.
4. Be sure any chemical formulae with subscripts are actually displayed with
subscripts in the document.
5. Make sure chemical formulae are displayed with proper chemical symbols.
Microsoft Word will sometimes change the capitalization in chemical formu-
lae, so be careful.
6. Never refer to the “week” in which part of a laboratory was conducted unless
the timing was important for the chemistry involved.
30 Writing an Experimental Section
6.1 Introduction
31
32 Melting Point Range Determination
⌘ A narrow melting point range is Using the technique described in this chapter, pure substances will be observed
evidence that a substance is pure.
to melt over a narrow temperature range of between 0.5ı C and 2ı C. In fact, a
narrow melting point range is good evidence that the substance being melted
is pure. If the determination of the melting point range is performed carefully,
the literature value for the melting point of a substance should fall just below or
within the experimentally determined melting point range.
⌘ A wide melting point range is If the substance being melted is actually a mixture of more than one substance,
evidence that a substance is impure.
the melting point range will not be narrow. The range will typically be greater
than 2ı C. In fact, the observation of a wide melting point range is good evidence
that a substance is not pure.
In addition, impure substances will melt at a lower temperature than the pure
substance, providing the level of impurity is low. If the level of impurity is high,
the situation is more complicated, and few general statements can be made.
Let’s say you have just measured the melting point range of an unknown com-
pound to be 133ı C to 133:5ı C. You also know, because your instructor has told
you, that the substance must be one of 4 compounds: benzoic acid, 2-naphthol,
urea, or trans-cinnamic acid. Can you identify the unknown substance?
First, you know that your unknown substance is probably pure since the
melting point range is narrow. Second, if you look up the melting points of the
four compounds listed above, you will find that only urea and trans-cinnamic
acid are possible matches. These two compounds have known melting points
near 132ı C while benzoic acid and 2-naphthol have melting points near 121ı C.
Since urea and trans-cinnamic acid have the same known melting point and
since that melting point is a good match to your unknown substance’s observed
melting point range, how can you possibly identify your unknown? This is
actually easy.
For the sake of argument, let’s say that your unknown substance is urea. If
you mix a small quantity of urea with your unknown and determine the melting
point range of the mixture, you will observe nearly the same melting point range
as you did for your unknown alone. However, if you mix a small quantity of
trans-cinnamic acid with your unknown and determine the melting point range
of that mixture, you will observe a melting point range that is wider than that
for the unknown. In addition, the melting for this mixture will begin at a lower
temperature than it did for the unknown alone.
6.2. Experimental Procedure 33
Prepare Sample
1. Obtain Melting Point Capillary: All samples to be melted must be placed
into the open end of a glass melting point capillary tube. These capillaries Figure 6.1
are provided in a plastic tube, as shown in Figure 6.1. Find where these A container of melting point
are located and obtain one for each melting point range experiment to be capillaries.
conducted.
2. Pulverize Sample If Needed: Since the open end of the melting point
capillary is small (see Figure 6.2), the sample to be melted must be finely
divided. Samples such as those shown in Figure 6.3 will easily fit into the
melting point capillary. Samples such as those in Figure 6.4 will not and must
be pulverized into a fine powder in a mortar and pestle (Figure 6.5) before
being placed into the capillary.
Figure 6.2
Melting point capillaries,
showing the open end (left
three) and the closed end
(right three).
3. Place Small Quantity of Sample into Melting Point Capillary: Push the Figure 6.5
open end of the melting point capillary into the finely divided sample powder A mortar and pestle used
to force a small quantity into the capillary. Invert the capillary and tap the to grind samples into a fine
closed end on the lab bench to force the sample to the bottom. You may have powder.
to repeat this process to get enough sample into the capillary. In the end, you
should have approximately 1 to 2 mm of sample in the tube. Figure 6.6 shows
a melting point capillary filled to the proper depth.
4. Be Forceful with the Capillary if Necessary: Sometimes the sample will ⌘ The glass capillary will not break. It
will, in fact, bounce off the bench,
not go to the bottom of the capillary after tapping the capillary on the lab which is a cool thing to see glass do.
bench. In these cases, we have a glass “drop tube” about 1 meter in length
and open on both ends that will help. Obtain the drop tube, place one end on
34 Melting Point Range Determination
the laboratory bench, and drop the melting point capillary through the top
(closed end down). Repeat as necessary.
Melt Sample
1. Take Capillary to Mel-Temp: Take the filled melting point capillary to the
Mel-Temp apparatus shown in Figure 6.7. Check the temperature of the
Mel-Temp to make sure it is below the melting point of your sample. If you
do not know the melting point of your sample, make sure the Mel-Temp
temperature is below the lowest melting point you expect to measure. If you
are completely unsure of what melting point range you will measure, make
sure the Mel-Temp is at a temperature of no higher than 30ı C
2. Place Capillary Into Mel-Temp: The melting point capillary fits into a slit
in the Mel-Temp that is located just in front and to the right of the thermometer
Figure 6.6 as indicated in Figure 6.7. There are three slots in the slit that can hold the
A melting point capillary capillary. It does not matter which slot you use for your capillary. Place the
filled to the proper depth. capillary into one of these slots.
Thermometer
Capillary goes
in here.
Heating Rate Dial
On/Off Switch
Figure 6.7
View sample The Mel-Temp apparatus with an expanded view of the place where melting
through here. point capillaries are inserted.
3. Begin Heating Sample: Turn the heating rate dial on the Mel-Temp (see
Figure 6.8 Figure 6.7) to between 3 and 4 to achieve a heating rate of between 5ı C and
View the sample capillary 10ı C per minute. Then turn the on/off switch to the on position. A light
through this window and should come on in the viewing window, allowing you to see the capillary
lens. through the viewing lens as shown in Figure 6.8.
⌘ The more slowly the sample is 4. Monitor Sample: Continue viewing the sample in the capillary through the
heated the better your results will be.
However, slower heating means that it viewing lens, and periodically check the temperature and the rate of change
will take more time to collect the
melting point range. You have to make
of the temperature. If the temperature changes too rapidly (more than 10ı C
a trade off between time and the quality per minute, turn the heating rate dial to a lower number. You can twirl the
of your results.
capillary in its slot from time to time to inspect both sides of the sample.
6.3. Working With a Partner 35
5. Record Temperature When Melting Begins: At some point, you will no-
tice liquid forming in the capillary tube. Record the temperature at the
thermometer when you make this observation.
Cleanup
1. Turn Off Mel-Temp: When the sample has completely melted and you have
recorded the melting point range in your laboratory notebook, turn off the
Mel-Temp and remove the sample capillary.
2. Dispose of Sample Capillary: Dispose of the sample capillary in the broken ⌘ If you need to record a melting point
range for the same substance, prepare
glass waste container in the back of the room. Do not attempt to reuse the a new capillary. Never reuse the
sample after it has melted.
capillary. Do not throw the capillary into the normal waste container.
7.1 Introduction
Defining the Boiling Point
When you heat a liquid, a temperature is eventually reached at which bubbles ⌘ The bubbles that form along the
walls of the container early in the
begin to form in the liquid along the container’s walls. As the temperature heating process are usually just
dissolved air being forced out of the
continues to increase, the bubbles occasionally break free from the container liquid.
and rise to the surface. At some temperature, a constant stream of bubbles rises
to the surface from the walls of the container and from everywhere else in the
liquid. At that point, the temperature of the liquid is observed to remain constant
until all the liquid has turned to a gas. This temperature is the boiling point of
the liquid.
That was an experimental, or empirical, description of the boiling point. It is
defined in terms of things we can easily see or measure with just a thermometer.
More formally, the boiling point is defined as the temperature at which the vapor
pressure of a liquid equals the atmospheric pressure. That may sound cryptic,
but the two definitions are consistent with each other.
37
38 Boiling Point Determination
out of the liquid is imprecise because one has to make a decision about when
the boiling point has been reached based on the number of bubbles reaching the
surface of the liquid. This is subjective. Even if you wait for the liquid to reach
a constant temperature you will encounter problems. Near the boiling point the
temperature will change very slowly, and unless your container of liquid is large,
you will observe temperature fluctuations at the boiling point.
Figure 7.1 Instead, it turns out that it is much easier (and more precise) to detect when
Ring stand burette clamp. the vapor pressure of the liquid equals the pressure of the atmosphere pushing
down on the sample. In other words, from a practical point of view it is easier to
employ the formal definition of the boiling point to determine the boiling point.
This is what we will do in this procedure description.
Figure 7.4
Inverted melting point cap-
illary attached to thermome-
ter.
7.2. Experimental Procedure 39
Prepare Sample
1. Place Liquid In Test Tube: Add approximately 3 mL of the liquid to be
tested to the 5-inch test tube. Add a single boiling stone to the liquid in the
test tube.
Figure 7.6
The thermometer and cap-
Figure 7.7 illary should be about 5-10
The final setup for a boiling mm above the bottom of the
point determination should test tube.
look something like this.
2. Begin Heating Water Bath: Turn the hot plate on and turn the heating dial
to a middle position (medium). If after 10 minutes the water temperature
has not increased more than 10ı C, you might consider increasing the heating
rate.
3. Monitor Sample and Capillary: Keep monitoring the sample liquid and
the capillary until bubbles begin to come out of the open end of the melting
point capillary. At first the bubbles will come out slowly and appear to “stick”
to the end of the capillary. Wait for the bubbles to come out regularly and
without “sticking” to the end of the capillary.
40 Boiling Point Determination
4. Remove Test Tube from Water Bath: When the bubbles come out of the
capillary regularly, loosen the screw holding the burette clamp to the ring
stand poll and raise the test tube completely out of the water. Retighten the
clamp’s screw.
5. Look for Liquid Rise in Capillary: Immediately begin observing the melt-
ing point capillary in the liquid. The liquid will eventually begin to rise in
the capillary. The instant this begins to happen, record the temperature at the
thermometer. This is the boiling point.
7.3 Clean Up
1. Dispose of Liquid Properly: Dispose of the liquid according to the proper
waste disposal guidelines. If the liquid is an organic liquid, you will likely
have to dump it into the appropriate waste containers.
3. Turn Off Hot Plate and Disassemble Setup: Turn off and unplug the hot
plate. Break down the ring stand and burette clamp and return them from
where you obtained them.
bottom of the capillary, being displaced by warmer vapor. The cooled vapor
exits the capillary as a bubble.
When you know there is nothing in the capillary except liquid vapor (when
you see bubbles coming out of the capillary), you pull the test tube out of
the water bath. Everything begins to cool. As the liquid begins to cool, its
vapor pressure decreases. This means the pressure of vapor in the capillary also
decreases. When it decreases to just below atmospheric pressure, liquid will
begin to rise in the capillary.
Since the boiling point is defined as the temperature at which the vapor
pressure of the liquid and atmospheric pressure are equal, the temperature at
which the liquid rises in the capillary is a measure of the boiling point.
In your study of chemistry you will often need to summarize repeated experimen-
tal measurements, and the typical way to do that is to compute the average and
standard deviation of the measurements. This chapter describes how to calculate
these quantities and provides some insight into their meaning.
8.1 Introduction
If five different people measure your height on the same day using the same
measuring device, all five results are likely to be different. Such is the nature of
the measurement process. Random errors always conspire to make the results of
repeated measurements different. Are all of these results wrong? Are all of them
correct? Is there a single correct result?
These are all valid questions. The answer to each question is “no.” No
result obtained from measuring your height has any more claim to correctness
than any other as long as the measurement technique is appropriate. Instead,
each measurement is considered just one sample from the entire universe of
all possible values that could be determined for your height using the given
measurement process.
If no value is more correct than any other, what is your true height? Do you
have a true height? Yes, you have a true height, but you do not know that true
height. In fact, some would argue you cannot know your true height because
the “true” value is exact with no uncertainty, but all measured quantities have
uncertainty. Regardless of your interpretation, what you can always know is the
human approximation of your height, which includes an uncertainty.
This human approximation of the truth is obtained by making many mea- ⌘ The average is also called the
mean, and the two terms will be used
surements of a quantity and then computing the average of the measurements. interchangeably.
The averge of a set of numbers representing a physical quantity is our best guess
of the truth.
To quantify our confidence in the average as a measure of the truth, we ⌘ The standard deviation is a
measure of the precision of an
often compute the standard deviation of the measurements about the average. experimental measurement.
This quantity is a direct measure of our uncertainty in determining the average
43
44 Basic Statistical Analysis Of Results
1 X
N
xi (8.4)
N
i D1
where xi stands for any of the measured values. Equation 8.4 means exactly the
same thing as Equation 8.3.
Now that we have a compact definition of the mean in Equation 8.4, we need
a symbol to represent the mean. A typical symbol used is x,
N or any other variable
with the horizontal bar over it.
1 X
N
xN D xi (8.5)
N
i D1
⌘ The table measured table lengths We need a way to express this mathematically. We will derive the expression
are (in meters) x1 D 2:45,
x2 D 2:40, x3 D 2:48, x4 D 2:60, using reasoning similiar to that for deriving the expression for the mean in
x5 D 2:33, and x6 D 2:40
Equation 8.5. We will use the same set of measured table lengths to work
through this derivation.
The deviation from the mean for each measured table length can be calculated
by taking the difference between each measured value and the mean, x. N For
instance, .x1 x/N is the deivation of measurement x1 from the mean. To be more
specific, .x1 x/N D 2:45 2:44 D 0:01, in units of meters. This is, undeniably,
a measure of how much that single measurement deviates from the mean.
We can also carry out this same calculation for all other measured values.
The results are in units of meters, of course.
.x1 N D .2:45
x/ 2:44/ D C0:01 .x2 N D .2:40
x/ 2:44/ D 0:04
.x3 N D .2:48
x/ 2:44/ D C0:04 .x4 N D .2:60
x/ 2:44/ D C0:16
.x5 N D .2:33
x/ 2:44/ D 0:11 .x6 N D .2:40
x/ 2:44/ D 0:04
These values are the deviation of each measured value from the mean. How do
we combine them into a single measure of the deviation of the measurements
from the mean? You might think that you should average these deviations. This
would be a good first guess, but it is incorrect.
⌘ The average of the individuals The problem with summarizing the individual deviations by averaging them
deviations of the table length
measurements from the mean is 0.00 is that normally the average of the individual deviations will turn out to be 0.
meters when significant figures are
properly accounted for.
If the errors in measurement are truly random (as we expect), there will be an
equal number of measurements above and below the mean, leading to an average
deviation from the mean of 0. Obviously this will not be satisfactory. It would
imply that all measurements are perfect!
⌘ Technically, we do not calculate the Instead, we first compute the square of each individual deviation and then
average, but that detail will be handled
later. compute the average of the square of the deviations. Finding the square of each
deviation transforms all negative deviations into positive deviations, giving us an
all-positive measure of deviation from the mean. This prevents the deviations
from averaging to 0.
⌘ Some of these results have more .x1 N 2 D C0:0001
x/ .x2 N 2 D C0:0016
x/
than the proper number of significant
figures. This is acceptable because
these are intermediate results. They .x3 N 2 D C0:0016
x/ .x4 N 2 D C0:0256
x/
are not the final result we want.
.x5 N 2 D C0:0121
x/ .x6 N 2 D C0:0016
x/
Adding up all these values (the square of the deviations) we obtain a value of
0:0426.
The calculation we have just done can be summarized mathematically as
X
N
.xi N 2 D 0:0426
x/ (8.6)
i D1
This is the sum of the squares of the deviation of each measurement from the
mean. We can now find the average of the deviations, with one small twist. The
8.4. Interpretation 47
1 X
N
.xi N 2 D 0:00852
x/ (8.7)
.N 1/
i D1
where N is again the number of measurements. Notice that we have divided by ⌘ We divide by N 1 rather than N
because we have lost a “degree of
N 1 rather than N to find something I call an “average” of the squares of the freedom” when we calculated xN . After
we did that, we really only had N 1
deviation from the mean. This is for technical reasons, but for all practical pur- unique values left, not N .
poses, this is an average. In fact, if you were to make hundreds of measurements,
N 1 essentially equals N , and this is truly an average.
Are we there yet? No. This is not the standard deviation. Instead, Equa-
tion 8.7 is called the variance. The variance is just the square of the standard
deviation. The standard deviation is
v
u
u XN
p
t 1
.xi x/ N 2 D 0:00852 D 0:09 (8.8)
.N 1/
i D1
in units of meters and to the proper number of significant figures. ⌘ Standard deviations are always
reported to one significant figure.
Of course, we need a symbol for standard deviation. The symbol that is
traditionally used for standard deviation is :
where xi stands for all the measured values from x1 to xN , and the symbol
˙ means “sum of.” To calculate a standard deviation you must have at least
three measured values.
8.4 Interpretation
We have determined that for our measurements of the table length that xN D
2:44 m and D 0:09 m. Notice that both the mean and the standard deviation ⌘ The standard deviation does have
units.
about the mean have units. We can summarize both results by saying that the
length of the table is 2:44 ˙ 0:09 m. Everything after the ˙ is the standard
deviation.
With this statement, we are saying that our best guess of the length of the
table is 2.44 m and that our measurements are expected to show a deviation from
the mean of 0.09 m. When we write 2:44 ˙ 0:09 m we are also saying that the
true value of the table’s length may lie anywhere from 2.35 m to 2.53 m with
about 66% confidence.
48 Basic Statistical Analysis Of Results
Note that the value of xN should never have more decimal places than . In
fact, determines how many decimal places in xN are significant. This is true
regardless of whether the rules for dealing with significant figures in calculations
tells you that xN should have more decimal places.
8.5 Example
Let us assume you have performed a series of titrations to determine the concen-
⌘ Do not worry about the units if you tration of calcium in a solution. You obtained the results ŒCa2C ç D 0:01104 M
do not understand them. Just make
sure you keep them. for trial 1, ŒCa2C ç D 0:01198 M for trial 2, and ŒCa2C ç D 0:01157 M for trial 3.
What is the average value of the concentration of calcium, ŒCa2C ç, in solution?
What is the standard deviation?
The mean is calculated using Equation 8.5 with N D 3.
1
Mean D xN D .0:01104 C 0:01198 C 0:01157/ D 0:01153M (8.10)
3
The standard deviation is calculated with Equation 8.9. The best way to approach
a standard deviation calculation is to make a table showing xi , .xi x/, N and
.xi x/ N 2 . This way you will not forget something. For this example, such a
table would look like that in Table 8.1. It is then a simple matter to sum the
Table 8.1
Example table for calculation of a standard deviation.
X
N
.xi N 2 D 4:6 ⇥ 10
x/ 7
(8.11)
i D1
We can then divide this result by N 1 D 2 and take the square root to
obtain D 0:0005 M. Since the standard deviation reflects the precision of our
measurements we report it to one significant figure.
Our final answer for our best guess as to the concentration of calcium ion
in this solution is 0:0116 ˙ 0:0005 M. Note that I have rounded the average
to 0.0116 from 0.01157 because the standard deviation tells us that the first
uncertain digit is the forth one after the decimal point. Including more digits is
meaningless.
Chapter 9
Preparing Acceptable Graphs
9.1 Software
Many software packages can present numerical data in graphical form. Some of
these include Microsoft Excel, Wolfram Mathematica, Apple Numbers, Omni-
GraphSketcher, Plot, KaleidaGraph, Minitab, IGOR Pro, pro Fit, and gnuplot.
Each package has its advantages and disadvantages. In this course, we will use
the charting capabilities of Microsoft Excel to present numerical data in graphi-
cal form. Microsoft Excel is not the best for this purpose, but it is universally
available on campus and easy to learn.
49
50 Preparing Acceptable Graphs
3. If a physical quantity is plotted along an axis, that axis must display the units
of the values plotted on that axis.
4. Most small data sets are best represented as scatter plots in Microsoft Excel.
This is a plot in which each data point is represented by a marker at the
appropriate x and y value.
5. All data point markers should be open or closed black circles at a size that
does not overwhelm the graph. For most purposes, the size of the data point
marker in Microsoft Excel should be near 5 points.
⌘ Fitting data to a straight line is 6. Never connect the dots. Never. There are exceptionally few instances in
different than connecting the dots. You
will fit data to a straight line many times. chemistry when you want to connect the dots in plotted data.
You will never connect the dots.
7. The data should fill the area of the graph. Adjust the range of the axes so that
the data markers fill the graph area.
8. No legend is necessary for simple graphs like the ones produced in general
chemistry. Microsoft Excel will insert a legend by default. You should remove
it.
9. Most graphs should not have grid lines displayed. They are normally distract-
ing and unhelpful. Microsoft Excel includes grid lines by default. Remove
them.
10. Axes should include tick marks at regular intervals along each axis.
11. Graphs for publication will typically have axes drawn on all four sides of
the graph. This is not possible in Microsoft Excel. Thus, you do not have to
worry about this guideline.
12. The entire graph should appear in black and white. No color and no grays
should be used unless it is for communicating something important. In most
cases, the use of color is merely aesthetic and should be avoided.
13. Sometimes, Microsoft Excel will create graphs with a gray background.
Because of the previous guideline, you will need to change the background
to white if Microsoft Excel makes it gray.
Table 9.1
Boiling points and molar masses of the first eight aliphatic aldehydes as col-
lected from Wikipedia.
was produced. I have omitted the details of how to go from the default graph
produced by Microsoft Excel to one like that in Figure 9.1. You can find these
details on the course website. For now, just pay attention to the final result. ⌘ For details on how to create and
customize graphs in Microsoft Excel,
see the course website, ask your
instructor, or click around in the
Boiling'Point'Versus'Molar'Mass'for'Aldehydes' software until you make what you want
to make.
200.0%
150.0%
Boiling'Point'(degrees'C)'
100.0%
50.0%
0.0%
!50.0%
20.0% 30.0% 40.0% 50.0% 60.0% 70.0% 80.0% 90.0% 100.0% 110.0% 120.0% 130.0%
Molar'Mass'(g/mol)'
Figure 9.1
Graph of the boiling point of eight aliphatic aldehydes as a function of their
molar mass that illustrates the guidelines for preparing acceptable graphs.
Notice how the graph in Figure 9.1 is very simple. The data markers fill the
graph area; the axes are well labeled with units; the only colors are solid black
and white. The graph in Figure 9.1 displays the data and enough information
to make sense of the data. Nothing extraneous is present. There is nothing in
Figure 9.1 to distract the viewer from the data. You should work to prepare
graphs of this quality.
52 Preparing Acceptable Graphs
where x and y are variables and m is the slope, the factor that describes how y
changes when x changes.
To test how well data obey a linear relationship, we fit those data to a straight
line. Technically, this is called a linear least-squares fit. A linear fit finds the
straight line that minimizes the square of the difference between the line and the
data points. In simpler terms, a linear fit finds the best line that goes through
the data. This is called the best-fit line. If the data points fall on or very near
the best-fit line, the fit is considered good. If the data points clearly fall off the
best-fit line, the fit is considered poor. The quality of the fit can be quantified by
a calculated value called R2 . When R2 is 1:0, the fit is perfect, meaning that all
the data points fall exactly on the best-fit line. The data follow an exactly linear
relationship. A smaller value of R2 indicates a fit that is less good, with more
and more data points falling off the best-fit line.
We can examine the data in Table 9.1 to determine if there is a linear relation-
ship between molar mass and boiling point. A quick look at the data in Table 9.1
shows that the boiling point of an aldehyde increases roughly in proportion to
the increase in molar mass. The relationship is not exact, but there might be a
linear relationship. The graph of the data, shown in Figure 9.1 appears linear.
How good is this linear relationship?
Software that can plot data often has the ability to fit data to models such
⌘ In Microsoft Excel, fitting data to a as a straight line. The procedure is different for each software package. When
mathematical model is called adding a
trendline. For details about how to do the data in Figure 9.1 are fit to a straight line in Microsoft Excel, the result in
this, see the course website.
Figure 9.2 is obtained.
The fact that the data points in Figure 9.2 lie fairly close to the best-fit line
from low molar mass to high molar mass indicates that there is a fairly good linear
relationship between molar mass and boiling point for these compounds. The
R2 value is 0:99298, which is a good value, indicated a good fit. The equation
of the best-fit line on the graph shows that when the molar mass increases by one
unit, the boiling point increases by 1:9ı C.
In general chemistry, you should always include the equation for the best-fit
line and the R2 value on the graph if you fit the data to a linear model. These
pieces of information are often helpful.
9.5. Language and Graphs 53
Boiling'Point'Versus'Molar'Mass'for'Aldehydes'
200.0"
150.0"
Boiling'Point'(degrees'C)'
100.0"
y"="1.9023x"+"66.541"
R²"="0.99298"
50.0"
0.0"
+50.0"
20.0" 30.0" 40.0" 50.0" 60.0" 70.0" 80.0" 90.0" 100.0" 110.0" 120.0" 130.0"
Molar'Mass'(g/mol)'
Figure 9.2
Graph of the boiling point of eight aliphatic aldehydes as a function of their
molar mass along with the best-fit line. The equation of the line and the R2
value are shown on the graph.
Laboratory Projects
Chapter 10
Chemical Information
10.1 Introduction
The quantity of chemical information in the world is growing as you read this.
By the time you finish this lab, chemical and/or physical data for at least one
new molecule will be published in the literature or stored in a database. Where
is this information? How is it stored? How do you find it? How do you retrieve
the data? How do you know it is reliable data?
As a scientist studying chemistry, it is important to be familiar with how to
find and access reliable chemical data in the vast ocean of available chemical
information. The number of resources available is large, and we can not cover
them all in one lab meeting. Instead, we will start simple. In this project you
will search for chemical formulas, physical properties, and uses for particular ⌘ Examples of physical properties
include melting point, boiling point,
chemicals in a selection of information sources. solubility, density, and appearance.
57
58 Chemical Information
Merck Index
Unlike the CRC, the Merck Index is a reference handbook focused primarily on
the properties of various chemicals and drugs. Also unlike the CRC, the index
of the Merck Index can be used to look up chemicals.
The index at the back of the Merck Index is called “Cross Index of Names.”
It lists alternate names for compounds, including brand names for drugs. Next to
each name is the monograph number. This number refers to the brief monograph
for that compound. No information is given about the page number on which the
monograph appears.
Wikipedia
The data on Wikipedia does not qualify as peer-reviewed and authoritative;
however, Wikipedia’s own policies require that any data presented on the site
have an authoritative source. Wikipedia’s standards for “authoritative source” are
not the same as a chemist’s standards. In practice, this means that the chemical
and physical data for compounds found on Wikipedia can be used tentatively
but should never be relied upon when publishing. In my experience, the data on
Wikipedia is sufficiently accurate for all work at the general chemistry level.
Wikipedia is edited collaboratively and can be changed at any time. With
many individuals involved in editing Wikipedia, it is unlikely that vandalism
of the site will go unnoticed and uncorrected for long, but this can happen.
Thus, when you look up data on Wikipedia, be aware that it cannot be assumed
to be accurate. Accordingly, citing Wikipedia as a source in any professional
journal publication would be considered unacceptable. Only fixed, peer-reviewed
sources are considered appropriate.
In this project, we will compare data from the CRC and the Merck Index to
that from Wikipedia to assess reliability of Wikipedia.
10.2. Safety Considerations 59
Goggles
You are not required to bring or wear your goggles because all work will be
conducted in the student computer lab this week.
3. Organize Your Laboratory Notebook: Before rushing into the next section
to look up data for your compounds, make sure your laboratory notebook is
organized for the task. Since you know what data you have to look up, you
can make a table in your notebook to hold that data. You also know you will
have to look up most of the data twice: once in the CRC or Merck Index and
once in Wikipedia. Therefore, you might consider making a table in your
notebook with properties listed along the left followed by two columns, one
for the CRC or Merck data and one for the Wikipedia data.
1. Look Up the Chemical Formula of Your Compound(s): Using the CRC or ⌘ Chemical Formula
the Merck Index, look up and record the chemical formula for your assigned
compound(s).
⌘ Molecular Mass 3. Look Up the Molecular Mass of Your Compound(s): Using the CRC or
the Merck Index, look up and record the molecular mass for your assigned
compound(s) in units of grams/mole. Then look up and record the molecular
mass of your compound(s) as reported by Wikipedia.
⌘ Boiling Point 4. Look Up the Boiling Point for Your Compound(s): Using the CRC or
the Merck Index, look up and record the boiling point for your assigned
compound(s) in units of Celsius. Then look up and record the boiling point
of your compound(s) as reported by Wikipedia.
⌘ Density 5. Look Up the Density for Your Compound(s): Using the CRC or the Merck
Index, look up and record the density for your assigned compound(s). Be sure
to record the units. Then look up and record the density of your compound(s)
as reported by Wikipedia.
⌘ Use or Occurrence 6. Look Up the Use or Occurrence of Your Compound(s): Using the CRC
or the Merck Index, look up and record the use or occurrence of your assigned
compound(s).
⌘ NFPA Diamond 7. Look Up the NFPA Diamond for Your Compound(s): Using Wikipedia,
look up the NFPA Diamond for your assigned compound(s) and record it
in your notebook. Wikipedia will not display an NFPA diamond for all
compounds. In these cases, you will have to look elsewhere on the Internet.
An alternate source for NFPA data are MSDS sheets. You can search for
these with the search term “compound name MSDS”. These will typically
not show the NFPA diamond, but they will list the numerical ratings for each
portion of the diamond.
Compile Data
1. Post Your Data: When you have finished looking up the data for your
compound(s), find your compound(s) on the board at the front of the room
and fill in the requested data. Always put up the data from the CRC or the
Merck Index. If the data from Wikipedia agrees with the CRC or Merck Index
data, put the data on the board in black. If Wikipedia disagrees with the data
from the CRC or Merck Index, put the data on the board in red. This way we
can quickly tell how reliable Wikipedia is.
2. Copy Data From Board Into Your Notebook: After you have placed your
data on the board, copy the three tables on the board (and all the data in them)
into your laboratory notebook. Make sure the tables are labeled properly with
the headings on the board: Alkanes, Alcohols, and Acids.
10.3. Experimental Procedure 61
1. Plot Molecular Mass vs. Boiling Point for Alkanes: Using Microsoft
Excel, plot the molecular mass on the x axis and the boiling point on the
y axis for all compounds listed in the table labeled “Alkanes.” The phrase
“Figure 1” should be part of the graph title.
2. Fit Alkane Data to Straight Line: Using the plot prepared in the previous
step, fit the alkane data to a straight line. Be sure to add the equation for the ⌘ See Chapter 9 for information about
fitting data to a straight line. See the
line and the R2 value to the plot. course website for details about how to
fit data to a straight line in Microsoft
Excel.
3. Plot Molecular Mass vs. Boiling Point for Alcohols: Using Microsoft
Excel, plot the molecular mass on the x axis and the boiling point on the
y axis for all compounds listed in the table labeled “Alcohols.” The phrase
“Figure 2” should be part of the graph title.
4. Fit Alcohol Data to Straight Line: Using the plot prepared in the previous
step, fit the alcohol data to a straight line. Be sure to add the equation for the
line and the R2 value to the plot.
5. Plot Molecular Mass vs. Boiling Point for Acids: Using Microsoft Excel,
plot the molecular mass on the x axis and the boiling point on the y axis
for all compounds listed in the table labeled “Acids.” The phrase “Figure 3”
should be part of the graph title.
6. Fit Acid Data to Straight Line: Using the plot prepared in the previous step,
fit the acid data to a straight line. Be sure to add the equation for the line and
the R2 value to the plot.
Write Report
1. Begin Report: Open Microsoft Word or Apple Pages and begin a new
document. In the header, insert your name flush against the left-hand margin
and the date flush along the right-hand margin.
2. Enter Report Title: On the first line of the document, insert the title “Report
for Experiment 1” using a Title style.
3. Enter Compound Information: On the next line of the report, create the
heading “Compound Information” using a Heading style. Under this heading,
list the information you found for your compound(s): compound name,
compound formula, molecular mass, boiling point, density, use or occurrence,
NFPA rating, and drawing. Be sure to cite your sources. You can drag the
drawing you downloaded directly into the word processing document.
62 Chemical Information
4. Create Results Section: On a new line, create the heading “Results” using a
Heading style. Using full sentences in paragraph form, describe the appear-
ance of the graphs you produced. Refer to the graphs as Figure 1, Figure 2,
and Figure 3.
⌘ There is a difference between 5. Create Conclusions Section: On a new blank line, create the heading “Con-
results and conclusions.
clusions” with a Heading style. In this section, comment briefly on the
relationship between molecular mass and boiling point seen in the graphs you
prepared. In other words, draw a conclusion.
6. Include Graphs: After the last line of text, insert a page break to create a
new page. Copy each graph from Microsoft Excel to a separate page of your
word processing document. Make sure the pages are labeled appropriately as
Figure 1, Figure 2, and Figure 3. Save the your document.
Submit Report
1. Convert Report to PDF: Once you are happy with your report, save a copy
of it as a PDF document.
2. Check The PDF: Open the PDF version of your document and check to be
sure it appears exactly the way you want it to appear. If it does not, make
changes and generate the PDF again.
3. Submit Your Report: Submit your report as your instructor wants: either by
email or by electronic upload to a web site.
2 Make sure you have the date next to the start of your experimental work.
2 Make sure all pages in your laboratory notebook have been numbered.
11.1 Introduction
Early in your chemistry experience you may find the variety of equipment
available in a general chemistry lab confusing. For instance, during the first
semester of general chemistry alone you will encounter no fewer than six pieces
of equipment for measuring the volume of a liquid.
To know which piece of glassware to use, you will need to know what you
are trying to accomplish and the precision with which you need to accomplish
that. For example, if you need to add 12:5 ˙ 0:1 mL of acetic acid to a reaction,
you will need a piece of equipment capable of measuring volume with a precision
of 0.1 mL. This means you must know the precision of all the glassware for ⌘ Achieving greater precision
normally takes more time. Because of
measuring volume so that you can make an informed choice. this, it is advisable to use a piece of
equipment designed for a precision no
After you have decided which piece of glassware to use, you will then need greater than you require.
to know how to use that glassware.
Common Glassware
Common glassware for containing liquids and measuring volumes include gradu-
ated cylinders, beakers, and Erlenmeyer flasks. Graduated cylinders can measure
volumes to an accuracy of about ˙0:1 mL. They are not, however, designed to
deliver with such accuracy. With a graduated cylinder, the uncertainty in the
volume of liquid you pour out is greater than the uncertainty of the measured
volume in the cylinder.
Beakers and flasks are mainly intended for containing liquids used in reac-
tions. They are poor choices for dispensing known volumes of liquids. They
have a minimum uncertainty of ˙10 mL.
All of these devices are relatively easy to use. Glassware with greater volume
precision is less easy to use.
Volumetric Glassware
Typical volumetric glassware includes volumetric pipets, volumetric flasks, and
burettes. Volumetric pipets are designed to deliver a given volume of liquid with a ⌘ Volumetric pipets can also be
designed to contain a specific volume
of liquid, but you will not use these in
general chemistry.
63
64 Volumetric Glassware
known uncertainty. The volumetric pipets you will use in general chemistry have
a typical uncertainty of ˙0:01 mL. Volumetric flasks are designed to contain a
given volume of liquid with low uncertainty, typically ˙0:01 mL. Burettes are
designed to measure an arbitrary volume of liquid delivered with a precision of
˙0:01 mL.
Volumetric pipets are used when you need to add to a container a certain
volume of a liquid with high precision. Volumetric flasks are used when you
need to prepare a solution of a known volume. Burettes are used in titrations.
Of all of these, the volumetric pipet is the most difficult to use. It is, however,
important to know how to use it, which is why we dedicate an entire laboratory
project to its use.
This Project
In this project, you will gain experience using a volumetric pipet by first calibrat-
ing your pipet so that you know exactly how much liquid it delivers (along with
the correct uncertainty). You will then use your calibrated pipet to determine
the density of a solution of unknown density. Along the way, you will gain
experience using the top loading balances, another important piece of equipment
in the general chemistry laboratory.
Calibration
Goggles
As with all laboratory experiments, you are expected to wear your goggles at all
times while in the lab. Failure to do so may result in expulsion from the lab.
Waste Disposal
In this lab, we can pour all waste in the sink. There will be no need to use special
waste containers in the hood.
11.3. Experimental Procedure 65
Broken Glass
Do not work with any broken glassware. Dispose of broken glassware in the bins
labeled “broken glass” as shown in Figure 11.1. Do not use the normal waste
baskets for broken glass.
2. Set Flask Aside: Place a thermometer into the flask and set both aside until
the temperature of the water stabilizes (does not change any more). ⌘ This flask of distilled water will be
your personal water reserve so that you
do not have to use the large laboratory
bottles of distilled water as often.
Calibrate Volumetric Pipet with Water
Follow these steps to collect the data that will allow you to determine the actual
volume delivered by your pipet. To complete the calibration, you will have to
look up the known density of water at the temperature of the water reserve.
You should practice using a volumetric pipet before you use it for this
procedure. The practice provides a good opportunity to allow the water in your
water reserve to reach a stable temperature.
1. Rinse 10 mL Pipet: Rinse a 10.00 mL volumetric pipet thoroughly with ⌘ You never need to dry the inside of
the pipet before using it. You should
distilled water three times. understand why this is true and seek
help if you cannot figure it out.
2. Document Pipet Used: In your laboratory notebook, record the information
on the stem of the volumetric pipet you are using.
3. Clean and Dry a 50 mL Beaker: Clean and dry a 50 mL beaker. After the
beaker is dry, handle the beaker as little as possible by hand.
4. Weigh Empty Beaker: Weigh the 50 mL beaker and record the mass in your
laboratory notebook.
5. Add 10.00 mL Water to Beaker with Pipet: Using the volumetric pipet, ⌘ You do not really know that you are
adding 10:00 mL. You only know you
add 10.00 mL deionized water from your water reserve to the 50 mL beaker. have added the volume up to the line.
6. Weigh Beaker with Water: Use a balance to find the mass of the beaker
with the water in it.
7. Empty Beaker: Dump the contents of the 50 mL beaker into the sink.
8. Repeat: Repeat steps 3 to 7 three additional times such that you have a total
of four mass and volume measurements.
66 Volumetric Glassware
⌘ Rinsing ensures that the pipet 2. Rinse Pipette with Unknown Solution Three Times: Pour about 10 mL of
contains only the solution of unknown
volume. the unknown solution into another small beaker and then suck some of this
solution into the pipet to rinse it. Do this a total of three times. Dispose of
the waste rinse in the sink.
3. Clean and Dry a 50 mL Beaker: Clean and dry a 50 mL beaker. After the
beaker is dry, handle the beaker as little as possible by hand.
4. Weigh Empty Beaker: Weigh the 50 mL beaker and record the mass in your
laboratory notebook.
⌘ Actually, it won’t be 10.00 mL that 5. Add 10.00 mL Solution to Beaker with Pipet: Using the volumetric pipet,
you add. The exact volume was
determined in the previous section. add 10.00 mL of your unknown solution to the beaker.
6. Weigh Beaker with Solution: Use a balance to find the mass of the beaker
with the solution in it.
7. Empty Beaker: Dump the contents of the 50 mL beaker into the sink.
8. Repeat: Repeat steps 3 to 7 three additional times such that you have a total
of four mass and volume measurements.
2 Return the volumetric pipet to the tray in the front of the room.
2 Draw a line at the end of your experimental work and sign on the line.
1. Look up the known density of water at the temperature you recorded for the
water reserve. Be sure to record a proper source citation.
2. Convert the literature value for water’s density to g/mL if it is not already in
those units.
a) Calculate the volume of water delivered in each trial using the literature
value of the density of water to convert mass to volume.
b) Calculate the average volume of water delivered.
c) Calculate the standard deviation of the volume of water delivered. ⌘ You need to show your work in your
notebook. Do not use your calculator’s
d) Summarize these results in your laboratory notebook by writing the av- statistical functions.
a) Calculate the density of solution for each trial using the calibrated
volume delivered by your pipet.
b) Calculate the average density of the solution from these measurements.
⌘ You need to show your work in your
c) Calculate the standard deviation of the solution density from these notebook. Do not use your calculator’s
measurements. statistical functions.
Questions
Write answers to these questions in your notebook. You should not put the
answers to these questions in with your experimental work.
1. Compare your value for the calibrated delivery volume of your pipet to that
printed on the end of the pipet. How do they compare?
Chapter 12
Compound Identification Using Physical Properties
12.1 Introduction
From one perspective, chemists can be thought of as chemical detectives. Chemists
have the skills and knowledge to identify substances of unknown identity using
clues about the substance’s physical and chemical properties.
In this lab you will take a step toward becoming a better chemical detective
by experimentally determining some physical properties for an unknown solid
compound and an unknown liquid compound. You will then compare these
experimentally determined values to known values for a set of eight compounds.
Based on your own experimental work, you will have to properly identify the
unknown compounds.
2. Vapors: The vapors released by the solvents in this lab (acetone and toluene)
have a distinctive odor and can make some people nauseous in high concen-
tration. High concentrations should never develop in this lab, but you should
still do your best to work with all solvents under your bench hood so that the
vapors are sucked away.
Goggles
As with all laboratory experiments, you are expected to wear your goggles at all
times while in the lab. Failure to do so may result in expulsion from the lab.
69
70 Compound Identification Using Physical Properties
Waste Disposal
1. Solvents: The solvents used in this lab (acetone, ethanol, and toluene) cannot
be dumped into the sink when you are finished using them. Instead, dispose
of all solvents in the appropriate chemical waste containers in the back of the
room.
2. Unknown Samples: Any unknown sample that remains at the end of the
experiment outside of the original test tube in which it was supplied must be
disposed of in the appropriate chemical waste containers in the back of the
room.
Broken Glass
Do not work with any broken glassware. Dispose of broken glassware in the bins
labeled “broken glass” as shown in Figure 12.1. Do not use the normal waste
baskets for broken glass.
Figure 12.1
Broken glass container. 12.3 Experimental Procedure
This section provides procedures for determining the chemical identity of a liquid
and a solid based on their physical properties. You may work with a partner
during any step of the procedure. In fact, during some indicated steps you are
encouraged to work with a partner. However, you are responsible for identifying
your own unknown solid and liquid.
Organize Yourself
⌘ If the identification numbers do not 1. Record Identification Numbers: At your lab bench you will find an un-
appear in your lab notebook, some
parts of your work cannot be evaluated. known solid and an unknown liquid. Each will be in a corked test tube. Each
You may receive no points for those
portions of the evaluation.
test tube will have a label on it with a number. This number is the identifi-
cation number that allows your instructor to determine which unknown you
were given. Write these numbers down in your lab notebook immediately
along with the sample type for each (solid or liquid).
2. Determine Which Group You are In: To avoid long lines at the balances,
infrared spectrometer, and Mel-Temp apparatus, students will begin this
experiment at different points in the experimental procedure. Your instructor
will divide your lab section into groups for this purpose, each with a different
starting position in the procedure. Figure out which group you are in and
begin with the appropriate experimental procedure.
2. Add Solvents to Test Tubes: Add 3.0 mL of water to the first test tube, 3.0.
mL ethanol to the second test tube, and 3.0 mL toluene to the third test tube.
3. Stopper and Shake: Cork each test tube and shake. Record your observa- ⌘ Be attentive to whether the solid
crystals dissolve or not. If they dissolve,
tions. the solid is soluble in that solvent. If the
crystals do not dissolve, the unknown
solid is not soluble in that solvent.
Determine Melting Point Range of Unknown Solid
1. Determine Melting Point Range: Follow the procedure in Chapter 6 starting ⌧ Work with a partner as described
on page 35 to save time and obtain
on page 31 to obtain the melting point range for your unknown solid. better results.
2. Add Solvents to Test Tubes: Add 2 mL water to the first test tube, 2 mL
ethanol to the second, and 2 mL toluene to the third.
3. Gently Agitate: Gently agitate each test tube for about 30 seconds. Carefully ⌘ If it appears as though there are
two layers of liquid, then your unknown
observe the liquid in each test tube and record your observations. liquid is not soluble in the solvent. If
there is just one layer, then your
unknown dissolved in the solvent.
4. Confirm If Necessary: If you have a question about whether your unknown
liquid is soluble or not, add a few additional drops of the unknown liquid and
observe the changes (if any).
2. Collect Infrared Spectrum: Obtain the infrared spectrum of your sample ⌘ Spectra should appear in a lab
notebook on a page by itself, taped
according to the instructions given by your laboratory instructor. Print out the along one edge, folded, and labeled on
the outside.
collected spectrum and include it in your lab notebook.
72 Compound Identification Using Physical Properties
2 Return the test tubes containing the unused portions of your unknown solid
and liquid samples to the box on the front desk.
2 Check to be sure all solid and liquid wastes (other than the unknowns) have
been poured into the proper waste container.
2 Return the volumetric pipet to the tray at the front of the room.
2 Return clamps and rings to the drawers from which you got them.
2 Check your lab notebook to ensure that you have recorded your unknown
numbers.
2 Draw a line at the end of your experimental work and sign on it.
2 Have your instructor sign on the line at the end of your experimental work.
Calculations
All calculations should appear in your laboratory notebook. If you make an error,
just cross through the error with a single line and then move on.
1. Calculate the density of your unknown liquid from the data you collected. Be
sure to do this to the proper number of significant figures.
1. What is the identity of your unknown solid? Compare all physical properties
data for your unknown solid (melting point and solubility) to the data for
the possible compounds. Decide what your unknown solid is based on these
comparisons. Be sure to justify your conclusion based on your data.
3. What is the identity of your unknown liquid? Compare all physical properties
data for your unknown liquid (boiling point, density, solubility, and infrared
spectrum) to the data for the possible compounds. Decide what the identity
of your unknown liquid is based on these comparisons. Be sure to justify
your conclusions based on your data.
Spectrophotometric analysis is used to determine the percentage of copper by ⌘ This method is based on physical
properties; therefore, it is a
mass in a copper salt of unknown identity. The formula mass of the copper salt non-chemical method.
is determined from this information.
13.1 Introduction
Spectrophotometric analysis in this experiment relies on the absorption of visible
light by complexes containing Cu2C . The light absorbed induces no chemical
change in the copper compounds. The amount of light absorbed can be related
directly to the concentration of copper in solution, which is ultimately the
information you need to determine the formula mass of the unknown copper salt.
The instrument that does this work for us is called an ultraviolet-visible spec-
trophotometer, or UV/Vis spectrometer for short. You will use this instrument in
this lab. The particular model you will use was made by Hewlett-Packard (now
Agilent).
Standard Curve
The problem with this technique is that you rarely know exactly how concen- ⌘ Spectrophotometric analysis is
almost always a two step process:
tration relates to absorption of light for your sample of unknown concentration. preparation of a standard curve
followed by analysis of your own
Therefore, the first step in an analytical spectrophotometric analysis is normally sample of unknown concentration.
to prepare something known as a standard curve. A standard curve is a plot
showing how the absorbance of light changes as the concentration changes for
your unknown species. In other words, preparation of a standard curve tells you
exactly how absorption of light depends on concentration.
How do you make such a curve if your solution is of unknown concentration?
The short answer is that you don’t prepare such a curve with your sample of
unknown concentration. You first have to prepare other solutions, solutions that
are of known concentration. These are called standards. The absorbance of light
75
76 Spectrophotometric Determination of a Copper Salt’s Formula Mass
Mathematical Treatment
To make this analysis work, we have to be more mathematical. The concentration
of a species in a solution is directly proportional to a measure of how much
light is absorbed when it passes through the solution. The exact mathematical
relationship is
A D ✏cb (13.1)
which is called Beer’s Law. In Equation 13.1, A stands for absorbance, which
is a measure of how much light is absorbed. The quantity ✏ is called the molar
absorptivity, and it is a measure of how much light is absorbed by each molecule
in solution. The quantity c is the concentration of the species in units of molarity,
and b is the length of the path the light travels through the solution.
In our case, b D 1 cm because the cells you will use to record the absorbance
of the solutions always have a width of 1 cm. The instrument you will use reports
⌘ Absorbance is actually the base-10 absorbance directly as a unitless number. This is one of the rare cases in which
log of a ratio of two numbers that do
have units, but those units cancel. This it is appropriate to leave units off of a physical quantity (absorbance).
is why absorbance has no units.
Summary
This laboratory experiment involves considerable new information that may
not be familiar. In particular, the concept of a standard curve and its use in
determining the concentration of species in samples of unknown concentration
can be confusing. As such, it is easy to get lost in the details of the experimental
work which can seem tedious at times.
To help you stay focused, Figure 13.1 shows an overview of the steps you
will carry out in this lab. In this figure, the steps highlighted in tan are related
to preparation of the standard curve. The steps highlighted in blue are related
directly to the determination of the concentration of your unknown copper
13.2. Safety Considerations 77
solution. Regardless of the complexity and tedium of the experimental steps, the
experiment is just a five step process.
Goggles
As with all laboratory experiments, you are expected to wear your goggles at all
times while in the lab. Failure to do so may result in expulsion from the lab.
Waste Disposal
1. Copper Solutions: All copper solutions should be poured into the waste
container in the back of the room when you are finished with them. No
solutions should be poured down the drain.
Broken Glass
Do not work with any broken glassware. Dispose of broken glassware in the
bins labeled “broken glass” as shown in Figure 13.2. These containers are in the
back of the lab against the outside wall. Do not use the normal waste baskets for
broken glass.
Figure 13.2
Broken glass container.
13.3 Experimental Procedure
Prepare Standard Solutions
The instructions here allow you to complete task 1 in Figure 13.1.
1. Obtain Five Clean and Dry Beakers: Obtain five clean and dry beakers
of size 150 mL or smaller. Line these beakers up on your work bench and
place a single label on each. Label these beakers “Standard A,” “Standard B,”
“Standard C,” “Standard D,” and “Standard E.”
2. Prepare Beaker Labeled “Standard A”: Pour approximately 50 mL of ⌘ Be sure to record the exact
concentration of the stock solution from
stock Cu2C solution into the beaker labeled “Standard A.” the reagent bottle.
⌘ What is the concentration of this 4. Prepare Beaker Labeled “Standard B”: Use a 25.00 mL volumetric pipet
solution?
to transfer 25.00 mL of the Standard A solution into the 50.00 mL volumetric
flask. Add DI water to the mark, cap the flask, and thoroughly mix the
solution by inverting the flask back and forth ten times. Pour this solution
into the beaker labeled “Standard B.”
5. Clean Volumetric Flask: Rinse the volumetric flask four times with 10 mL
portions of distilled water and shake excess water out of the flask.
⌘ This is to make sure no extra 6. Clean Volumetric Pipet: Rinse the volumetric pipet twice with 5 mL por-
copper is transferred to the beaker
labeled “Standard C.” tions of the solution in the beaker labeled “Standard B.”
⌘ What is the concentration of this 7. Prepare Beaker Labeled “Standard C”: Use a 25.00 mL volumetric pipet
solution?
to transfer 25.00 mL of the solution in the beaker labeled “Standard B” to
the 50.00 mL volumetric flask. Add DI water to the mark, cap the flask, and
thoroughly mix the solution by inverting the flask back and forth ten times.
Pour this solution into the beaker labeled “Standard C.”
8. Clean Volumetric Flask: Rinse the volumetric flask four times with 10 mL
portions of distilled water and shake excess water out of the flask.
⌘ This is to make sure no extra 9. Clean Volumetric Pipet: Rinse the volumetric pipet twice with 5 mL por-
copper is transferred to the beaker
labeled “Standard D.” tions of the solution in the beaker labeled “Standard C.”
⌘ What is the concentration of this 10. Prepare Beaker Labeled “Standard D”: Use a 25.00 mL volumetric pipet
solution?
to transfer 25.00 mL of the solution in the beaker labeled “Standard C” to
the 50.00 mL volumetric flask. Add DI water to the mark, cap the flask, and
thoroughly mix the solution by inverting the flask back and forth ten times.
Pour this solution into the beaker labeled “Standard D.”
11. Clean Volumetric Flask: Rinse the volumetric flask four times with 10 mL
portions of distilled water and shake excess water out of the flask.
⌘ This is to make sure no extra 12. Clean Volumetric Pipet: Rinse the volumetric pipet twice with 5 mL por-
copper is transferred to the beaker
labeled “Standard E.” tions of the solution in the beaker labeled “Standard D.”
⌘ What is the concentration of this 13. Prepare Beaker Labeled “Standard E”: Use a 25.00 mL volumetric pipet
solution?
to transfer 25.00 mL of the solution in the beaker labeled “Standard D” to
the 50.00 mL volumetric flask. Add DI water to the mark, cap the flask, and
thoroughly mix the solution by inverting the flask back and forth ten times.
Pour this solution into the beaker labeled “Standard E.”
14. Clean Volumetric Pipet and Flask: Rinse both the volumetric pipet and
volumetric flask with DI water several times.
1. Obtain Five Clean and Dry Cuvettes: In the lab you will find a box with
new plastic cuvettes. Bring five of these to your work area.
2. Obtain Five New Pasteur Pipettes: Find where the Pasteur pipettes are
stored and bring five new ones to your work area.
3. Fill Cuvettes with Standard Solutions: Using a new Pasteur pipet for each
solution, fill a cuvette with each of the standard solutions you have prepared:
Standard A, Standard B, Standard C, Standard D, and Standard E.
5. Collect Background Spectrum: Fill a cuvette with DI water and collect a ⌘ There will probably already be a
cuvette near the spectrophotometer
background spectrum. with DI water in it. Look for it.
6. Record Absorption Spectrum of “Standard C” Solution: Using the cu- ⌘ Yes, this is out of order, but there is
good reason for doing this. Really, use
vette with Standard C in it, record an absorption spectrum. Standard C first.
7. Set Spectrometer to Record Absorbance at max : One wavelength in the ⌘ Be sure to record in your laboratory
notebook the wavelength used here.
resulting spectrum will have the highest absorbance. Instruct the UV/Vis
instrument to always report the absorbance at that particular wavelength.
⌘ Remember that absorbance is a
8. Record Absorbance at max for “Standard C”: Write down the absorbance unitless number.
of the solution labeled “Standard C” as reported by the UV/Vis at max .
13. Dump Cuvette Contents Into Waste Container: Pour out the contents of
the cuvettes into the waste containers.
80 Spectrophotometric Determination of a Copper Salt’s Formula Mass
⌘ Without the identification number in 1. Record Identification Number: A copper salt sample will be at your bench
your notebook, there may be no way to
grade your results, which means no in a corked test tube. The test tube will have a label on it with a number. This
points can be granted.
number is the identification number that allows your instructor to determine
the true identity of your copper salt. Record this number in your laboratory
notebook.
⌘ If you need to use a mortar and 2. Prepare Salt: Inspect your unknown salt. If the salt appears in large clumps,
pestle, make sure they are clean and
dry before using them. you should attempt to grind the salt in a mortar and pestle before weighing it
out. Otherwise, you will find it difficult to get the salt to go into the volumetric
flask later.
⌧ Do not waste time making the mass 3. Mass Salt: Mass out approximately 3.75 g of your copper salt on weighing
exactly 3.75 g. Get close and record
whatever mass you have. paper. Knowing precisely how much salt you use is critical for this experiment,
but the mass used does not have to be exactly 3.75 g.
⌘ If some salt sticks to the weighing 4. Transfer Salt to Conical Funnel: Insert a conical funnel into a 50 mL
paper, you can use a squirt of DI water
from your water bottle to force it off the volumetric flask. Transfer the salt to the funnel. Be sure all the salt is
paper and into the funnel.
transferred. Leave none behind. Also, be very careful not to spill any.
5. Rinse Salt Into Volumetric Flask: Using your DI water bottle, begin to
squirt DI water into the funnel to help force the salt into the volumetric flask.
Continue this until all the salt is in the flask.
⌘ Be sure not to use too much water. 6. Rinse Funnel and Remove: Once the salt has been pushed out of the funnel
If you fill the volumetric flask past the
line you will have to start over. into the flask, rinse the funnel one more time to be sure all the salt has been
rinsed into the flask.
7. Dissolve Salt in Water: If you have not done so already, fill the volumetric
flask to within 10 mL of the 50 mL mark. Swirl the flask for several minutes
to dissolve the salt. Do not proceed to the next step until the salt completely
dissolves.
8. Fill Volumetric Flask To Line: Using a Pasteur pipet or a clean eye dropper,
carefully fill the volumetric flask to the 50 mL line with DI water.
9. Cap and Mix: Cap the flask or cork the flask and then invert it several times
to be sure it is thoroughly mixed and uniform throughout.
⌘ Do not rinse the volumetric flask
with water and pour into the beaker. 10. Transfer Solution to Clean and Dry Beaker: Pour the solution into a clean
This will dilute the solution. and dry 100 mL beaker. Label the beaker “Cu Unknown Solution A.”
1. Obtain Three Clean and Dry Beakers: Obtain three clean and dry beakers
of size 150 mL or smaller. Line these beakers up on your work bench and
place a single label on each. Label these beakers “Unknown B,” “Unknown
C,” and “Unknown D.”
3. Clean Volumetric Flask: Rinse the volumetric flask with DI water several
times.
4. Clean Volumetric Pipet: Rinse the volumetric pipet twice with 5 mL por-
tions of the solution in the beaker labeled “Unknown B.”
6. Clean Volumetric Flask: Rinse the volumetric flask with DI water several
times.
7. Clean Volumetric Pipet: Rinse the volumetric pipet twice with 5 mL por-
tions of the solution in the beaker labeled “Unknown C.”
1. Obtain Four Clean and Dry Cuvettes: In the lab you will find a box with
new plastic cuvettes. Bring four of these to your work area.
2. Obtain Four New Pasteur Pipettes: Find where the Pasteur pipettes are
stored and bring four new ones to your work area.
82 Spectrophotometric Determination of a Copper Salt’s Formula Mass
10. Record Absorption Spectrum of Solution “Unknown D”: Using the cu-
vette with solution “Unknown D” in it, record an absorption spectrum. Write
down the absorbance value reported by the UV/Vis instrument at the previ-
ously determined max .
⌧ Before doing this, be sure that at 11. Dump Cuvette Contents Into Waste Container: Pour out the contents of
least one of your absorbance readings
falls between 1.0 and the smallest the cuvettes into the waste containers.
absorbance value recorded for the
standard solutions. If not, see your
instructor. Save “Cu Unknown Solution A”
If you have not already completed the laboratory project titled “Gravimetric
Determination of a Copper Salt’s Formula Mass,” you will need to save your
remaining solution and label it “Cu Unknown Solution A.” Otherwise, you can
discard it.
⌘ You should have about 30 mL of 1. Transfer “Cu Unknown Solution A” to Storage Bottle: Pour the remain-
solution remaining.
ing “Cu Unknown Solution A” into a capped storage bottle that will be
provided to you. Seal it tightly and label it. Place it in your laboratory drawer
until next week.
13.4. Before Exiting Lab 83
2 Check your lab notebook to ensure that you have recorded your unknown
number.
2 Draw a line after all your experimental work and sign on that line.
2 Have your instructor sign your notebook on the line you just drew below the
experimental work.
2. Plot a graph of standard solution absorbance at max versus concentration of ⌘ Absorbance goes on the y axis,
and concentration goes on the x
Cu2C (in mg Cu2C /mL solution). axis.
3. Determine the best-fit line (linear least squares line) through these data points ⌘ See Chapter 9 and your lab
notebook for information about fitting
and add that to the graph. data to a straight line. See the course
web site for details about how to do this
in Microsoft Excel.
4. Add the equation for the best-fit line and the R2 value to the graph.
5. Tape one short edge of this plot onto a blank page in your laboratory notebook
and fold in half. Label it on the outside so that it is clear what is inside.
2. Using this absorbance reading, use the standard absorbance curve to determine
the concentration of Cu2C in that solution in units of mg Cu2C /mL solution.
84 Spectrophotometric Determination of a Copper Salt’s Formula Mass
3. Calculate the concentration of Cu2C (in g Cu2C /mL solution) in the original
unknown solution (Cu Unknown Solution A).
4. If you have several absorbance readings from the unknown solutions that lie
along the standard absorbance curve, use them to determine the concentration
of copper ions in the Cu Unknown Solution A as well.
⌘ You will use this value in all 5. Calculate the average concentration of copper ions in the Cu Unknown Solu-
subsequent calculations.
tion A using all usable absorbance measurements.
2. Calculate the percent Cu2C in the original copper salt of unknown identity.
Refer to your laboratory notebook for the total mass of unknown copper salt
originally used.
3. Calculate the formula mass of the original copper salt, assuming only one
Cu2C per formula unit.
Chapter 14
Gravimetric Determination of a Copper Salt’s Formula Mass
14.1 Introduction
Gravimetric analysis in this experiment relies on precipitating the copper in a salt
compound of unknown identity then massing the precipitate. This is a chemical
method because it chemically alters the copper ions in solution.
To carry out the gravimetric analysis you will first dissolve the salt in water
and then use an oxidation-reduction reaction to convert the copper ions to
elemental copper. The elemental copper is not soluble in water and therefore
precipitates out of solution. The reaction that takes place is
The Cu2C .aq/ is blue in solution, but Mg2C .aq/ is colorless. As the Cu2C is
reduced to Cu.s/ and Mg is oxidized to Mg2C , the solution containing the copper
salt will slowly change from blue to colorless.
The solid elemental copper will be at the bottom of the reaction beaker when
the reaction is complete, and it can then be collected via gravity filtration. All
the copper that is collected by this technique was originally in the copper salt.
Thus, the mass of the collected elemental copper is a direct measure of the mass
of copper in the original copper salt.
The mass percent of copper in the original salt can easily be calculated as
85
86 Gravimetric Determination of a Copper Salt’s Formula Mass
Goggles
As with all laboratory experiments, you are expected to wear your goggles at all
times while in the lab. Failure to do so may result in expulsion from the lab.
Figure 14.1
Waste Disposal
Broken glass container.
⌘ The elemental copper is no different 1. Elemental Copper: The elemental copper you produce in this experiment
than copper wire or a pre-1982 penny. should be disposed of in a normal waste basket when you are finished.
It is therefore safe to dispose of it like
normal trash.
2. Other Liquid Wastes: All other liquid wastes generated in this lab are dilute
and can be dumped down the drain with plenty of water.
Broken Glass
Do not work with any broken glassware. Dispose of broken glassware in the bins
labeled “broken glass” as shown in Figure 14.1. Do not use the normal waste
baskets for broken glass.
⌘ Without the identification number in 1. Record Identification Number: A copper salt sample will be at your bench
your notebook, there may be no way to
grade your results, which means no in a corked test tube. The test tube will have a label on it with a number. This
points can be granted.
number is the identification number that allows your instructor to determine
the true identity of your copper salt. Record this number in your laboratory
notebook.
⌘ If you need to use a mortar and 2. Prepare Salt: Inspect your unknown salt. If the salt appears in large clumps,
pestle, make sure they are clean and
dry before using them. you should attempt to grind the salt in a mortar and pestle before weighing it
out. Otherwise, you will find it difficult to get the salt to go into the volumetric
flask later.
14.3. Experimental Procedure 87
3. Mass Salt: Mass out approximately 3.75 g of your copper salt on weighing ⌧ Do not waste time making the mass
exactly 3.75 g. Get close and record
paper. Knowing precisely how much salt you use is critical for this experiment, whatever mass you have.
but the mass used does not have to be exactly 3.75 g.
4. Transfer Salt to Conical Funnel: Insert a conical funnel into a 50 mL ⌘ If some salt sticks to the weighing
paper, you can use a squirt of DI water
volumetric flask. Transfer the salt to the funnel. Be sure all the salt is from your water bottle to force it off the
paper and into the funnel.
transferred. Leave none behind. Also, be very careful not to spill any.
5. Rinse Salt Into Volumetric Flask: Using your DI water bottle, begin to
squirt DI water into the funnel to help force the salt into the volumetric flask.
Continue this until all the salt is in the flask.
6. Rinse Funnel and Remove: Once the salt has been pushed out of the funnel ⌘ Be sure not to use too much water.
If you fill the volumetric flask past the
into the flask, rinse the funnel one more time to be sure all the salt has been line you will have to start over.
rinsed into the flask.
7. Dissolve Salt in Water: If you have not done so already, fill the volumetric
flask to within 10 mL of the 50 mL mark. Swirl the flask for several minutes
to dissolve the salt. Do not proceed to the next step until the salt completely
dissolves.
8. Fill Volumetric Flask To Line: Using a Pasteur pipet or a clean eye dropper,
carefully fill the volumetric flask to the 50 mL line with DI water.
9. Cap and Mix: Cap the flask or cork the flask and then invert it several times
to be sure it is thoroughly mixed and uniform throughout.
10. Transfer Solution to Clean and Dry Beaker: Pour the solution into a clean ⌘ Do not rinse the volumetric flask
with water and pour into the beaker.
and dry 100 mL beaker. Label the beaker “Cu Unknown Solution A.” This will dilute the solution.
11. Clean Volumetric Flask: Clean your volumetric flask and return it to your
drawer. You will not need it again this lab period.
2. Add Magnetic Stir Bar: Obtain a magnetic stir bar for each beaker and drop
one into each beaker.
3. Place Beakers Onto Stir Plate: Place each beaker onto its own stirring hot
plate. Make sure the heating element is turned off on both stirring hot plates.
We only want to stir.
4. Begin Stirring Solutions: Turn on the stirring portion of the stirring hot
plate so that the solutions are stirred at a low but steady rate.
88 Gravimetric Determination of a Copper Salt’s Formula Mass
Monitor Reactions
For each reaction mixture, you need to do the following.
1. Make Sure Stirring Continues: Make sure the stir bar continues to stir the
reaction mixture continuously. If the stirring stops, adjust the position of
the beaker on the stirring hot plate or adjust the knob controlling the rate of
stirring until stirring is returned to normal.
2. Add HCl If Needed: If the solution turns cloudy white or yellow-brown, add
6 M HCl drop-wise until the solution clears.
1. Obtain Watch Glasses: Retrieve two watch glasses from your laboratory
drawer. Make sure they are clean and dry.
⌘ Do not use pen or wax pencil to 2. Label Watch Glasses: Obtain two adhesive labels and write “Reaction 1”
write on the labels. You need to use
normal pencil, which will not melt when on one of them and “Reaction 2” on the other in pencil. Attach one to each
heated.
watch glass.
⌘ Do not write on the filter paper. 3. Place Filter Paper on Watch Glass: Obtain two pieces of filter paper and
place one on the watch glass labeled “Reaction 1” and the other on the watch
glass labeled “Reaction 2.”
4. Weigh Watch Glass and Filter Paper: Weigh the watch glass and filter
⌘ Do not mix up the filter papers. paper combination for the watch glass labeled “Reaction 1.” Do the same for
They must remain with the watch glass
they were weighed with.
the watch glass labeled “Reaction 2.”
14.3. Experimental Procedure 89
2. Filter “Reaction 1” Product: Place the filter paper from the watch glass
labeled “Reaction 1” into the bottom of the Buchner funnel. Pour the reaction
mixture (liquid and copper precipitate) out of the beaker labeled “Reaction 1”
and onto the filter paper in the suction filtration apparatus.
4. Rinse Copper with Water: Rinse the copper in the Buchner funnel several
times with 5-10 mL portions of DI water from your water bottle.
5. Rinse Copper with Acetone: After a few minutes of suction filtration, rinse ⌘ This helps to remove water present.
the copper in the filtration apparatus with two 5-10 mL portions of acetone.
7. Allow Product to Dry in Air: Place the watch glass and product for “Reac-
tion 1” under the hood at your bench and allow it to dry while you filter the
product from the beaker labeled “Reaction 2.”
8. Filter Product from Beaker Labeled “Reaction 2”: Repeat steps 2 to 7 for
the beaker and watch glass labeled “Reaction 2.”
2. Dry Product in Oven: Place the watch glass labeled “Reaction 1” and its
contents into an oven at 110ı C for 10 minutes.
3. Cool Watch Glass Labeled “Reaction 1”: After 10 minutes in the oven,
remove the watch glass labeled “Reaction 1” and allow it to cool to room
temperature.
4. Weigh Watch Glass Labeled “Reaction 1”: Weigh the watch glass labeled
“Reaction 1” with its contents.
5. Repeat Until Mass Remains The Same: Repeat steps 3 to 4 until you no
longer observe a change in mass.
90 Gravimetric Determination of a Copper Salt’s Formula Mass
6. Repeat Process for Watch Glass Labeled “Reaction 2”: Repeat steps 1 to
5 for the watch glass labeled “Reaction 2.”
⌘ You should have about 30 mL of 1. Transfer “Cu Unknown Solution A” to Storage Bottle: Pour the remain-
solution remaining.
ing “Cu Unknown Solution A” into a capped storage bottle that will be
provided to you. Seal it tightly and label it. Place it in your laboratory drawer
until next week.
2 Return the test tube containing the unused portion of your unknown to the
box in the hood.
2 Make sure all equipment that does not belong in your personal lab drawer has
been returned to its designated spot.
2 Draw a line in your notebook at the end of your experimental work. Sign on
that line.
1. Calculate the total mass of copper present in each reaction beaker (Reaction 1
and Reaction 2).
2. Calculate the total mass of copper in the entire original 50 mL of “Cu Un-
known Solution A” using data from each reaction beaker independently.
14.5. Post-Lab Assignments 91
3. Calculate the percent copper in the original copper salt you weighed out in
step 3 on page 87. Use data from each reaction beaker independently.
4. Calculate the formula mass of the original copper salt, assuming only one ⌘ Be sure to use proper units and
significant figures.
Cu2C per formula unit. Do this using data from each reaction beaker inde-
pendently.
Chapter 15
Survey of Chemical Reactions
15.1 Introduction
One of the objectives of General Chemistry is to learn to predict chemical
reactions and write chemical equations. No other aspect of chemistry has such
overriding importance in all branches of the science, primarily because virtually
all chemical problems have their basis in some type of chemical transformation.
Chemical reactions are all around us: the combustion of gasoline in your car,
the neutralization of excess stomach acid with an antacid, and the fermentation of
grape juice. Our very existence is dependent upon countless chemical reactions
occurring in our bodies every day. Anyone working in technical areas such as
engineering, medicine, geology, biology, physics, or chemistry can benefit from
a basic knowledge of chemical reactions.
Even if one does not work in a technical area, the prevalence of chemicals
in modern society means that we all can become better citizens with some
awareness as to the reaction properties of these chemicals.
This experiment is designed to allow you to experience a wide variety of
reactions. We will divide the experiment into general reaction types and ask that
you observe the changes that occur within each example and, in some cases,
verify the nature of the products by means of simple chemical tests.
Reaction Classification
There are a variety of ways of classifying chemical reactions, most of which
are equally acceptable. The classification used here will enable you to quickly
acquire the ability to predict and write chemical reactions. The classifications
used are:
93
94 Survey of Chemical Reactions
1. Metathesis Reactions
2. Acid-Base Reactions
Metathesis Reactions
A metathesis reaction is characterized by two soluble ionic substances exchang-
ing ion partners. The result of such an exchange is often the formation of a
precipitate, the evolution of a gas, or the formation of a weak electrolyte. For
example, the reaction between barium chloride and sodium sulfate is a metathesis
reaction.
Both barium chloride and sodium sulfate are soluble in water; however, barium
sulfate is not. Thus, the precipitate BaSO4 .s/ forms in this reaction.
Another example of a metathesis reaction is that between magnesium carbon-
ate and hydrochloric acid in which a gas (carbon dioxide) and a weak electrolyte
are formed.
In reaction 15.2 some students are confused about where the carbon dioxide
came from on the product side. Because of this, it can sometimes be difficult to
see how reaction 15.2 is a metathesis reaction.
You have to keep in mind that when CO23 .aq/ is mixed with excess acid
(HCl), H2 CO3 .aq/ will form. However, H2 CO3 .aq/ is unstable and will almost
immediately decompose into carbon dioxide and water. That is where the carbon
dioxide came from in reaction 15.2.
Knowledge of solubility rules (from your text and lecture materials) is
essential to the predictions of the course of these reactions.
Acid-Base Reactions
Acid-base reactions are a special type of metathesis reaction, but a very important
one. For our purposes here, we shall consider acids to be substances donating
protons and bases as substances donating hydroxide ions. The reaction between
an acid and a base, termed a neutralization reaction, produces water and a salt
(an ionic compound produced in an acid-base reaction).
15.1. Introduction 95
For example, consider the reaction between potassium hydroxide and nitric
acid shown in reaction 15.3.
KOH.aq/ C HNO3 .aq/ ! H2 O.`/ C KNO3 .aq/ (15.3)
Here, you can see that the base potassium hydroxide donates the hydroxide ion
.OH / while the acid donates a proton .HC / to yield water and the potassium
nitrate salt.
will take place, yielding excess hydroxide and a basic solution. This provides a
way for you to test if a metal oxide has been formed in a combination reaction.
2. Acids In Test Tubes: When you are asked to shake a test tube containing an
acid, make sure you cover the tube with a cork and not your finger or thumb.
Experimental Precautions
In this lab you will heat metal and a test tube in a flame. In all cases, this work
should be performed in a hood. When heating test tubes, always point them
away from you and anybody else in the room.
15.3. Experimental Procedure 97
Goggles
As with all laboratory experiments, you are expected to wear your goggles at all
times while in the lab. Failure to do so may result in expulsion from the lab.
Waste Disposal
You will generate waste in this lab that cannot be thrown down the drains or into
the trash can. Please adhere to all disposal policies. When in doubt, ask your lab
instructor.
Broken Glass
Do not work with any broken glassware. Dispose of broken glassware in the bins
labeled “broken glass” as shown in Figure 15.1. Do not use the normal waste
baskets for broken glass.
Figure 15.1
Broken glass container.
15.3 Experimental Procedure
In all of the following experimental steps, you are to record your observations as
clearly as possible. Ultimately, you will have to explain your observations with a
balanced reaction. Even though you are not asked to produce a balanced reaction
until after all the experimental steps are complete, you might think about what
reaction is relevant as you carry out the experimental steps.
Reaction Set 1
1. Mix Copper Wire and Silver Nitrate: Clean a piece of copper wire with Do not get silver nitrate on your
steel wool. Place the copper wire in a test tube and add 5 mL of AgNO3 .aq/ hands. It leaves ugly brown stains
that will not come off for days. Use
solution. Allow the test tube to stand 30 minutes. Observe the results after gloves if desired.
this 30 minute period.
Reaction Set 2
1. Mix Copper Wire and Nickel Sulfate: Clean a piece of copper wire with
steel wool. Place the copper wire in a test tube and add 5 mL of a NiSO4 .aq/
solution. Allow the test tube to stand for 30 minutes. Observe the results after
this 30 minutes period.
Reaction Set 3
1. Mix Barium Chloride with Sulfuric Acid: Dissolve a spatula-full of BaCl2
in about 5 mL of distilled H2 O in a test tube. Add about 2 mL of 1 M H2 SO4
to the solution.
98 Survey of Chemical Reactions
Reaction Set 4
1. Add Nickel Nitrate to Water in Test Tube: In a test tube, dissolve a spatula-
full of Ni.NO3 /2 in 5 mL of DI water.
2. Add Sodium Carbonate to Water in Test Tube: In a separate test tube, add
and dissolve a spatula-full of Na2 CO3 in 5 mL of water.
3. Mix The Two Solutions: Mix the aqueous nickel nitrate and aqueous sodium
carbonate solutions by dumping one into the other.
Reaction Set 5
Make a table in your laboratory notebook to record the observations for this
reaction set in tabular form.
⌘ Long range pH paper is not the 1. Test pH of 1 M HCl: Put 5mL of 1 M HCl into a clean and dry beaker.
same as litmus paper.
⌘ A pH less than 7 indicates an acidic Determine the pH of the solution with long range pH paper.
solution; a pH greater than 7 indicates
a basic solution.
2. Add Sodium Hydroxide and Test pH: Add 1 mL of 1 M NaOH to the HCl
solution and mix thoroughly. Determine the pH of the mixture with long
range pH paper.
3. Repeat Step 2 9 Times: Repeat the procedure in step 2 9 more times until
you have added a total of 10 mL NaOH.
Reaction Set 6
1. Mix Copper Sulfate Solution and Sodium Hydroxide: Put 5 mL of CuSO4 .aq/
solution in a test tube. Add several drops of a 1 M NaOH solution to the same
test tube.
2. Add Sulfuric Acid: To this mixture, add 1 M H2 SO4 .aq/ until a homoge-
neous solution results.
Reaction Set 7
1. Mix Zinc and Hydrochloric Acid: Place a small amount of zinc metal in a
test tube. Add 5 mL of 6 M HCl solution.
⌘ Use the test tube holder to make 2. Test for Presence of Hydrogen: After a reaction begins in the test tube with
sure you don’t drop the tube.
⌘ If you hear a “pop” sound when you the zinc and HCl, bring a lighted wooden splint to the mouth of the test tube.
bring the lighted splint to the test tube,
hydrogen was present.
Reaction Set 8
1. Mix Copper and Hydrochloric Acid: Put a piece of copper wire in a test
tube. Add 5 mL of 6 M HCl.
15.4. Before Exiting Lab 99
Reaction Set 9
1. Place Potassium Chlorate in Test Tube: Place a couple of spatulas full of
KClO3 .s/ in a test tube. Attach a test tube holder to the test tube so that you
don’t have to hold the test tube directly.
2. Prepare Wooden Splint: Light a wooden splint and have it ready as you ⌘ Working in pairs will be particularly
effective here. One of you can heat the
carry out the next step. test tube while the other prepares the
wooden splint.
3. Heat Test Tube: Heat the test tube with potassium chlorate in a flame until
the solid melts and a blanket of gas rises to the top of the test tube. Heat the test tube in a hood
with the tube opening pointing away
4. Bring Glowing Splint to Test Tube Mouth: Stop heating the test tube and from people.
blow out the burning wooden splint. Immediately place the glowing splint
into the middle of the test tube. ⌘ If oxygen is present, the splint will
glow more brightly.
5. Add Water and Silver Nitrate to Test Tube: After the test tube has cooled,
add 5 mL of DI water to dissolve the residue. Then add several drops of
AgNO3 .aq/ solution.
Reaction Set 10
1. Burn Magnesium Metal in Flame: With a pair of tongs, grab a piece of
magnesium metal. Ignite the metal in a flame. Exercise extreme caution when
burning magnesium. The flame is
bright and hot. Do all work in a
hood.
15.4 Before Exiting Lab
Before leaving lab for the day, go down this checklist to make sure you have
done everything on it.
2 Place all liquid waste into the waste container marked “liquid waste” located
in the hood in the back of the room.
2 Return all reagent bottles to the tray at the center of your lab bench and put
all your laboratory equipment back into your drawer.
2 Draw a line at the end of your experimental work and sign on that line.
⌘ Your reactions must be consistent 1. For each reaction set, write all the balanced reactions necessary to explain
with your observations. Do not write
reactions based on what you think what was observed. Your reactions must be balanced, have proper phase
should have been observed. Write
them based on what actually was
indications (aq, s, g), and must use standard notation for chemical element
observed. symbols.
2. For each reaction in each reaction set, classify the reaction as metathesis,
acid-base, redox displacement, redox decomposition, or redox combination.
Chapter 16
What Is the Heat of Formation of MgO?
16.1 Introduction
Chemical reactions can either absorb energy when they take place (endothermic
reactions) or release energy (exothermic reactions). The magnitude of this energy
change is determined by the chemical participants in the reaction and the quantity
of product formed.
The energy absorbed or evolved by a chemical reaction as heat when carried
out at constant pressure is called the enthalpy of reaction and is given the symbol ⌘ Enthalpy of reaction is sometimes
referred to as heat of reaction.
H . Sometimes it is symbolized by Hrxn to emphasize that it represents an
enthalpy change for a reaction. H is often expressed in units of kJ/mole, where
the “mole” refers to the amount of a specific reactant or product. To make sense
of Hrxn , the reaction must be specified.
In this experiment, you will measure the enthalpy changes accompanying
several exothermic reactions utilizing a simple calorimeter. This calorimeter
consists of an insulated vessel, a thermometer, and a lid. This constitutes an
open system because the calorimeter is not truly isolated from its surroundings.
Matter and energy can therefore be transferred between the system and the
surroundings. A styrofoam cup will be used as the insulated vessel in this
experiment to help retain the heat. The energy given off by any reaction carried
out in the calorimeter is absorbed by both the calorimeter and the solvent (water).
This causes an increase in the temperature of the calorimeter and solvent that
can be measured. The heat, q, that is absorbed by the calorimeter and solvent is
calculated from the equation
qcalorimeter D C T (16.1)
where C is the heat capacity of the calorimeter and solvent, and T is the
change in temperature of the water (the solvent) in the calorimeter. Heat capacity
is defined as the amount of energy required to raise the temperature of an object
by 1ı C. In this experiment, the vessel and the amount of solvent remain constant,
so C is a constant as long as you use the same calorimeter throughout the
experiment.
101
102 What Is the Heat of Formation of MgO?
qreaction D n H (16.2)
From Equation 16.3 you can derive an expression that will give you C as a
function of the enthalpy change for a reaction. This is what you will need to do
when you calibrate the calorimeter (determine C ). You can also rearrange this
equation to give the enthalpy change as a function of the temperature change.
This is what you will need to do when determining the unknown heats of reaction.
As you may recall, a heat of formation ( Hf ) is a specific type of enthalpy
change. It is the enthalpy change in a reaction that forms one mole of a species
from the elements in their standard states. For MgO, the balanced equation for
this reaction is
1
Mg.s/ C O2 .g/ ! MgO.s/ . (16.4)
2
It would be very difficult to measure the enthalpy change for this reaction directly.
It can be determined by indirect methods, however.
Hess’s Law tells us that we can obtain the enthalpy change for any reaction
by measuring and adding the enthalpy changes for any series of reactions that
add up to give the reaction we are interested in. This is what we will do in this
experiment.
The formation reaction for solid MgO can be obtained by adding the reactions
corresponding to the formation of water, the reaction of solid Mg with HCl, and
the reaction of solid MgO with HCl. The details of doing this will not be spelled
out for you here. Instead, you will be expected to write and add these equations
on your own.
Goggles
As with all laboratory experiments, you are expected to wear your goggles at all
times while in the lab. Failure to do so may result in expulsion from the lab.
16.3. Experimental Procedure 103
Waste Disposal
All waste containing magnesium must be poured into the appropriate waste
container. Waste that does not contain magnesium can be poured down the drain
with plenty of water.
Broken Glass
Do not work with any broken glassware. Dispose of broken glassware in the bins
labeled “broken glass” as shown in Figure 16.1. Do not use the normal waste
baskets for broken glass.
1. Obtain Cups and Lids: Select two styrofoam cups, and place one inside the
other. Select a tight-fitting lid, and place it on the top cup. This is now your
calorimeter.
8. Add HCl to NaOH Solution: Add the HCl solution quickly into the NaOH
solution in the calorimeter and start the timer. Replace the lid on the calorime-
ter with the thermometer in place. Immediately begin collecting and recording
104 What Is the Heat of Formation of MgO?
⌘ Be careful not to tear, rip, puncture, temperature readings at 30-second intervals for 7 minutes. Swirl the calorime-
or otherwise mutilate your calorimeter
from this point forward. If you do, you ter to mix the reactants well with the thermometer and lid in place.
can repeat steps 1 through 8 above on
a new calorimeter.
9. Clean Calorimeter: When data collection is complete, pour the contents of
the calorimeter down the drain and rinse the calorimeter with distilled water.
Dry the calorimeter as completely as possible.
3. Determine Mass Of Weighing Boat: Record the mass of the weighing boat
after the transfer.
5. Add HCl to Calorimeter: Add the 100:0 mL of 1:0 M HCl to the calorime-
ter containing the MgO and start the timer. Replace the lid and insert the
thermometer. Begin swirling the mixture and immediately record the temper-
ature. Record the temperature at one-minute intervals in the same manner
described above in the reaction of Mg with HCl.
6. Be Sure to Swirl: In this reaction all the MgO should react since HCl is
used in excess. However, if the solid MgO is allowed to sit on the bottom or
sides of the cup it will not dissolve and hence it will not react. Make sure it
dissolves by constantly and gently swirling and/or stirring the solution during
the reaction process.
7. Check That All MgO Has Dissolved: Before discarding this solution, check
to see that all of the MgO has reacted. If solid MgO remains, the results from
this portion of the experiment are not accurate. If any solid is present, this
portion of the experiment must be repeated.
8. Clean Calorimeter: When data collection is completed, pour the contents
of the calorimeter into the waste container at the front of the lab. Rinse the
calorimeter with distilled water and dry as completely as possible. The rinses
can be poured down the drain.
4. Read the temperature off the graph at this time=0 extrapolation. This is the
Tfinal for the calorimeter calibration.
5. Compute the heat capacity of the calorimeter using the above temperature
change and the value of Hrxn for Reaction D that you determined in your
pre-lab assignments. Be sure to attach appropriate units.
2. Using the graph paper that has been provided, make a plot of temperature
versus time for your collected data.
3. From this graph and using a ruler, extrapolate back to time=0 that portion of
the graph showing a linear decrease in temperature.
4. Read the temperature off the graph at this time=0 extrapolation. This is the
Tfinal for the reaction of Mg with HCl.
5. Using the calorimeter heat capacity that was determined above, calculate H
for this reaction (Reaction B) and label it Hb . This number should have
units of kJ/mol.
2. Using the graph paper that has been provided, make a plot of temperature
versus time for your collected data.
3. From this graph and using a ruler, extrapolate back to time=0 that portion of
the graph showing a linear decrease in temperature.
4. Read the temperature off the graph at this time=0 extrapolation. This is the
Tfinal for the reaction of Mg with HCl.
5. Using the calorimeter’s heat capacity that was determined above, calculate
H for this reaction (Reaction C) and label it Hc . This number should
have units of kJ/mol.
H 3C N
C OH
The reaction between nickel and dimethylglyoxime in ethanol is examined to
confirm the stoichiometry and to calculate the percent yield. The concept of C OH
H 3C N
limiting reagent is illustrated.
Figure 17.1
Dimethylglyoxime is a
17.1 Introduction reagent used in the forma-
tion of NiDMG.
In this experiment you will examine the stoichiometry of the reaction between
nickel(II) nitrate and dimethylglyoxime to form nickel(II) dimethylglyoxime. OH O
CH3
H 3C
A solution of nickel(II) nitrate contains nickel(II) ions and nitrate ions while C N N C
a solution of dimethylglyoxime contains dimethylglyoxime in molecular form Ni
as shown in Figure 17.1. When the solutions are mixed, the nickel ions and C N N C
dimethylglyoxime react to form nickel(II) dimethylglyoxime. This compound, H 3C CH3
O HO
shown in Figure 17.2, is a water-insoluble molecule that precipitates out of
solution when formed. The net ionic reaction is shown in Figure 17.3. Figure 17.2
Nickel(II) dimethylglyoxime
H 3C
OH O
CH3
(NiDMG) is the main prod-
H 3C N
N C
uct of interest in this lab.
C OH C N
Ni2+ + 2 Ni + 2H+
C OH
C N N C
H 3C N
H 3C CH3
O HO
Figure 17.3
The net ionic reaction for the formation of nickel(II) dimethylglyoxime.
107
108 Nickel Dimethylglyoxime Formation Stoichiometry
Goggles
As with all laboratory experiments, you are expected to wear your goggles at all
times while in the lab. Failure to do so may result in expulsion from the lab.
Waste Disposal
You will generate waste in this lab that cannot be thrown down the drains or into
the trash can. Please adhere to all disposal policies. When in doubt, ask your lab
instructor.
Broken Glass
Do not work with any broken glassware. Dispose of broken glassware in the bins
labeled “broken glass” as shown in Figure 17.4. Do not use the normal waste
baskets for broken glass.
Figure 17.4
Broken glass container.
17.3 Experimental Procedure
Prepare Nickel(II) Solution
⌧ You can save yourself time in lab by 1. Mass Out Nickel Nitrate: Using a top loading electronic balance, mass
doing this calculation before lab.
out on weighing paper sufficient Ni(NO3 )2 6H2 O to make 50 mL of an
approximately 0.050 M Ni2C solution.
⌘ This2Csolution will be referred to as 3. Fill Flask to the Mark: Fill the volumetric flask to the 50 mL mark with
the Ni stock solution.
ethanol using an eyedropper to achieve a volume of 50.00 mL.
2. Label Beakers: With a wax pencil, label one beaker as “Reaction 1” and the
other beaker as “Reaction 2.” It does not matter which beaker receives which
label.
4. Clean and Dry Graduated Cylinder: Thoroughly rinse the graduated cylin- ⌘ Failure to thoroughly clean the
graduated cylinder before the next step
der with water three times and then with ethanol twice. It is essential that you will result in the formation of a red
get rid of all traces of Ni2C . mess in the cylinder.
2. Stir Beakers Occasionally: Allow both beakers to sit for at least 10 minutes,
stirring occasionally with separate glass rods.
3. Allow Precipitate to Settle: Allow the precipitate to settle to the bottom of ⌧ While the precipitate settles to the
bottom of the flask you can prepare the
the beakers for about 10 minutes without stirring or otherwise disturbing the watch glasses for massing (next
beakers. section).
2. Label Watch Glasses: Obtain two adhesive labels and write “Reaction 1” ⌘ Do not use pen or wax pencil to
write on the labels. You need to use
on one of them and “Reaction 2” on the other in pencil. Attach one to each normal pencil, which will not melt when
heated or dissolve in ethanol.
watch glass.
3. Place Filter Paper on Watch Glass: Obtain four pieces of filter paper and ⌘ Do not write on the filter paper.
place two on the watch glass labeled “Reaction 1” and the other two the watch
glass labeled “Reaction 2.”
4. Weigh Watch Glass and Filter Paper: Weigh the watch glass and filter ⌘ Do not mix up the filter papers.
They must remain with the watch glass
paper combination for the watch glass labeled “Reaction 1.” Do the same for they were massed with.
the watch glass labeled “Reaction 2.”
110 Nickel Dimethylglyoxime Formation Stoichiometry
4. Filter “Reaction 1” Product: Place the filter papers from the watch glass
labeled “Reaction 1” into the bottom of the Buchner funnel. Pour the reaction
mixture (liquid and precipitate) out of the beaker labeled “Reaction 1” and
onto the filter paper in the suction filtration apparatus.
8. Allow Product to Dry in Air: Place the watch glass and product for “Reac-
tion 1” under the hood at your bench and allow it to dry while you filter the
product from the beaker labeled “Reaction 2.”
9. Filter Product from Beaker Labeled “Reaction 2”: Repeat steps 4 to 8 for
the beaker and watch glass labeled “Reaction 2.”
2. Dry Product in Oven: Place the watch glass labeled “Reaction 1” and its
contents into an oven at 110ı C for 10 minutes.
3. Cool Watch Glass Labeled “Reaction 1”: After 10 minutes in the oven,
remove the watch glass labeled “Reaction 1” and allow it to cool to room
temperature.
4. Weigh Watch Glass Labeled “Reaction 1”: Weigh the watch glass labeled
“Reaction 1” with its contents.
17.4. Before Exiting Lab 111
5. Repeat Until Mass Remains The Same: Repeat steps 2 to 4 until you no
longer observe a change in mass.
6. Repeat Process for Watch Glass Labeled “Reaction 2”: Repeat steps 1 to
5 for the watch glass labeled “Reaction 2.”
2 Clean your filtration apparatus thoroughly with water. If it is still stained red,
use dilute HCl to clean it. Pour all HCl waste from cleaning into the waste
container at the back of the room.
2 Rinse the filtration apparatus one final time with water and dry the filtration
apparatus thoroughly.
2 Make sure your work area is scrupulously clean. The compound NiDMG has
a habit of being difficult to clean up. Use Softscrub if necessary. Clean your
bench and your hands several times.
2 Draw a line in your notebook where your experimental work ends. Sign on
this line.
2 Have your instructor sign your notebook on the line at the end of your
experimental section.
1. From your data, calculate the actual experimental mass of product collected
for the reaction in the beaker labeled “Reaction 1.”
2. From your data, calculate the actual experimental mass of product collected
for the reaction in the beaker labeled “Reaction 2.”
3. Calculate the theoretical yield expected for the reaction in the beaker labeled
“Reaction 1.”
4. Calculate the theoretical yield of NiDMG expected for the reaction in the
beaker labeled “Reaction 2.”
5. Calculate the percent yield for the reaction in the beaker labeled “Reaction
1.”
6. Calculate the percent yield for the reaction in the beaker labeled “Reaction
2.”
Chapter 18
Synthesis of Aspirin and Oil of Wintergreen
18.1 Introduction
One of the activities commonly associated with chemists is the making of new
compounds and materials. Synthesis, as this is otherwise known, is integral to
our modern way of life. Many of the items we depend on every day are, in fact,
synthesized by chemists from compounds that may be very different. Aside from
the practical benefits of synthesis, the ability to carry out complex transforma-
tions of matter from one form to another is a great intellectual achievement for
humans.
In this project, you will get to try out synthesis. Specifically, you will make carboxylic acid group
two compounds with different chemical and physical properties from the same
HO O
starting molecule. You will synthesize aspirin, which can be used to relieve C
pains, and you will synthesize oil of wintergreen, which can be used to flavor
H C OH
foods. You will not be expected to understand how these transformations take C C
place, but you will be expected to develop the laboratory skills required to carry hydroxyl group
C C
out a simple synthesis and to isolate the synthesized material. H C H
113
114 Synthesis of Aspirin and Oil of Wintergreen
acetyl group
HO O
C About Aspirin and Its Synthesis
H C O O Aspirin, also known as acetylsalicylic acid, is a common drug used to combat
C C C
pain, fever, inflammation, and the recurrence of heart attacks. Like salicylic acid,
C C CH3 it is just one example of a salicylate, but it is commercially the most important
H C H
member of this group of compounds. Aspirin can be synthesized from salicylic
H acid by replacing the hydrogen atom (H) of the hydroxyl group ( OH) with
an acetyl group (O D C CH3 ). The result of this substitution is shown in
Figure 18.2
Figure 18.2, where the acetyl group has been circled.
Aspirin, also known as
Aspirin can be synthesized according to the reaction shown in Figure 18.3.
acetylsalicylic acid.
In this reaction salicylic acid (Figure 18.1) is mixed with acetic anhydride
O (Figure 18.4) in the presence of a catalytic amount of sulfuric acid. The products
of this reaction are aspirin (Figure 18.2) and acetic acid (Figure 18.5).
CH3
O HO O HO O
C O C
O H C OH CH3 H C O O
H 3C OH
C C H+ C C C C
+ O +
H 3C Heat
C C O C C CH3
O
H C H H C H
Figure 18.4 H 3C
H H
Acetic anhydride, one of the
reagents in the synthesis of Figure 18.3
aspirin. The overall reaction for the synthesis of aspirin, also known as acetylsalicylic
acid.
H 3C OH
C
H
18.2 Experimental Design Considerations
Figure 18.6 Most experiments are simple in concept. The execution is often more challenging.
Methyl salicylate, also This section contains some information about the experimental details you will
known as oil of wintergreen. have to worry about while working through this project.
18.2. Experimental Design Considerations 115
HO O O O
C H 3C C
H
H C OH H C OH
C C H+ C C
+ H C OH + H 2O
Heat
C C C C
H
H C H H C H
H H
Figure 18.7
The overall reaction for the synthesis of oil of wintergreen, also known as
methyl salicylate.
Isolating Product
In many syntheses, the product you are trying to produce will not be the only
substance in the reaction vessel when you decide the reaction is complete. Other
products (call byproducts) are often present, and sometimes some of the reagents
are still present. Synthesis is a messy business, and isolating the product of
interest can sometimes be complicated. Many of the experimental details in this
project are driven by the need to effectively isolate the product of interest. The
following sections explain why some of these decisions were made.
Isolating Aspirin
Isolating aspirin is relatively easy. Aspirin is a solid at and below room tempera-
ture, and it is not very soluble in water. Therefore, if we add a reaction mixture
containing aspirin to water in an ice bath, solid crystals of aspirin should form.
However, the reagent salicylic acid is also a solid at room temperature, and it
also has low solubility in water. If any salicylic acid remains at the end of the
reaction, it will crystalize with the aspirin, giving impure product.
To guard against this possibility, we have designed the project such that the
acetic anhydride is present in excess. This means that if the reaction is carried
out for long enough, there should be no salicylic acid left in the reaction vessel.
Through experience, we know that heating the reaction mixture for 6 minutes is
“long enough.”
Because acetic anhydride is present in excess, there will be some of this left
at the end of the reaction. However, acetic anhydride reacts rapidly with water
to produce acetic acid. This is why we have you pour the reaction mixture into
water when you are done heating the mixture. Acetic acid, in turn, is very soluble
in water. When you filter your product crystals, the liquid, which contains the
acetic acid, will simply fall away into the filter flask. The result is an effective
isolation of aspirin, assuming you actually made any aspirin.
a solid. Steps must be taken to ensure that only the desired product is present.
In this synthesis, salicylic acid will remain at the end of the reaction. To
remove this excess reagent, you will pour the reaction mixture into water, which
will cause the salicylic acid to form a white solid. This solid can be filtered out
of the reaction mixture. What remains should be a mixture of methanol, oil of
wintergreen, and water. It will mostly be water.
⌘ This process is called extraction. To further isolate the oil of wintergreen, you will add small amounts of
dichloromethane to your product liquid. Oil of wintergreen is much more soluble
in dichloromethane than in water or methanol. This means it will move into the
dichloromethane. Because dichloromethane and water do not mix, it is possible
to then remove the dichloromethane and put it in a separate container. If this is
repeated several times, the result will be a quantity of dichloromethane with oil
of wintergreen in it.
⌘ Decision You Make When you add the dichlormethane to your reaction mixture, two layers of
liquid will form. You want to remove the dichloromethane after the extraction.
To do this, you will have to decide which layer is dichloromethane. To make this
decision, look up the density of water and of dichloromethane. The liquid with
the lower density will float on top of the liquid with the higher density.
Chemical Hazards
Goggles
You are expected to wear goggles at all times in the lab. Failure to do so may
result in expulsion from the lab.
18.4. Experimental Procedure 117
Waste Disposal
No liquid or solid waste may be poured down the drain in this lab unless you
are specifically instructed to do so. Everything must be disposed of in the waste
containers in the hoods.
Broken Glass
Do not work with any broken glassware. Dispose of broken glassware in the bins
labeled “broken glass” as shown in Figure 18.9. Do not use the normal waste
baskets for broken glass.
You can set up a water bath with another student who is also carrying out the
synthesis of aspirin because there will be plenty of room in the water bath for
two test tubes.
1. Obtain Hot Plate: Obtain a hot plate and plug it in near your work area. Be
sure the hot plate is under a hood so that fumes evolved during heating are
pulled away by the hood.
2. Fill Beaker with Water: Fill a 600 mL beaker about two-thirds full of tap
water and place it on the hot plate.
3. Heat Water to Boiling: Begin heating the water in the water bath so that it ⌧ Continue work in the next section
boils. while the water boils.
1. Obtain Ice Bath Pan: From a drawer in the back of the laboratory, obtain a
metal pan in which to make an ice bath.
2. Add Ice to Pan: Add one scoop of crushed ice to the pan from the styrofoam
container in the back of the room.
4. Obtain Clean and Dry Beaker: Obtain a 150 mL beaker from your labora-
tory drawer. Make sure it is clean and dry.
6. Place Beaker In Ice Bath: Place the beaker in the ice bath.
118 Synthesis of Aspirin and Oil of Wintergreen
obtain one from the front of the room. test tube and attach a label with your name to the top of the test tube.
1. Attach Test Tube To Ring Stand: Secure the 8-inch test tube to a ring stand
with a single burette clamp.
2. Suspend Test Tube Over Water Bath: Orient the ring stand and burette
clamp on the ring stand such that the test tube can be easily lowered into the
water bath.
⌘ Wait for the water to boil before 3. Place Reaction Mixture In Boiling Water Bath: Lower the test tube con-
placing the test tube in the water bath.
taining the reaction mixture into the boiling water bath and leave it there for
6 minutes.
⌘ Leave the beaker with boiling water 4. Remove Test Tube from Boiling Water Bath: After 6 minutes have passed,
on the hot plate until later.
raise the test tube out of the boiling water. Observe any changes that have
taken place.
Crystallize Product
1. Pour Reaction Mixture into Cold Water: Pour the contents of the test tube
into the DI water that has been cooled in the 150 mL beaker immersed in the
iced water bath.
2. Rinse Test Tube Into Cold Water: Rinse the test tube with several milliliters
of DI water, adding rinse to reaction mixture.
⌘ Any unreacted acetic anhydride 3. Swirl Beaker Contents: Gently swirl the flask to aid in the mixing of the
reacts with water to form acetic acid.
solution for about 30 seconds.
⌘ Once you have finished with this 4. Reheat Mixture: Remove the boiling water bath from the hot plate and place
step you may turn off and unplug the
hot plate. the 150 mL beaker containing the reaction mixture onto the hot plate. Wait
for the reaction mixture to achieve a gentle boil and then immediately remove
it from the hot plate.
18.4. Experimental Procedure 119
5. Wait for Crystals to Form: Allow the entire mixture to cool on your bench ⌘ Slow cooling facilitates the
formation of crystals.
until crystals form. This may take 30 minutes or more.
1. Obtain Watch Glass and Filter Paper: Obtain a clean and dry watch glass
from your laboratory drawer. Obtain a piece of filter paper from the reagent
tray at your bench. Place the filter paper on the watch glass.
2. Mass Watch Glass and Filter Paper: Determine the mass of the watch ⌘ You do this now so that you can
determine the mass of aspirin isolated.
glass and filter paper using an electronic top loading balance.
2. Filter Product Crystals: Place the filter paper from the watch glass into the
bottom of the Büchner funnel. Pour the reaction mixture (liquid and crystals)
out of the beaker onto the filter paper in the suction filtration apparatus.
3. Dry Crystals for Several Minutes: Allow air to be pulled over the crystals
for several minutes to help dry them.
4. Remove Crystals from Büchner Funnel: Carefully remove the crystals and ⌘ You may have to use your spatula
to lift the edge of the filter paper.
filter paper from the funnel and place them on the watch glass.
5. Store Crystals in Laboratory Drawer: Once you have returned all items to
your laboratory drawer, carefully place the watch glass with product crystals
in your drawer to be stored until next week.
You can set up a water bath with another student who is also carrying out the
synthesis of oil of wintergreen because there will be plenty of room in the water
bath for two test tubes.
1. Obtain Hot Plate: Obtain a hot plate and plug it in near your work area. Be
sure the hot plate is under a hood so that fumes evolved during heating are
pulled away by the hood.
2. Fill Beaker with Water: Fill a 600 mL beaker about two-thirds full of tap
water and place it on the hot plate.
3. Heat Water: Begin heating the water in the water bath so that it reaches a ⌧ Continue work in the next section
while the water heats.
constant temperature of 75ı C. It is important that the water not boil.
120 Synthesis of Aspirin and Oil of Wintergreen
1. Obtain Ice Bath Pan: From a drawer in the back of the laboratory, obtain a
metal pan in which to make an ice bath.
2. Add Ice to Pan: Add one scoop of crushed ice to the pan from the styrofoam
container in the back of the room.
4. Obtain Clean and Dry Beaker: Obtain a 50 mL beaker from your laboratory
drawer. Make sure it is clean and dry.
6. Place Beaker In Ice Bath: Place the beaker in the ice bath.
2. Add Salicylic Acid to Test Tube: Transfer the salicylic acid to a 5-inch test
tube and attach a label with your name to the top of the test tube.
6. Stir Contents of Test Tube: Stir the contents of the test tube with a glass
stirring rod until the bulk of the salicylic acid dissolves.
1. Attach Test Tube To Ring Stand: Secure the 5-inch test tube to a ring stand
with a single burette clamp.
2. Suspend Test Tube Over Water Bath: Orient the ring stand and burette
clamp on the ring stand such that the test tube can be easily lowered into the
water bath.
⌘ Be sure the waterıbath is at a 3. Place Reaction Mixture In Hot Water Bath: Lower the test tube containing
temperature near 75 C but not above.
the reaction mixture into the water bath and leave it there until the volume of
the reaction mixture has decreased to half its original volume.
18.5. Before Exiting Lab 121
4. Remove Test Tube from Hot Water Bath: After the volume of the reaction
mixture has decreased by 50%, raise the test tube out of the hot water. Observe ⌘ Leave the beaker with hot water on
the hot plate until later.
any changes that have taken place. Gently waft air near the top of the test
tube to your nose and note what you smell.
Extract Product
2. Gravity Filter Reaction Mixture: Insert a funnel into your smallest Erlen-
meyer flask and filter the reaction mixture through filter paper in the funnel.
It may take 10 minutes for all the liquid to drain into the flask.
4. Add Dichloromethane: Add about 1 mL dichloromethane to the conical ⌘ You will have to figure out how
many drops there are per milliliter.
centrifuge tube using either an eye dropper or Pasteur pipet. Cap the tube and
shake for about 30 seconds.
5. Remove Appropriate Layer: You should see two separate liquid layers in ⌘ This was a decision you were to
make before coming to lab.
the conical centrifuge tube. Use a pasteur pipette to remove the appropriate
layer. Place the removed liquid into a small test tube.
6. Repeat Extraction Twice More: Repeat steps 4 and 5 two more times, each
time adding the removed liquid to the same small test tube.
8. Gravity Filter Contents of Test Tube: Pour the contents of the test tube
through filter paper in a funnel and collect the filtrate in a 4-inch test tube for
storage. This will filter out the sodium sulfate particles.
9. Seal Test Tube with Product: Place a cork in the test tube containing the
extracted, dried, and filtered liquid. Wrap parafilm around the cork and top of
the test tube to prevent evaporation of the liquid.
10. Store Test Tube with Product Liquid: Store the test tube with the product
liquid as directed by your instructor.
2 Return clamps and rings to the drawers from which you got them.
2 Draw a line in your notebook at the end of your experimental work and sign
on that line.
In this experiment you will carry out a number of analyses on the products
you previously synthesized from salicylic acid. These tests are intended to
characterize the identity and purity of the product.
19.1 Introduction
Analyzing Product of Aspirin Synthesis
You should have already carried out the synthesis shown in Figure 18.3 on
page 114. This reaction indicates that aspirin and acetic acid are the only
products. The acetic acid should have dissolved in water and been flushed away
during filtration of the product. Therefore, your product should be exclusively
aspirin, right?
Just because the reaction in Figure 18.3 says that your product should be
aspirin alone does not mean that it is. Even if most of your product is aspirin,
it is not likely that it is pure. Some of the original salicylic acid may remain in
the product because it did not react. Thus, characterization of the product of
a synthesis serves two purposes: to confirm the identity of the product and to
ascertain the level of purity of the product. After a synthesis, you must always
characterize your product using appropriate tests.
To characterize the product of the aspirin synthesis you will perform a
chemical test to identify any salicylic acid present in your product, obtain a
melting point range for your product, carry out thin layer chromatography of
your product, and collect an infrared spectrum of your product.
The chemical test for salicylic acid is a test of purity. The melting point range
of your product will help quantify purity. It can also help confirm identity as long
as the sample is pure. When carried out properly, the thin layer chromatography
test can help confirm identity and purity. Of all of these tests, however, the
infrared spectrum will be the most conclusive in determining the identity of your
product.
123
124 Characterization of Synthesized Aspirin and Oil of Wintergreen
Broken Glass
Do not work with any broken glassware. Dispose of broken glassware in the bins
labeled “broken glass” as shown in Figure 19.1. Do not use the normal waste
baskets for broken glass.
Figure 19.1
Broken glass container.
19.3 Experimental Procedure
The characterization tests described in the following sections can be performed
in any order. To help make efficient use of equipment and time, your instructor
will probably tell different individuals to start with different characterization
tests. Be attentive for this announcement.
1. Obtain Three Test Tubes: Obtain three test tubes from your laboratory
drawer and line them up in a test tube rack at your work area. Make sure they
are clean and dry.
2. Add Salicylic Acid to Test Tube: Add a few crystals of pure salicylic acid
to one of the test tubes.
3. Add Product to Test Tube: Add a few crystals of your aspirin synthesis
product to another test tube.
4. Add Aspirin to Test Tube: Add a few crystals of authentic (pure) aspirin to
the last test tube.
6. Add Ferric Chloride Solution to Test Tubes: Add 2 drops of a solution ⌘ Ferric chloride is FeCl3
that is 1% in ferric chloride.
1. Obtain Three Test Tubes: Obtain three clean and dry test tubes from your
drawer. Line them up in a test tube rack.
3. Add Ethanol/Ethyl Acetate Solution to Test Tubes: To each test tube add
20 drops of a solution that is 50% ethanol and 50% ethyl acetate by volume.
Agitate the test tubes to dissolve the samples in the solvent.
1. Obtain a TLC Jar: Find where the TLC jars are located and retrieve one. ⌘ TLC is short for thin layer
chromatography.
Make sure it has a lid.
2. Add Developing Solvent to TLC Jar: Add about 10-15 mL of the develop- ⌘ In this lab the developing solvent is
30% hexane and 70% ethyl acetate.
ing solvent to the TLC jar.
3. Check Depth of Solvent: Using a ruler, measure the depth of the solvent in
the jar. You can do this from outside the jar. The ruler does not have to be
immersed in the jar. Be sure the depth is no more than 7.5 mm. Adjust if
necessary.
126 Characterization of Synthesized Aspirin and Oil of Wintergreen
4. Cover TLC Jar with Lid: Place the lid on the TLC jar and allow it to stand
while you proceed to preparing the TLC plates.
1. Obtain a TLC Plate: Obtain a TLC plate from your instructor. Be sure to
always handle the TLC plate by its edges. Never touch the surface with your
fingers.
2. Mark TLC Plate: Using a pencil, lightly draw a very narrow and faint line
across one short side of the TLC plate about 1 cm from the bottom. Lightly
mark three equally spaced X marks on the line. The marks on the outside
⌘ Be very gentle marking the TLC should be at least 0.5 cm from the left and right edges.
plate. Do not use pen.
4. Spot TLC Plate: Using a different micropipette for each solution, spot each
of the three solutions you prepared onto its own X on the TLC plate. Be sure
to write down in your lab notebook which solution is on which X.
5. Verify Spots on TLC Plate: After applying all three solutions to the TLC
plate, verify that enough of each sample has been spotted on the plate. This
is confirmed by checking that a dark spot exists on each X when the plate is
viewed under UV light. Spot more solution on the plate if needed.
1. Develop TLC Plate: Place the TLC plate in the TLC jar prepared earlier and
place the lid on the jar. Make sure the end containing the spotted samples is
placed in the bottom of the jar. Also be sure the spots are not submerged by
the developing solvent. If they are, you will have to start over.
2. Monitor TLC Plate Development: Let the developing solvent rise to within
0.5 to 1.0 cm of the top of the plate. When the solvent has reached that height,
remove the TLC plate from the TLC jar.
3. Allow TLC Plate to Dry: Set the TLC plate on a paper towel face up. Allow
it to dry in air for a few minutes.
4. Outline Spots on TLC Plate: After the solvent has evaporated from the
plate, expose the plate to UV light and outline all spots in pencil.
Melting Point
This section describes how to determine the melting point of the aspirin synthesis
⌧ It will be helpful if you work with a product. Be sure to refer to Melting Point Range Determination in Chapter 6
partner as described in Section 6.3 on
page 35. starting on page 31 for detailed information about how to collect a melting point.
Only brief instructions are given here.
19.4. Before Exiting Lab 127
1. Obtain Melting Point Capillaries: Find where the melting point capillaries
are located and retrieve three of them. Take these back to your work area.
2. Obtain Weighing Paper: Obtain three pieces of weighing paper and bring
them back to your work area.
4. Pack Capillaries with Samples: Pack each melting point capillary with one
of the samples you just poured out. Each capillary should have enough sample
to bring the sample depth to a few millimeters as shown in Figure 6.6 on
page 34.
Infrared Spectrum
Your instructor or your laboratory assistant will provide considerable help in
collecting the infrared spectrum of the products from the aspirin synthesis and
the oil of wintergreen synthesis.
2. Prepare Sample: Place some of your product sample onto salt plates in the
manner described by your instructor.
2. Place all used developing solvent in the bottle labeled “used developer” in
the hoods in the back of the room.
128 Characterization of Synthesized Aspirin and Oil of Wintergreen
5. Draw a line at the end of your experimental work and sign on it.
6. Have your instructor sign on the line at the end of your experimental work.
2. What does the thin layer chromatography tell you about the identity and
purity of the aspirin synthesis product?
3. What does the ferric chloride test tell you about the identity and purity of the
aspirin synthesis product?
4. What does the infrared spectrum of the aspirin synthesis product tell you
about its identity and purity? If you have performed molecular modeling
of the vibrations in aspirin, compare the infrared spectrum predicted by the
modeling software to the infrared spectrum you obtained for your actual
product.
5. What does the infrared spectrum of the oil of wintergreen synthesis product
tell you about its identity and purity? If you have performed molecular mod-
eling of the vibrations in oil of wintergreen, compare the infrared spectrum
predicted by the modeling software to the infrared spectrum you obtained for
your actual product.
Chapter 20
Molecular Modeling of Infrared Absorptions
20.1 Introduction
In this laboratory project we will use molecular modeling techniques to inves-
tigate the infrared absorption spectra for a series of molecules to learn how
infrared spectroscopy can be used to identify and distinguish molecules based
on common structural features. Along the way, you will learn how the atoms ⌘ These common structural features
are called functional groups.
in a molecule move when exposed to infrared light. This project is relatively
straightforward to carry out, but it requires some background information on
spectroscopy, molecular modeling, and how we describe molecular structure. O
H H
129
130 Molecular Modeling of Infrared Absorptions
*
Bond Angle Molecular Vibration
When we draw diagrams of molecules, such as those in Figures 20.1 and 20.4,
we get the impression that the atoms are stationary. This is never true. The
atoms in all molecules are constantly in motion, and these motions are called
*
Bond Angle vibrations because the motions occur in a regular and repeating pattern. If you
Bond Length
have a physics background, you might call this periodic motion. The atoms do
Figure 20.4 not move by much, but they are always moving relative to one another. The
Codeine with a bond subject of molecular vibration is complicated, and its detailed exploration is well
length and two bond angles beyond the scope of this project. For this project, all you need to understand is
marked. that there are two basic types of vibration: stretches and bends.
O A stretch is a type of vibration in which the length of a bond changes. If the
H H two atoms defining the ends of a bond get further apart, the bond is undergoing a
stretching vibration. Because vibrations are regular and repeating, the length-
ening cannot continue forever. It eventually stops and becomes compression.
Figure 20.5 That eventually stops, too, and becomes lengthening again. In other words, in a
Displacement arrows for a stretching vibration, the two atoms defining a bond move away from each other
stretch in water. and then toward each other in a repeating pattern.
A bend occurs when atoms move in such a way to increase or decrease a
O bond angle in a regular and repeating manner. So, for instance, when the two
hydrogen atoms in water in Figure 20.1 move closer together, the H-O-H bond
H H angle changes. This is a bending type of vibration.
Figure 20.6
Displacement arrows for a Indicating Vibrations with Displacement Arrows
stretch in water.
Words become too cumbersome when discussing vibrations. Therefore, chemists
O use a short hand notation to indicate the type of vibration. Chemists use arrows
on atoms to show which way they move in a vibration. Arrows that move
H H directly along a bond indicate stretches as shown in Figure 20.5. The arrows
on the hydrogen atoms in Figure 20.5 indicate stretches of the H-O bond. This
same stretch could be indicated with arrows going the other way as shown in
Figure 20.7 Figure 20.6. Either is acceptable.
Displacement arrows for a When indicating a bend with arrows, the arrows are typically close to being
bend in water. at a right angle to the direction of a bond. If a chemist wanted to indicate the
bending motion of water, the arrows in Figure 20.7 or Figure 20.8 would be
O acceptable. Each shows the same bend. In all cases, the arrows placed on the
H H molecule to show the type of vibration are called displacement arrows because
they indicate which way the atoms displace during a vibration.
Figure 20.8
Displacement arrows for a
Atomic Spectroscopy
bend in water.
In lecture you have seen that hydrogen atoms exposed to electromagnetic radia-
tion (light) will absorb specific wavelengths of that light to produce an absorption
spectrum. You have also learned that these absorptions result in hydrogen’s elec-
tron moving from one stable orbit to another stable orbit. When the energy of
the light exactly matches the energy difference between two stable orbits of the
electron, the atom will absorb that wavelength. All other wavelengths of light
20.1. Introduction 131
are not absorbed; they are transmitted. When light is absorbed by hydrogen, we
say that it has undergone a transition. All atoms can undergo transitions when
exposed to the right wavelength of light.
Every atom has a different absorption spectrum. In fact, the absorption
spectra for atoms are so unique that they can be used to identify the elements
present in a sample. Another way of saying this is that the absorption spectrum
of each element serves as a fingerprint for that element. It is a unique identifier.
Of course, experimental realities complicate this somewhat, but it is largely true.
Molecular Spectroscopy
Molecules can also undergo transitions in which electrons move from one “orbit”
to another, and you will learn about these transitions in later laboratory projects
that involve ultraviolet/visible spectroscopy. For now, however, we want to
focus on another type of transition that can take place for molecules that is
called a vibrational transition. In this type of transition, the atoms in a molecule
begin to move relative to each other in response to being exposed to a particular
wavelength of light. Vibrational transitions can typically be caused by light in the
infrared region of the spectrum. When molecules are exposed to infrared light
and the absorptions are recorded, the result is an infrared absorption spectrum.
These vibrations involve atoms getting closer together and further apart in a
repeated manner, much like a mass oscillating on the end of a spring or a clock
pendulum moving back and forth. Vibrational transitions can involve stretches ⌘ Yes, clocks used to have
pendulums. The motion of the
or bends. An infrared absorption spectrum is characteristic of a molecule in the pendulum is so regular that it can be
used to . . . keep time.
same way an atomic absorption spectrum is characteristic of an atom because
the number and type of vibrations in a molecule are unique to that particular
molecule. This can be used to identify molecules.
Vibrational Spectra
So far, I have almost exclusively talked about the wavelength at which molecules
or atoms absorb light. However, most chemists do not talk about the wave-
length at which molecules absorb infrared light to excite molecular vibrations.
Instead, most chemists will talk about such transitions as occurring at a particular
wavenumber. This means we need to understand what a wavenumber is.
A wavenumber is a unit that is directly proportional to energy and to fre-
quency. It is not equal to either, but it can be used like them because it is directly
proportional to both. A wavenumber is defined as 1 , where is the wavelength
of the light. It is given the symbol ⌫.
Q So, in mathematical form,
1
⌫Q D : (20.1)
Molecular Modeling
Molecular modeling involves predicting the properties of molecules, including
their spectra, using nothing but mathematical models. These models can some-
132 Molecular Modeling of Infrared Absorptions
times be quite complicated, and the details of how these models work are well
outside the scope of this course. However, thanks to modern computers, we can
easily use these models to obtain meaningful predictions about the behavior of
molecules without understanding every detail of how the models work. In this
project you will use known models to predict the spectra for a set of molecules
and to obtain information about how the atoms vibrate after each absorption.
2. Draw Molecule in Scigress and Save: Draw one of your assigned molecules
in Scigress, valence beautify it, and then save the file with the name of the
molecule.
3. Set Up Computational Experiment to Predict Spectrum: Set up a new ⌘ Property of: chemical sample
Property: IR Transitions
experiment in the Scigress software by selecting New from the Experiment Using: MOG PM5 FORCE
menu. In the Experiment window that appears, select IR Transitions next to
Property and MOG PM5 FORCE next to Using. Leave the setting next to
Property of: at the default setting of chemical sample.
12. Record Wavenumber of Assigned Bend: When you have found the tran-
sition that corresponds to the indicated bend, double click on the triangle
for that transition (or select Transition Attributes... from the View menu) and
record the wavenumber of that transition to one decimal place. Close the
Transition Attributes window when finished.
13. Provide Data To Class: When you have collected the absorption wavenum-
ber for each indicated stretch and bend in all your assigned molecules, provide
the data to the class in the manner indicated by your instructor.
H O H
C C O 14. Record Conclusions Drawn from Class Data: Your instructor will com-
H C C C
ment on the meaning of the class data when all the data are submitted. You
should record in your laboratory notebook the major conclusions to be drawn
C C O
from the class data.
H H H
Salicylic Acid
Aspirin, Oil of Wintergreen, and Salicylic Acid
After your instructor has helped you see what the group data implies, you are
H O H
to predict the infrared absorption spectra for salicylic acid, oil of wintergreen,
C C O and aspirin. The procedure presented below is a condensed version of the more
H C C C detailed procedure enumerated in the previous section. You should fill in the
detailed procedure from your previous experience.
C C O
H H C H
1. Predict IR Absorption Spectrum of Salicylic Acid: Draw salicylic acid in
Oil of Wintergreen H H a new Scigress window and predict its infrared absorption spectrum using
MOG PM5 FORCE with the procedure you previously employed. Salicylic
O acid is shown at the top of Figure 20.9.
H
2 Work through as many of the Post-Lab Assignments as you can before the
end of the lab period so that you can take advantage of your instructor’s help.
2 Draw a line at the end of your experimental work and sign on the line.
1. For a given bond in a molecule, does it take more energy to stretch that bond
or to carry out a bend involving that bond? You should be able to answer this
question based on the data you gathered today. Cite specific evidence from
your work today to support your answer.
This lab introduces the use of molecular modeling software to visualize molec-
ular structure and to calculate molecular properties. The structure of H2 SO4
and SO24 are investigated and compared to their Lewis structures. The se-
ries of molecules H2 ; HF; LiF;and NaF are investigated to observe the effect
electronegativity differences have on the ionic nature of a bond.
21.1 Introduction
Molecular Modeling
Humans are terrific at making models that have predictive capacity. For instance,
if you know about gravity and the nearly circular orbits of the planets around the
sun, you can predict what stars and planets can be seen in the sky at any time of
year.
This image of the planets traveling around the sun is a model. It is mostly
correct, and it gives you the ability to make predictions. You can physically
build this model from some balls and wire or you can simply make it in your
head. As long as you apply the rules of the model (Newton’s Law of Universal
Gravitation) fairly, you will obtain reasonably correct predictions.
Plants and stars are huge objects. In chemistry we are interested in modeling
incredibly small things such as atoms and molecules. Chemists have traditionally
modeled molecules as consisting of balls (the atoms) connected by sticks (the
bonds). Such stick and ball models of molecules has great predictive power.
Once the structure of a molecule is known, a great deal can be said about its
functions.
This is not an easy process, however, because the model of how atoms are
held together is quite complex. You have already learned a little about this model
that is called quantum mechanics. By comparison, gravity is simple.
But, fortunately, we live at a time when computers can make complex tasks
easy. What once took trained chemists and physicists years to do by hand can
today be done by a general chemistry student in a few minutes.
137
138 Examining Molecules with Molecular Modeling
The Department of Chemistry has computer software that applies the rules
of quantum mechanics (with some approximations!) to atoms in a molecule
and generates a prediction of what a molecule will look like. You will use this
software in this lab to explore the structure of several molecules.
Goggles
There is no need to wear goggles this week because all your work will be in the
computer lab with no chemicals or glassware.
21.3. Experimental Procedure 139
1. Open the Scigress molecular modeling program and using the Drawing tool
draw H2 SO4 in a manner consistent with the most likely Lewis structure.
2. After drawing the molecule, push the Select tool button and then click any-
where in the blue background to make sure the entire molecule is selected.
5. The default options in the window that pops up are all appropriate. Simple
click the Start button.
6. You will be prompted to save the molecule. You need to save it so select Yes
and then give it a name.
7. The experiment will run after you save the molecule. When the computer
tells you that it is done calculating, close the calculation windows and look at
the results.
8. Measure all the S-O bond lengths. Why are they different?
10. Now, delete the hydrogen atoms by selecting them one by one and pushing
the delete key.
11. Select the oxygen atoms to which these hydrogen atoms were connected and
change their charge to -1.
14. Measure the S-O bond lengths and the O-S-O bond angles again. Can you
explain what has happened?
1. Draw each of these molecules in the Scigress program. You can draw only
one per window.
140 Examining Molecules with Molecular Modeling
4. From the experiment window that pops up, pull down the “Property” list and
scroll down until you see “electrostatic potential on electron density.” Select
this option.
5. Next pull down the “Using” list and scroll down until you see “PM5 geometry
using PM5 wavefunction” and Select this option.
7. When the computer has finished, show the surface and describe the results in
your laboratory notebook.
8. Repeat this procedure for all the molecules in this list and then explain the
trend that you observe.
2 Make sure page numbers appear on all the used pages of your laboratory
notebook.
2 Draw a line at the end of your experimental work and sign on it.
2 Have your instructor sign on the line below your experimental work.
2. Explain the results you obtained for the bond lengths in SO24 . Is it what you
expected?
22.1 Introduction
If you know the mass of a sample of molecules and the quantity of molecules
in that sample, it is a relatively simple matter to compute the molar mass of
the molecules in the sample: just divide the mass (in grams) by the quantity
of molecules in units of moles. That gives a value with units of molar mass,
g/mol. Any experiment that allows you to independently determine the mass
of a sample and the moles of substance present in the sample provides a way
to determine the molar mass of the substance. In this project we will use this
method to determine the molar mass of a liquid.
141
142 Molecular Mass by the Dumas Method
When the liquid was a vapor filling the container as a gas, its volume,
temperature, and pressure were known. Using the ideal gas law,
P V D nRT ; (22.1)
the moles of gas present can be computed. Because the mass of liquid is
already known, it is simple to determine the molar mass of the substance. In
Equation 22.1, P is the pressure of the gas, V is the volume occupied by the gas,
n is the moles of gas particles, R is the Universal Gas Constant, and T is the
temperature of the gas.
Table 22.1
Decisions you must make before you can effectively carry out this experiment.
Help in answering each question is provided in this section.
The Container
The container you will use in this laboratory experiment is a 125 mL Erlenmeyer
flask with a rubber septum on top as a cap. You will insert a syringe needle
through the septum to provide a small hole as the vent for excess vapor. The
flask will be immersed in boiling water to heat the liquid in the flask. When you
remove the flask from the boiling water, you will have to be very careful to make
sure you dry off all water, even the water that condenses around the septum cap.
You will need to know the volume of this container, and it is not 125 mL.
The gas will fill the flask to the top (to the septum), but the 125 mL mark is well
below the top of the neck of the flask. You will have to come up with a way to
determine the volume of the flask.
22.2. Experimental Design Decisions 143
Pressure
To use the ideal gas law (Equation 22.1) to compute the moles of vapor present
in the flask, you must also know the pressure of the the gas in the flask. When a
liquid boils, the vapor pressure of the liquid is equal to the current atmospheric
pressure. Therefore, the pressure of liquid vapor inside the flask when all the
liquid has just finished boiling will be the current atmospheric pressure. All you
need is a current reading from a barometer
Table 22.2
Mass of flask plus liquid after experiment when the initial volume of liquid is
varied from 2 mL to 5 mL.
The data in Table 22.2 show how the volume of liquid introduced to the flask
at the start of the experiment influences the final mass of the flask plus liquid
when the experiment is complete. These data provide enough guidance for you
to determine the volume of liquid that should be introduced at the start of the
experiment.
the flask. Therefore, the Schlieren pattern will disappear. When the Schlieren
pattern disappears, all the liquid has vaporized.
Table 22.3
Mass of flask plus liquid when the flask is removed from the water bath after
an increasing time following the vaporization of all liquid in the flask.
Table 22.4
Mass of flask plus unknown after cooling for the indicated time.
Waste Disposal
All chemical wastes have their appropriate receptacles in the large hoods in
the back of the laboratory. The volume of liquid waste remaining after your
experiments will be small, but it should still be poured into the appropriate waste
container.
Broken Glass
Do not work with any broken glassware. Dispose of broken glassware in the bins
labeled “broken glass” as shown in Figure 22.1. Do not use the normal waste
baskets for broken glass.
Figure 22.1
22.4 Experimental Procedure Broken glass container.
This section provides a suggested procedure for determining the molar mass of a
volatile liquid by the Dumas method.
1. Set Up Boiling Water Bath: Fill a 600 mL beaker about half full with water ⌘ Add water as needed during the lab
period, but never add water during an
and place it on a hot plate. Add a few boiling stones and begin heating the experimental trial.
beaker quickly until the water boils. Turn down the heat until the water boils
gently but constantly.
3. Weigh Container with Septum: Measure the mass of the flask with the
septum in place.
146 Molecular Mass by the Dumas Method
4. Attach Flask to Ring Stand: Attach the flask to a ring stand with a single
burette clamp.
⌘ The volume of unknown liquid to 7. Add Unknown Liquid Sample to Container: Add the appropriate amount
add was a decision you were to make
on your own as described on page 143. of unknown liquid to the flask through the septum cap by injecting the liquid
through the septum with a syringe. When the injection is finished, remove
⌘ There should now be two needles the syringe from the needle, but leave the needle inserted in the septum.
in the septum.
8. Immerse Flask in Boiling Water: Immerse the flask into the boiling water
bath as deeply as possible with the clamp attached. Avoid allowing water to
touch the septum.
⌘ How long to leave the flask in the 10. Remove Flask from Water Bath: When you are convinced the liquid in the
boiling water after the Schlieren pattern
disappears was a decision you were to flask has completely vaporized and the Schlieren pattern has disappeared,
make on your own as described on
page 144. remove the flask from the water bath after the time interval you previously
determined.
⌘ How long to let the flask cool was a 11. Allow Flask to Cool: Allow the flask to cool for the time period you previ-
decision you were to make on your
own as described on page 144. ously determined. While cooling, you can take the flask out of the clamp.
12. Thoroughly Dry Flask: Dry the outside of the flask as completely as possi-
ble, including areas close to the bottom of the septum.
13. Mass the Flask: After the cooling period you previously determined, mass
the flask. Be sure to remove the needles from the septum before weighing the
flask.
14. Complete Two Replicate Trials: Repeat steps 6 to 13 twice more. There
is no need to replace the septum or remove the liquid that is already in the
container.
15. Pour Remaining Liquid into Waste Container: Remove the septum cap
and pour the remainder of the liquid in the appropriate waste container.
2 Draw a line at the end of your experimental work and sign on the line.
1. Compute the mass of liquid remaining in the flask after each experimental
run.
2. Compute the moles of liquid remaining in the flask after each experimental
run. For this, you will have to know the volume of the flask, the atmospheric
pressure, and the temperature of the flask. The temperature of the flask is
the temperature of the boiling water, but recall that the temperature of the
boiling water will not be 100ı C unless the atmospheric pressure is exactly
760 mmHg.
3. Compute the molar mass of the liquid for each experimental run.
4. Compute the average molar mass of the liquid along with a standard deviation.
Chapter 23
Identification of an Unknown by Freezing Point Depression
23.1 Introduction
Freezing Point Depression
When a solute is dissolved in a solvent, the freezing point of the solution is
lower than that of the pure solvent. This is called freezing point depression. It is
typically given the symbol Tf and is defined as the normal freezing point of
the pure solvent minus the freezing point of the solution. The value of Tf is
always positive, and it is understood that it refers to the amount by which the
freezing point of a pure solvent is lowered by addition of a solute.
Freezing point depression is directly proportional to the molal concentration ⌘ Molality of solute particles is
defined as the moles of solute particles
of solute particles. The identity of the solute particles does not matter. The divided by the kilograms of solvent.
constant of proportionality that relates the molal concentration of solute particles
to Tf is the freezing point depression constant. It is normally given the symbol
Kf . It is unique for each solvent. This verbal description of freezing point
depression can be expressed mathematically as
149
150 Identification of an Unknown by Freezing Point Depression
using freezing point depression when Tf does not depend on the identity of
the solute. This is possible because the molar mass of a solute can be determined
by measuring the freezing point depression of a solution composed of a known
mass of solute and a known mass of solvent. Molar mass by itself may not be
enough to identify an unknown compound, but it can be helpful when used in
Time
combination with other physical or chemical data.
Figure 23.1 In this project you will measure the freezing point depression of cyclohexane
Idealized cooling curve for when a known mass of an unknown compound is dissolved in a known mass
pure solvent. The tempera- of cyclohexane. You will compute the molar mass of the compound from the
ture remains constant while freezing point depression. You will use this in combination with a measured
freezing. melting point to suggest the most likely identity of the compound from a list of
candidates.
To measure the freezing point of pure cyclohexane you will place the liquid
in a test tube which you will immerse in an ice water bath. You will record the
freezing point
Temperature
experiment proceeds. You will have to do your best to find the region of constant
temperature in the case of cooling pure solvent and, in the case of cooling the
solution, the region of intersection shown in Figure 23.2.
When cooling a solution, you may record temperatures that go down but then
Time go back up as illustrated in Figure 23.3. If you encounter this, the freezing point
is not the lowest point on the graph. Instead, you can determine the freezing
Figure 23.3 point by extrapolating the data points in the high-slope region and those in
Experimental cooling data the low-slope region until the extrapolations intersect. This intersection is the
extrapolated to find the freezing point. The region where the temperature goes down before going back
intersection between the up is results from not thoroughly stirring the solution.
low-slope and high-slope
regions.
23.2. Safety Considerations 151
Plotting Data
You will have to plot the temperature versus time data to finish your analysis.
You will most likely plot these data using a piece of software such as Apple
Numbers, OpenOffice, or Microsoft Excel. Regardless of the application you
use, the plots need to be constructed so that temperatures can be read from the
vertical axis with a precision of ˙0:1ı C. This can be accomplished by changing ⌘ It will also be helpful to plot your
data so that the temperature scale is
both the range of the vertical temperature axis and the spacing of the tick marks along the long side of a piece of paper.
This will require that you rotate the plot
on the axis. to be portrait and not landscape. It is
The vertical axis range should be set to something only slightly larger than not sufficient (or helpful) to print the
graph in the portrait orientation without
the temperature range of your actual data points so that no space is wasted. also rotating the plot. The goal is to
spread out the temperature axis as
Wasted space pushes tick marks closer together and makes the temperature scale much as possible.
more difficult to read. We want to avoid this by spreading the data out as much as
we can. Most software packages will ask you enter a minimum and a maximum
temperature to specify the axis range.
The interval for tick marks is also important. Major tick marks should be
placed every 1:0ı C, and minor tick marks should be placed every 0:2ı C. This
will provide you with a graph that can be read to a precision of ˙0:1ı C.
Goggles
You are expected to wear your goggles at all times while in the lab. Failure to do
so may result in expulsion from the lab.
Waste Disposal
All waste in this lab must be poured into the appropriate waste containers. No
waste can be poured down the drain.
152 Identification of an Unknown by Freezing Point Depression
Broken Glass
Do not work with any broken glassware. Dispose of broken glassware in the bins
labeled “broken glass” as shown in Figure 23.4. Do not use the normal waste
baskets for broken glass.
Figure 23.4 2. Record Unknown Number: At your lab station you will find a test tube
Broken glass container. or vial containing an unknown solid compound. Record the number of this
unknown in your laboratory notebook.
3. Set Up Ice Water Bath: Fill a 400 mL beaker about half full of tap water
and add ice so that the beaker is nearly full.
4. Obtain Test Tube: Obtain a 150 mm (6-inch) test tube from the table in front
of the lab. This is not one of the test tubes in your drawer.
5. Obtain Test Tube Clamp: Obtain a test tube clamp from the appropriate
drawer in the lab. You will use this to secure the 150 mm test tube to a ring
stand so that it can be lowered into and raised out of the ice water bath.
3. Weigh Test Tube with Cyclohexane: With the test tube containing the
cyclohexane in the same beaker used previously, find the mass of the beaker,
test tube, and cyclohexane.
⌘ Do not lower the test tube into the 4. Clamp Test Tube to Ring Stand: Using a test tube clamp, secure the test
ice bath yet.
tube containing cyclohexane to a ring stand. Place the ice water bath under
the test tube so that it can be lowered into the ice bath.
23.3. Experimental Procedure 153
8. Lower Cyclohexane Into Ice Bath: Lower the test tube apparatus into the
ice bath, making sure the top of the cyclohexane is below the surface of the
ice bath. Immediately start a stop watch and begin stirring the cyclohexane
gently with the thermometer.
9. Record Temperature Data: One partner (the observer) should stir the cyclo- ⌘ This part of the experiment is a bit
intense. If you miss a temperature
hexane and monitor the temperature continually during the experiment. The reading, just move to the next one.
other partner (the recorder) should monitor the stopwatch and record data.
Every ten seconds, the recorder should say “now”, and upon that prompt the
observer should read out loud the current temperature to the nearest 0:1ı C.
Continue collecting data for about 5 minutes overall or until the temperature
has remained constant for 2 minutes.
10. Remove Cyclohexane from Ice Bath: Raise the test tube apparatus contain-
ing the cyclohexane out of the ice bath. Allow the cyclohexane to melt and
to return to room temperature. Do not remove the thermometer from the test
tube. If you do, you will lose cyclohexane.
11. Repeat Measurement: Repeat the measurement of the cooling curve of pure
cyclohexane two more times using the same procedure as above.
3. Lower Cyclohexane Solution Into Ice Bath: Lower the test tube apparatus
into the ice bath, making sure the top of the cyclohexane solution is below
the surface of the ice bath. Immediately start a stop watch and begin stirring
the cyclohexane solution gently with the thermometer.
154 Identification of an Unknown by Freezing Point Depression
⌘ This part of the experiment is a bit 4. Record Temperature Data: One partner (the observer) should stir the cy-
intense. If you miss a temperature
reading, just move to the next one.
clohexane solution and monitor the temperature continually during the ex-
periment. The other partner (the recorder) should monitor the stopwatch and
record data. Every ten seconds, the recorder should say “now”, and upon
that prompt the observer should read out loud the current temperature to the
nearest 0:1ı C. Continue collecting data for about 5 minutes.
5. Remove Cyclohexane Solution from Ice Bath: Raise the test tube appa-
ratus containing the cyclohexane solution out of the ice bath. Allow the
cyclohexane solution to melt and to return to room temperature. Do not re-
move the thermometer from the test tube. If you do, you will lose cyclohexane
solution.
6. Repeat Measurement: Repeat the measurement of the cooling curve for the
cyclohexane solution two more times using the same procedure as above.
Check Data
Before disassembling your experimental setup and leaving the lab, you should
plot your temperature versus time data for the cooling of pure cyclohexane and
the cyclohexane solution. You should check that the data look roughly like the
expected idealized curves shown in Figures 23.1 through 23.3. If your data do
not look usable, you should go back to the lab and collect more data. You can
check with your instructor if you wish.
⌘ You need a laptop, tablet, or smart To visualize your data, the minimum you need is a computing device with
phone with access to the Internet.
access to Google Drive. A computing device with a native spreadsheet appli-
cation will probably make things easier. Using the application of your choice,
plot your data and assess its quality. In this visualization step you do not have to
produce beautiful graphs; you just have to examine the data.
2 Clean and dry the 150 mm test tube. Return it to the table at the front of the
lab.
2 Return the test tube for vial with the unknown compound to the front of the
room.
2 Draw a line at the end of your experimental work for the day. Sign your name
on the line.
2 Have your instructor sign your lab notebook before you leave the lab.
✏ Set the range for each axis to utilize all the space on the paper.
✏ Set minor tick marks on the temperature axis to be placed every 0:2ı C.
✏ Orient the graph so that the vertical temperature axis is along the long ⌘ It is not sufficient to print the plots in
the portrait orientation unless the
side of the paper onto which it will eventually be printed. This will spread temperature axis extends for the entire
length of the long side of the page.
out the temperature axis as much as possible. This must be done in the
plotting application.
✏ Be sure you follow all other guidelines for preparing graphs as discussed
in Chapter 9.
The only guideline for preparing graphs that you can violate in preparing graphs
for this project is the one regarding grid lines. These graphs are not for presenta-
tion of data to an external audience. Instead, they are “working” graphs for the
purpose of allowing you to extract freezing temperatures. Grid lines may help in
this.
2. For each cooling curve for pure cyclohexane, determine the freezing point.
2. Using a ruler, draw the best single line you can through the high-slope region
early in time. Do the same for the low-slope region. Do this for each cooling
curve.
156 Identification of an Unknown by Freezing Point Depression
3. Find the temperature at which these lines intersect on each cooling curve.
This temperature is the freezing point. Record this value for each cooling
curve.
4. Compute the average freezing point for the solution using the data from all
cooling curves.
5. Compute the freezing point depression, Tf , for the solution using the
average freezing points.
2. Compute the molar mass of the unknown compound you were assigned.
3. In conjunction with the melting point you determined for the unknown, select
the most likely identity of the unknown from the list of candidates.
Chapter 24
What Are the Kinetics of the t-Butyl Chloride Hydrolysis?
The rate law, rate constant, and activation energy of the hydrolysis of t-butyl
chloride are determined.
CH 3
24.1 Introduction
H 3C C Cl
In this experiment we will examine the kinetics of the hydrolysis of tertiary-butyl
chloride, .CH3 /3 CCl. Tertiary-butyl chloride is often abbreviated as tert-butyl
chloride or t-butyl chloride. Its molecular structure is shown in Figure 24.1. The CH 3
hydrolysis reaction we will study is given by the equation Figure 24.1
Drawing of tertiary-butyl
.CH3 /3 CCl C 2H2 O ! .CH3 /3 COH C H3 OC C Cl . (24.1)
chloride.
The molecule t-butyl chloride is a member of a group of organic compounds
called alkyl chlorides. They differ in composition by the hydrocarbon group
attached to the chlorine. All alkyl chlorides undergo a hydrolysis reaction similar
to that in Equation 24.1. Only the hydrocarbon portion is different. Because ⌘ An alkyl group is a collection of
carbon and hydrogen atoms that are all
these reactions are so similar, it is common to write the hydrocarbon portion of singly bonded. Symbolizing alkyl
groups with R is common throughout
the formula of alkyl chlorides as R, where R can be any alkyl group. This allows chemistry.
the hydrolysis of any alkyl chloride to be written as
If R is t-butyl, Equation 24.2 is the same as Equation 24.1. To save space and
to be consistent with common practice in chemistry, t-butyl chloride will be
abbreviated as RCl. The alcohol produce will be abbreviated as ROH.
157
158 What Are the Kinetics of the t-Butyl Chloride Hydrolysis?
We know the stoichiometric relationship between moles RCl used and moles
H3 OC formed. It is one to one. We also know the stoichiometric relationship
between moles H3 OC produced and moles OH added. It is also one to one.
⌘ You should write an equation This information allows us to write
showing the reaction between
hydroxide and hydronium ion.
moles RClremaining D moles RClinitial moles OHused to titrate . (24.4)
Goggles
As with all laboratory experiments, you are expected to wear your goggles at all
times while in the lab. Failure to do so may result in expulsion from the lab.
Waste Disposal
All waste in this lab can be poured down the drain with plenty of water.
Broken Glass
Do not work with any broken glassware. Dispose of broken glassware in the bins
labeled “broken glass” as shown in Figure 24.2. Do not use the normal waste
baskets for broken glass.
Figure 24.2
Broken glass container.
24.3 Experimental Procedure
Setup Equipment for Experiment
1. Setup Water Bath: Fill an 800 mL beaker with about 300 mL of tap water
that is close to room temperature. Allow this beaker to reach room temper-
ature, unless you were assigned a reaction temperature that is above room
temperature (see next step).
2. Place Water Bath on Hot Plate: If you belong to the part of the lab that will
carry out this experiment at an elevated temperature, place your water bath
on a hot plate and begin gently heating the water bath until your assigned
temperature is reached. Maintain this elevated temperature within ˙1ı C. ⌘ It is very important that you regulate
the temperature in your water bath to
Control the temperature by taking the beaker off the hotplate as necessary. within ˙1ı C. This means you will have
to suspend a thermometer in the water
bath to constantly monitor the
3. Obtain 250 mL Flask and Stopper: Obtain a 250 mL flask and make sure temperature.
it is clean and dry. Find a cork to fit the flask.
4. Fill Flask with Solvent: Using a graduated cylinder, add 100 mL of a 50:50
v/v isopropanol-water mixture to the flask and quickly stopper it.
5. Place Flask in Water Bath: Place the flask into the water bath, but do not
allow it to touch the bottom of the beaker. You may consider securing the
flask in the water bath with a clamp attached to a ring stand.
160 What Are the Kinetics of the t-Butyl Chloride Hydrolysis?
⌘ The NaOH is about 0.25 M but you 6. Prepare Buret: Obtain a buret and buret holder, and bring them back to
need to record the precise value which
appears on the bottle.
your work area. Rinse the buret twice with 5 mL aliquots of the standardized
NaOH in isopropanol-water solution. Place buret in the buret holder and
carefully add about 30 mL of the standardized NaOH solution to the buret.
Do not completely fill buret.
2. Add t-Butyl Chloride: When you are ready to begin the reaction, quickly
remove the flask from the water bath and take it to the hood where the t-
⌘ The moment the t-butyl chloride is butyl chloride is dispensed. Your instructor will then add 1:00 mL of t-butyl
added is t D 0. Start a stop watch or
record the clock time in your notebook. chloride to your flask. Stopper and swirl the flask to dissolve the t-butyl
chloride. Start a stop watch or write down the clock time as soon as the
t-butyl chloride is dissolved. Return the flask to its water bath as quickly as
possible.
3. Add Sodium Hydroxide to Flask: Record the initial buret reading in your
notebook. Room T: Add about 0.5 mL of NaOH solution (or enough to make
the pink color persist) from the buret to the solution in the flask and mix well
by swirling the flask. Record final buret reading. For T=26ı C: Add about
0.75 mL of NaOH solution (or enough to make the pink color persist) from
the buret to the solution in the flask and mix well with a stirring rod. Record
final buret reading. For T=30ı C: Add about 1.0 mL of NaOH solution (or
enough to make the pink color persist) from the buret to the solution in the
flask and mix well with a stirring rod. Record final buret reading.
⌘ All clock times should be recorded 4. Monitor Reaction Flask: Watch the flask carefully and record the clock
to the nearest 5 seconds.
time at which the solution fades to colorless. Record all buret readings (initial
and final) that correlate with the clock times at which the end points are
reached. These constitute essential data!
2. Dump Reaction Mixture: Discard the contents of the reaction flask down
the sink with plenty of water.
3. Unplug Hot Plate: Unplug the hot plate and allow it to cool. Then return it
to the shelf.
2 Draw a line at the end of your experimental work for the day. Sign your
notebook at the line.
2 Have your instructor sign your lab notebook before you leave the lab. This
helps verify where you stopped lab work for the week.
1. Compute the number of moles of t-butyl chloride you added to your reaction
flask.
162 What Are the Kinetics of the t-Butyl Chloride Hydrolysis?
5. Using the data in the spreadsheet you have just created, make a plot of ŒRClç
versus time. Add a linear trend line and make sure the equation for the line
appears on the graph. Print out the graph and include it in your notebook.
6. Using the data in the spreadsheet you have just created, make a plot of lnŒRClç
versus time. Add a linear trend line and make sure the equation for the line
appears on the graph. Print out the graph and include it in your notebook.
1
7. Using the data in the spreadsheet you have just created, make a plot of ŒRClç
versus time. Add a linear trend line and make sure the equation for the line
appears on the graph. Print out the graph and include it in your notebook.
8. From all the information you have just processed, determine the order of this
reaction and find the rate constant, k.
9. Pool the class data for the rate constant, k, at the three different temperatures
and make an appropriate plot to determine the activation energy of this
reaction. Print out the plot and include it in your notebook.
Chapter 25
How Can We Alter the Extent of a Reaction?
25.1 Introduction
Extent of Reaction
One of the complexities of chemistry is that reactions do not always go to
completion. For instance, if you place acetic acid (CH3 COOH) in water, some
of it will dissociate into acetate ions (CH3 COO ), producing hydronium ions
in the process. However, the bulk of the acetic acid will not dissociate. In other
words, the reaction does not go to completion.
The process described above can be written as the equation
where the double-headed arrow between reactants and products explicitly indi-
cates that the reaction is reversible, which means that this equation represents an
equilibrium process. To indicate that most of the acetic acid remains undissoci-
ated we would say that the equilibrium lies far to the left. There is nothing in
the equation itself that tells us to which side the equilibrium lies. This has to be
determined computationally or experimentally.
Any discussion of a reaction that does not convert all reactants to products
must be discussed in the context of equilibrium and reversibility. This is why we
normally include the double-headed arrow in equations describing such reactions.
However, you should keep in mind that just because a reaction is reversible does
not mean it does not go to completion. Technically, all reactions are reversible,
but many still go to completion.
A reaction that is known not to go to completion implies a reversible reaction
and an equilibrium process. However, reversibility does not imply that a reaction
does not go to completion.
The degree to which a reaction goes to completion is called the extent of
reaction. We would say that acetic acid dissociation in water has a small extent
of reaction. If your business is to produce large quantities of a product, such
as some anti-cancer drug, then you want to force all reactions involved in the
synthesis of that product to have a large extent of reaction. If you are in the
163
164 How Can We Alter the Extent of a Reaction?
and
Co2C (aq) C 4Cl (aq) ˛ ŒCoCl4 ç2 (aq)
(25.3)
pink colorless blue
In both of these equilibrium systems, any change in extent of reaction can be
monitored by color changes. In the first equilibrium system, a change in color
from brown to red indicates a greater extent of reaction. A change from red to
brown indicates a reduced extent of reaction. In the second equilibrium system,
a change in color from pink to blue indicates an increase in the extent of reaction.
Likewise, a change from blue to pink indicates a decrease in the extent of that
reaction.
The first step in successfully completing this lab is to accurately record your
observations. Do this without any regard for what you think “should” happen.
Just record what you see. After this, use your observations to determine if the
extent of reaction changed. This can be done based on the color change that was
observed, if any. Based on the observed color changes, you can determine if
the extent of reaction increased (equilibrium shifted to the right) or decreased
(equilibrium shifted to the left).
After you have determined how each change affected the equilibrium, you
can attempt to write an equation to describe that change. Remember, if a change
in the extent of reaction was observed, then the change you induced in the system
must have caused a change in reactant or product concentrations (including heat).
For instance, if you observe that a change results in a shift in equilibrium
to the right, either a product concentration must have been reduced by your
change or a reactant concentration must have increased. After you determine the
direction of change, you must determine how that change was made and then
describe it with an equation.
Chemical Hazards
1. Concentrated HCl: You will use 12 M HCl in this lab. Concentrated HCl is
corrosive and will cause burns if you get it on your skin. It will also damage
clothing. If you get concentrated HCl on your skin, wash the affected area
immediately with plenty of water.
Goggles
As with all laboratory experiments, you are expected to wear your goggles at all
times while in the lab. Failure to do so may result in expulsion from the lab.
Waste Disposal
No liquid or solid waste can be poured down the drain in this lab. Everything
must be disposed of in the waste containers in the hoods.
166 How Can We Alter the Extent of a Reaction?
Broken Glass
Do not work with any broken glassware. Dispose of broken glassware in the bins
labeled “broken glass” as shown in Figure 25.1. Do not use the normal waste
baskets for broken glass.
2. Prepare Ice Bath: Each student individually can add ice and water to an ice
bath pan. Continue to add ice as needed to keep the ice bath cold.
2. Divide Iron Solution: Divide the iron solution into three 50 mL portions.
Each student in your group can take the 50 mL for use in their own experi-
ments.
Be sure to add the acid to the 3. Prepare Cobalt System: Add 10 mL of 0.05 M Co(NO3 )2 and 10 mL of
aqueous solution and not the other concentrated (12 M) HCl to a 50 mL beaker and stir.
way around.
Dispose of Waste
1. Place All Waste in Appropriate Waste Container: Take all waste gener-
ated in this lab, including the contents of all test tubes and beakers, to the
hood and pour into the designated waste container.
2 Make sure all hot plates have been unplugged and returned to the shelves if
that is where you got them.
2 Draw a line at the end of your experimental work for the day. Sign your
notebook at the line.
2 Have your instructor sign your lab notebook before you leave the lab. This
helps verify where you stopped lab work for the week.
168 How Can We Alter the Extent of a Reaction?
a) state the direction the equilibrium shifted after the change and your
evidence for believing this,
b) indicate which reactant or product caused the change in equilibrium
position, and
⌘ No equation is necessary when c) write balanced equations showing how the reactant or product concen-
describing the results for the heating
and cooling changes. trations changed.
26.1 Introduction
According to United States Food and Drug Administration (FDA) guidelines,
any product labeled vinegar should contain no less than 4 grams of acetic acid
per 100: mL of product at 20ı C. Any product with less than this amount of acetic
acid cannot legally be called vinegar in the United States.
This guideline can be expressed in a more compact form as a percentage.
However, there is more than one way to compute this percentage. We could,
for instance, divide the required minimum mass of acetic acid by the volume of
vinegar to obtain a mass of solute per volume of solution percentage. We could
also divide the mass of required acetic acid by the mass of vinegar to obtain
a mass of acetic acid per mass of solution percentage. Because there is more
than one way to compute the percentage, a label is used to communicate which
method was used. When percentages are computed by dividing mass of solute by
the volume of solution, the percentage is reported with w/v after it. This stands
for weight divided by volume. Otherwise, it is reported as w/w.
Thus, we can say that the FDA guideline for the labeling of vinegar requires
vinegar to be at least 4% w/v acetic acid. Reporting the percentage this way,
although somewhat out of the ordinary, is convenient because it does not require
the density of vinegar that would be needed to obtain the w/w percentage.
As soon as a guideline like this is written, there is a need for a chemist
to analyze samples of vinegar to ensure industry complies with the guideline.
Without such monitoring, industry might get away with selling a product with
less than required quantity of acetic acid. In this laboratory project, we will carry
out an analysis of vinegar samples to determine the percent acetic acid (both w/v
and w/w) in those samples.
Method of Analysis
In this project we will determine the quantity of acetic acid in vinegar samples
by reacting all the acetic acid in the sample with sodium hydrogen carbonate
(sodium bicarbonate), a base. This is an acid-base reaction that produces carbonic
169
170 Analysis of Vinegar by Reaction with Sodium Bicarbonate
water vapor. You will need to account for this. It is left to you to determine how
to do this. The CRC and your text have tables giving water’s vapor pressure as a
function of temperature.
Density of Vinegar
⌘ Decision You want to determine the weight/volume (w/v) and the weight/weight (w/w)
percent acetic acid in the vinegar. The latter (w/w percent) will require that
you know the mass of your original vinegar sample. You could, in principle,
mass the reaction flask before and after the addition of the vinegar to obtain the
mass of the vinegar sample, but the balances we have in the general chemistry
laboratory begin to lose precision at higher masses. Therefore, we need an
alternate approach.
When you set up your reaction flask, you will transfer 5:00 mL of vinegar to
the flask using a volumetric pipet. If you knew the density of the vinegar, you
could determine the mass of the vinegar. It is not possible to just look up the
density of your particular vinegar sample. This means you will have to determine
the density of your vinegar sample. For this purpose, you will find a weighing
bottle at your lab station. It is left up to you to come up with the exact procedure
for determining the density based on your past experience.
Although it is good practice to make three measurements of the density, you
will only make one measurement in this project. The class data will be pooled
to determine an average density for the vinegar. You will then use this average
density in all your computations of the w/w percent acetic acid.
Goggles
As with all laboratory experiments, you are expected to wear your goggles at all
times while in the lab. Failure to do so may result in expulsion from the lab.
Waste Disposal
The chemicals you use today are standard household chemicals (vinegar and
sodium bicarbonate). When these two substances are mixed, the solution will
contain nothing but the salt sodium acetate and maybe excess sodium bicarbonate.
Because of this, it is safe to wash all waste down the sink with plenty of water.
Broken Glass
Do not work with any broken glassware. Dispose of broken glassware in the bins
labeled “broken glass” as shown in Figure 26.1. Do not use the normal waste
baskets for broken glass.
Figure 26.1
Broken glass container.
26.4. Experimental Procedure 173
1. Set Up Gas Collection Cylinder: Fill a large plastic tub about 75% full with ⌘ We set this up first so that the
temperature of water can become
room-temperature tap water. Fill a 100 mL graduated cylinder with water and stable.
immerse in the tub of water.
4. Mass Sodium Hydrogen Carbonate: Use the top loading balances to mass
out the amount of sodium hydrogen carbonate you have already determined
to be appropriate for this experiment. Mass this out in a weighing boat that
can be carried back to your bench.
5. Attach Hose for Gas Collection: Attach a length of rubber hose to the
sidearm of the filter flask.
6. Find Tight-Fitting Stopper: Find a tight-fitting stopper or cork for the flask.
Test to be sure it fits tightly before going on.
7. Insert Tubing in Graduate Cylinder: Insert the tube running from the flask
into the opening of the graduated cylinder. Invert the cylinder in the tub of
water and hold it in this inverted position. Be sure the tube does not come out
of the cylinder, and be sure there is no air in the cylinder.
8. Carry Out Reaction: When you are ready, quickly add all the sodium
hydrogen carbonate to the reaction flask and immediately stopper the flask.
Swirl the flask occasionally until no more bubbles are formed.
9. Remove Tube from Cylinder: When you are convinced the reaction has
stopped, carefully remove the tubing from the mouth of the graduate cylinder.
Do this without letting any of the collected gas out of the cylinder.
10. Determine Volume of Gas Collected: Using the procedure you have already
developed, determine, to an appropriate number of significant figures, the
volume of gas collected.
11. Repeat Twice More: Refill the cylinder with water, clean out the reaction
flask, and perform steps 3 to 10 again until you have four good measurements
of the volume of gas evolved.
174 Analysis of Vinegar by Reaction with Sodium Bicarbonate
2 Draw a line at the end of your experimental work and sign on the line.
6. Determine the percent (w/v and w/w) of acetic acid in each vinegar sample
for each experimental run.
7. Determine the average percent (w/v and w/w) acetic acid and the standard
deviation of the percent.
Chapter 27
Standardization of a Sodium Hydroxide Solution
27.1 Introduction
A standard solution is one for which the concentration of solute is known very
well. By “very well” I mean to at least three decimal places. To standardize
a solution means to determine the concentration of its solute to this level of
precision and accuracy.
Unfortunately, this is not always easy. One might think you could just
weigh out the solute and dissolve it in solvent to a known solution volume and
determine the concentration by simple division. Due to impurities, this often
leads to unacceptable errors. However, there are a few chemical reagents called
primary standards which can be obtained in a pure enough state that a standard
solution can be made by weighing out a known mass of the solid and dissolving
it in a known volume of solution.
Is it possible to prepare a standard solution of a solute that is not a primary
standard? Yes, it is. In order to do this you have to standardize the solution
by titration against a known mass of a primary standard. This is the procedure
you will carry out in this experiment. You will standardize a solution of sodium
hydroxide against a primary standard.
Primary Standards
The requirements which must be met by a primary standard, besides those
necessary for any titrimetric analysis, are:
✏ it should be easy to dry and should not pick up atmospheric moisture while it ⌘ A substance that easily absorbs
moisture from the atmosphere is called
is being weighed, hygroscopic.
175
176 Standardization of a Sodium Hydroxide Solution
In This Experiment
In this experiment, you will standardize a sodium hydroxide solution with
a concentration of approximately 0.15 M. You will do this by titrating the
sodium hydroxide solution against a known amount of the weak acid potassium
hydrogen phthalate, a primary standard. You will thus determine precisely the
concentration of the NaOH solution.
The net ionic equation describing the titration you will do in this experiment
is given by
If you add a known mass of KHP to a flask with water and place the sodium
hydroxide solution in the buret, you can titrate the contents of the flask until the
equivalence point. At the equivalence point, the moles of KHC8 H4 O4 used will
equal the moles of NaOH added. Since you will also know the volume of NaOH
added, you will be able to readily calculate the molarity of the NaOH solution.
It is imperative that the NaOH standardization be done well. Presumably, you
will use the results of this experiment in a subsequent experiment. To achieve
as much accuracy as possible, you will titrate three samples of KHP with the
NaOH solution. The average molarity will be considered the molarity of your
NaOH solution.
Titration Notes
It will take some time to become good at titration. Here are some notes on
carrying out a titration that may help make mastering this skill less frustrating.
✏ Before setting up a buret, make sure the stopcock works and that liquid drains
easily through the tip. There is no sense in spending time cleaning and setting
up a buret that does not work well.
✏ When cleaning a buret, be sure to drain some of the wash through the tip. You
want to be sure every surface along the entire length of the buret is washed.
✏ Use an appropriate background for the flask so that you can easily see faint
color changes. It is usually best to place a white background underneath and
behind the flask.
27.2. Safety Considerations 177
✏ If you are unsure whether you are at an end point, go ahead and record the
current buret level and then add another drop (or fractional drop). If the color
change is too much, you were likely at the end point before the added drop.
Fortunately, you just recorded that value.
✏ Be sure there is not a drop of titrant hanging from the tip of the buret when
you make a buret reading. That drop has already left the buret, and the buret
reading will reflect that. You need to make sure the drop is in the flask.
Goggles
As with all laboratory experiments, you are expected to wear your goggles at all
times while in the lab. Failure to do so may result in expulsion from the lab.
Waste Disposal
All waste in this lab can be put down the drain with plenty of water. Since the
product of the titration is just salt and water, this is considered safe.
Broken Glass
Do not work with any broken glassware. Dispose of broken glassware in the bins
labeled “broken glass” as shown in Figure 27.1. Do not use the normal waste
baskets for broken glass.
Figure 27.1
Broken glass container.
27.3 Experimental Procedure
Record NaOH Unknown Number
Record the unknown number on your bottle of sodium hydroxide before pro-
ceeding with anything else in this project.
178 Standardization of a Sodium Hydroxide Solution
Prepare Buret
1. Obtain Buret: Obtain a buret and buret clamp from the appropriate labora-
tory locations. Attach the buret clamp to a ring stand.
2. Prepare Buret: Empty the water out of the buret and rinse three times with
5 to 10 mL portions of the sodium hydroxide solution you will use in the
titration. Some of the rinse should be drained through the tip to make sure it
is clean.
3. Fill Buret: Using a clean and dry funnel, fill the buret with the NaOH solution
and drain sufficient solution from the tip to bring the meniscus slightly below
the top graduation. Remove the funnel from the buret.
4. Check Buret: Check for bubbles in the tip, clearing them if they are there
by draining more sodium hydroxide from the tip. If you are unsuccessful in
clearing any bubbles, see your instructor.
⌘ Burets can be read to two decimal 5. Read Buret: After allowing about a minute for complete drainage from the
places. Always record buret readings
to two decimal places. walls above the meniscus, read and record the position of the meniscus to the
nearest 0.01 mL.
⌘ This estimate will help you get to 1. Estimate Volume of NaOH Needed: Assuming that the sodium hydroxide
the endpoint more quickly. solution is approximately 0.15 M in NaOH, estimate the number of milliliters
of NaOH needed to titrate the KHP sample.
2. Titrate KHP Sample: Add base to the potassium acid phthalate sample in 1
to 2 mL aliquots. Swirl the flask at the same time to make sure everything
⌘ To detect the lightest shade of pink is well mixed. Do this until the pink color begins to linger for a longer time.
possible, place a sheet of blank white
paper under the flask as a background. You will know when you are close to the endpoint when you approach the
estimate you made in the previous step.
3. Approach Endpoint Carefully: As the pink color lingers longer, rinse the
sides of the flask with a little distilled water from your wash bottle to wash
down any splashed solution. As the end point is approached, add the titrant
27.4. Before Exiting Lab 179
one drop at a time with thorough swirling of the flask to obtain complete
mixing between additions.
4. Reach The Endpoint: Terminate the titration at the first perceptible ap- ⌘ The pink coloration will fade as
CO2 from the air is absorbed by the
pearance of a pink coloration throughout the solution that persists for 20-30 solution. You might want to think about
why this is.
seconds. Read and record the position of the meniscus at the end of the
titration.
6. Titrate Two More Samples: Prepare two more KHP samples and titrate
both of them in the same way. Do not waste time weighing out exactly the ⌘ If you screw up one of your
titrations, you will have to perform yet
same amount of KHP. You may need to adjust the amount of KHP used so another to make sure you walk away
from lab with three useable titrations.
you don’t use too much or too little NaOH solution (20-30 mL is a good
amount).
Clean Buret
1. Drain and Rinse Buret: When you are finished with the equipment, drain
the buret, rinse it once with 1 M HCl and then three times with DI water.
2. Fill Buret With Water and Store: Fill it with DI water, place a cork in the
top and return it to the drawer from which you obtained it.
Dispose of Waste
1. Pour All Waste Down Drain: You can pour all waste down the drain with
plenty of water.
2 Draw a line at the end of your experimental work for the day. Sign your
notebook at the line.
180 Standardization of a Sodium Hydroxide Solution
2 Have your instructor sign your lab notebook before you leave the lab. This
helps verify where you stopped lab work for the week.
1. Calculate the molarity of the NaOH for each titration from the known weight
of potassium acid phthalate and the measured volume of NaOH solution from
each titration.
3. Calculate the standard deviation of the molarity of your NaOH solution. You
may use a spreadsheet to compute the standard deviation, but make sure all
work is shown and all columns are well labeled.
Chapter 28
Analysis of Vinegar by Titration
28.1 Introduction
Chemists are traditionally good at analysis and synthesis. This project is about
the former skill: analysis. More specifically, in this project you will determine
the mass percent acetic acid in vinegar by titration analysis. Such analyses are
common in chemical industry. In many circumstances, commercial products are
required by law to have a specific composition. In such cases, accurate analysis
is required.
The analysis in this laboratory experiment is analogous to procedures per-
formed in virtually all labs, be they research labs, industrial quality control labs,
or hospital labs. The quantitative skills acquired in this type of experiment are
invaluable in virtually any type of laboratory.
Acetic Acid
181
182 Analysis of Vinegar by Titration
In This Experiment
In this experiment, you will take on the role of an analytical chemist to determine
the mass percent acetic acid in a commercial sample of vinegar. You will do
this by titration of a commercial vinegar sample with a standardized solution
of sodium hydroxide. Phenolphthalein will be used as the indicator since its
endpoint is very near the equivalence point for the reaction of acetic acid and
sodium hydroxide.
The titration reaction that is central to this experiment is
CH3 COOH.aq/ C OH .aq/ ! CH3 COO .aq/ C H2 O.`/ (28.1)
You will prepare samples of commercial vinegar with an unknown number of
moles of acetic acid. You will then add sodium hydroxide solution of known
concentration until the endpoint is reached. At that point you will know that
the moles of hydroxide added equals the moles of acetic acid originally present
in the sample. From there you should be able to calculate the concentration of
acetic acid in the vinegar by dividing the moles acetic acid by the volume of
solution originally titrated.
To find the mass percent acetic acid in the vinegar, you will need to convert
the molarity unit ( moles acetic acid mass acetic acid
liters vinegar ) to the unit mass vinegar solution and multiply by
100. To accomplish this you will need to know the density of vinegar so that you
can convert volume of solution to grams of solution. Thus, the first thing you
will do in this experiment is determine the density of your commercial vinegar
sample.
Titration Notes
It will take some time to become good at titration. Here are some notes on
carrying out a titration that may help make mastering this skill less frustrating.
✏ Before setting up a buret, make sure the stopcock works and that liquid drains
easily through the tip. There is no sense in spending time cleaning and setting
up a buret that does not work well.
✏ When cleaning a buret, be sure to drain some of the wash through the tip. You
want to be sure every surface along the entire length of the buret is washed.
✏ Use an appropriate background for the flask so that you can easily see faint
color changes. It is usually best to place a white background underneath and
behind the flask.
✏ If you are unsure whether you are at an end point, go ahead and record the
current buret level and then add another drop (or fractional drop). If the color
change is too much, you were likely at the end point before the added drop.
Fortunately, you just recorded that value.
✏ Be sure there is not a drop of titrant hanging from the tip of the buret when
you make a buret reading. That drop has already left the buret, and the buret
reading will reflect that. You need to make sure the drop is in the flask.
28.2. Safety Considerations 183
Goggles
As with all laboratory experiments, you are expected to wear your goggles at all
times while in the lab. Failure to do so may result in expulsion from the lab.
Waste Disposal
All waste in this lab can be put down the drain with plenty of water. Since the
product of the titration is just salt and water, this is considered safe. Vinegar
is something people at home throw down the drain every day. It is thus safe to
throw down the drain here.
Broken Glass
Do not work with any broken glassware. Dispose of broken glassware in the bins
labeled “broken glass” as shown in Figure 28.1. Do not use the normal waste
baskets for broken glass.
Figure 28.1
28.3 Experimental Procedure Broken glass container.
When you come to lab you should find a commercial vinegar sample at your
desk. If you do not, see your instructor.
4. Weigh the Weighing Bottle Plus Vinegar: Take the weighing bottle plus
vinegar back to the same top loading balance and weigh again.
2. Obtain Buret: Obtain a buret and buret clamp from the appropriate labora-
tory locations. Attach the buret clamp to a ring stand.
3. Prepare Buret: Empty the water out of the buret and rinse three times with 5
to 10 milliliter portions of your standardized sodium hydroxide solution you
will use in the titration. Be sure to drain some of the rinse through the tip.
4. Fill Buret: Using a clean and dry funnel, fill the buret with the standardized
NaOH solution and drain sufficient solution from the tip to bring the meniscus
slightly below the top graduation. Remove the funnel from the buret.
5. Check Buret: Check for bubbles in the tip, clearing them if they are there
by draining more sodium hydroxide from the tip. If you are unsuccessful in
clearing any bubbles, see your instructor.
⌘ Burets can be read to two decimal 6. Read Buret: After allowing about a minute for complete drainage from the
places. Always record buret readings
to two decimal places. walls above the meniscus, read and record the position of the meniscus to the
nearest 0.01 mL.
⌘ This estimate will help you get to 2. Estimate Volume of NaOH Needed: Assuming that the vinegar is about 5%
the endpoint more quickly and
accurately. acetic acid by mass, estimate the number of milliliters of your standardized
NaOH needed to titrate the vinegar sample.
⌘ To detect the lightest shade of pink 3. Titrate Vinegar Sample: Add standardized base to the vinegar sample in 1
possible, place a sheet of blank white
paper under the flask as a background. to 2 mL aliquots. Swirl the flask at the same time to make sure everything
is well mixed. Do this until the pink color begins to linger for a longer time.
You will know when you are close to the endpoint when you approach the
estimate you made in the previous step.
28.4. Before Exiting Lab 185
4. Approach Endpoint Carefully: As the pink color lingers longer, rinse the
sides of the flask with a little distilled water from your wash bottle to wash
down any splashed solution. As the endpoint is approached, add the titrant
one drop at a time with thorough swirling of the flask to obtain complete
mixing between additions.
5. Reach The Endpoint: Terminate the titration at the first perceptible ap- ⌘ The pink coloration will fade as
CO2 from the air is absorbed by the
pearance of a pink coloration throughout the solution that persists for 20-30 solution. You might want to think about
why this is.
seconds. Read and record the position of the meniscus at the end of the
titration.
7. Titrate Four More Samples: Prepare four more vinegar samples and titrate
each of them in the same way. ⌘ If you screw up one of your
titrations, you will have to perform yet
another to make sure you walk away
from lab with five usable titrations.
Clean Buret
1. Drain and Rinse Buret: When you are finished with the equipment, drain
the buret, rinse it once with 1 M HCl and then three times with DI water.
2. Fill Buret With Water and Store: Fill it with DI water, place a cork in the
top and return it to the drawer from which you obtained it.
Dispose of Waste
1. Pour All Waste Down Drain: You can pour all waste down the drain with
plenty of water.
4. Draw a line at the end of your experimental work for the day. Sign your
notebook at the line.
5. Have your instructor sign your lab notebook before you leave the lab. This
helps verify where you stopped lab work for the week.
186 Analysis of Vinegar by Titration
1. Calculate the acetic acid molarity for each of the samples you titrated.
3. Compute the standard deviation of the average acetic acid molarity for your
samples.
⌘ You can find the class data for 4. Compute the average vinegar density from all the data obtained by the lab
vinegar density on the course web site.
section. You should use a spreadsheet to compute the average.
5. Compute the average vinegar density’s standard deviation from all the data
obtain by the lab section. You should use a spreadsheet to compute the
standard deviation, but do not use any of the program’s built-in statistical
functions.
6. Using your average acetic acid molarity and the class’s average vinegar
density, compute the mass percent acetic acid in vinegar.
Chapter 29
Semimicro Qualitative Analysis of Known Anions
29.1 Introduction
Qualitative analysis is a type of analysis that seeks to identify whether a particular
substance is present, not to quantity the amount present. As long as the substance
is present above a certain threshold concentration, qualitative analysis only
provides a test that signifies whether the species is present or not. Semimicro
qualitative analysis is a type of qualitative analysis that is carried out on relatively
small quantities of material. ⌘ In this context, small means a few
milligrams of solid or a few drops of
The detection of anions by semimicro qualitative analysis involves elimi- solution.
nation tests to indicate which anions are not present followed by identification
tests to verify which of the remaining possibilities are present. These tests rely
heavily on acid-base reactions, oxidation-reduction reactions and precipitation
reactions.
This experiment is concerned with the identification of anions by semimicro
qualitative analysis. Small-scale qualitative tests like these are important in many
fields such as as forensics, medicine, geology, and genetics. After a discussion
of the chemistry behind a selected set of elimination and identification tests, the
actual laboratory experiment is presented.
In This Experiment
In this experiment you will determine how each of the ions CO23 , NO2 , NO3 ,
PO34 , S2 , SO24 , Cl , Br , and I behaves under a series of elimination and
identification tests. This experience will give you the needed background for
identifying the anion contained in a solution of unknown identity.
Throughout this experiment, test only one ion at a time. The purpose is to
determine the elimination and identification test results for each ion individually.
Do not mix ion solutions together.
It may be helpful if you record your results in tabular form as shown below.
Make one table for elimination tests and a separate (but similar) table for iden-
tification tests. Make careful observations since you will need these results to
identify the anion in a solution of unknown identity.
187
188 Semimicro Qualitative Analysis of Known Anions
This is a test for strongly basic anions such as S2 , PO34 , and CO23 . A positive
ET-1 means that a sample contains CO23 , S2 , or PO34 . A negative ET-1 test
eliminates these ions as possible constituents of the sample.
Why It Works
This test works because several anions for which you will test are relatively
strong bases in water. For example, the carbonate ion reacts with water to an
appreciable degree to form the bicarbonate ion and the hydroxide ion as in
The Procedure
Place a few drops of the solution to be tested in a test tube. Dip a clean stirring
rod into the solution, withdraw it, and touch it to a short length of wide-range in-
dicator paper. Determine the pH by comparing the color with the color standards
on the indicator paper dispenser.
The Interpretation
This is a test for volatile or unstable acids such as CO23 , S2 , and NO2 . A
positive ET-2 means that a sample contains CO23 , S2 , or NO2 . A negative
ET-2 eliminates these ions as possible constituents of the sample.
Why It Works
Several anions for which you will be testing react relatively vigorously with
strong acid to yield compounds which may or may not decompose. The result in
each case is a gas.
The Procedure
Put sufficient solid sample containing the anion of interest in a dry test tube to
make a layer about 1 mm deep (about the thickness of a wooden splint). Add
enough 6M H2 SO4 so that the solid is covered and there is enough solution
29.2. About The Elimination Tests 189
above it that you can watch for bubbles. Mix by flicking the bottom of the tube
with your forefinger. Watch for the evolution of gas. Note the odor by cautiously
wafting some of the gas to your nose. Do this under a hood and use a wafting
motion to smell the gases since some of them are obnoxious and toxic.
The Interpretation
If carbonate is present, the gas will be colorless and odorless CO2 . If nitrite is
present, colorless NO gas will be evolved, which will turn into red-brown NO2
gas in air. This gas has a sharp odor, and it is toxic. If sulfide is present, colorless
H2 S gas will be released. This gas has a vile odor.
Why It Works
Some of the ions you will test for are strong reducing agents. These ions will
reduce the Fe3C , in Fe(CN)36 to Fe2C , producing Fe(CN)46 . The Fe3C of
FeCl3 will then combine with Fe(CN)46 to form FeFe(CN)6 , in which one ion
is Fe2C and one is Fe3C . The combination of this complex ion with KC yields
KFeFe(CN)6.s/ , also known as Prussian blue due to its deep blue color.
The Procedure
Put a few drops of the solution to be tested into a depression in a porcelain spot
plate and acidify with HCl. To a separate depression add one small crystal of
K3 Fe(CN)6 and a few drops of water. Now add a drop of this solution and a
drop of FeCl3 to the anion solution.
The Interpretation
Only strong reducing agents will give a true positive Prussian blue test. Weaker
reducing agents, such as Br , may yield a color change, to a medium green, but
generally will not produce a true positive Prussian blue test.
This is a test for strong oxidizing agents such as NO2 and NO3 . A positive ET-4
means that a sample contains NO2 or NO3 . A negative ET-4 eliminates these
ions as possible constituents of the sample.
190 Semimicro Qualitative Analysis of Known Anions
Why It Works
The Procedure
To 5 drops of the anion solution to be tested, add 6 M H2 SO4 dropwise until the
solution is acidic. Now add 5 drops of freshly prepared 0.1 M FeSO4 . Carefully
observe the result, paying particular attention to whether the solution turns
brown.
If the solution does not turn brown, hold the test tube in a slanted position
and carefully (and slowly) add 5 to 10 drops of 18 M H2 SO4 , allowing it to
run down the inside of the tube. It should form a layer below the other solution.
⌘ If the two solutions are mixed Carefully straighten the tube to an upright position and set it in a test tube rack
together by careless addition of the 18
M H2 SO4 or by shaking, the test will or a beaker.
not work.
The Interpretation
If the solution turns brown after addition of FeSO4 , NO2 is present. If the
⌘ The brown ring is due to the solution does not turn brown after addition of FeSO4 but a brown ring does
formation of Fe(NO)2C .
form between the layers after addition of the concentrated sulfuric acid, NO3 is
present.
This is a test for anions that form insoluble silver salts, such as Cl , Br , I ,
and S2 . A positive ET-5 means that a sample contains Cl , Br , I , or S2 . A
negative ET-5 means that these ions are not in the sample.
Why It Works
The Procedure
Place a few drops of the solution under study into a test tube. Add a drop of silver
nitrate solution. If addition of a second drop produces more precipitate, continue
the addition of silver nitrate until precipitation appears to be complete. After
each addition, mix well by flicking the bottom of the tube with your forefinger.
Now add 6 M HNO3 to the test tube a drop at a time, mixing well after each
drop is added, until the solution is acidic to litmus. Finally, add a few drops of
acid in excess.
29.2. About The Elimination Tests 191
The Interpretation
This is a test for anions that form insoluble calcium salts, such as PO34 . A
positive ET-6 means that a sample contains PO34 . A negative ET-6 means that
the sample does not contain phosphate.
Why It Works
Many calcium salts are insoluble in water. Since precipitates are easy to identify
in solution, this is a simple and straightforward elimination test for ions that
form insoluble compounds with calcium.
The Procedure
Place a few drops of the solution to be analyzed into a test tube. make the
solution basic to litmus with 15 M NH3 to prevent formation of HPO24 , H2 PO4 ,
or H3 PO4 . Add a few drops of Ca(NO3 )2 solution.
The Interpretation
If phosphate is present and the solution is basic, calcium phosphate will precipi-
tate when a few drops of Ca(NO3 )2 are added.
This is a test for anions that form insoluble barium salts, such as SO24 . A positive
ET-7 test means that a sample contains SO24 . A negative ET-7 eliminates this
ion as a possible component of the sample.
Why It Works
Many barium salts are insoluble in water. Since precipitates are easy to identify
in solution, this is a simple and straightforward elimination test for ions that
form insoluble compounds with barium.
The Procedure
Add a few drops of the solution under test to a test tube. Add barium chloride
solution drop by drop until precipitation is complete. Centrifuge and draw off the
192 Semimicro Qualitative Analysis of Known Anions
solution above the precipitate and discard it. Treat the precipitate with several
drops of 6 M HCl.
The Interpretation
A white precipitate that is also insoluble in acid indicates the presence of sulfate
in the original sample.
This is a test for the identification of chloride ion, Cl . A positive IT-1 confirms
the presence of chloride ion so long as you have previously confirmed that there
are no other halide ions present.
Why It Works
The ammonia-silver complex ion that forms can be converted back to silver
chloride precipitate by the addition of acid according to the equation
Ag.NH3 /C C C
2 .aq/ C Cl .aq/ C 2H .aq/ ! AgCl.s/ C 2NH4 .aq/. (29.3)
The Procedure
⌘ A hazy opalescence that does not Acidify a few drops of the solution under test with 6 M nitric acid and add
centrifuge down to a solid is caused by
a trace of chloride and should not be
a drop of AgNO3 solution. A white precipitate may be AgCl. To confirm,
reported. centrifuge and discard the supernatant liquid. Add a few drops of 6 M NH3
⌘ Do not mistake pale yellow AgBr or to the precipitate. If it dissolves, acidify the solution with 6 M HNO3 . The
yellow AgI for AgCl. The absence of precipitate should re-form if the original precipitate was AgCl. This will confirm
Br or I must be proved before the
test for Cl can be conclusive. the presence of Cl .
29.3. About The Identification Tests 193
This is an identification test for bromide ion, Br . A positive IT-2 confirms the
presence of bromide ion in solution.
How It Works
Free bromine is more soluble in petroleum ether than in water and gives an
orange to brownish red color in that solvent.
The Procedure
Acidify a few drops of the solution under test with 6 M HNO3 and add 4 drops
of nitric acid in excess. Add several drops of petroleum ether. Add just enough
to clearly see two layers. Now add 0.02 M KMnO4 drop by drop, shaking after ⌘ Adding too much petroleum ether
will make the color more difficult to see
each addition, until an orange bead is obtained or the water layer remains pink if present.
for at least a minute.
The Interpretation
The presence of bromide is indicated by the orange upper layer due to the
formation of Br2 .
This test is an identification test for iodide ion, I . A positive IT-3 indicates the
presence of iodine ion in solution.
How It Works
HNO2 C I ! NO C I2 . (29.5)
Molecular iodine is much more soluble in petroleum ether than in water and
gives a violet solution in this nonpolar solvent.
194 Semimicro Qualitative Analysis of Known Anions
The Procedure
Acidify a few drops of the solution under test with 6 M H2 SO4 . Add a few
crystals of NaNO2 and several drops of petroleum ether. Shake vigorously to
extract the iodine.
The Interpretation
The presence of iodide is indicated by a violet upper layer due to the formation
of I2 .
This test is an identification test for sulfide ion, S2 . A positive IT-4 indicates
the presence of sulfide ion in solution. This test is the same as ET-2.
How It Works
See ET-2.
The Procedure
See ET-2.
The Interpretation
See ET-2
This test is an identification test for sulfate ion, SO24 . A positive IT-5 indicates
the presence of sulfate in solution.
How It Works
Of all the anions that form insoluble barium salts, only sulfate ion is too weakly
basic to react appreciably with acid, and thus only BaSO4 will precipitate in
strongly acidic solutions. If such a precipitate was obtained in ET-7, no other
test for sulfate is required.
The Procedure
See ET-7
29.3. About The Identification Tests 195
The Interpretation
See ET-7
This is an identification test for nitrite ion, NO2 . A positive IT-6 indicates the
presence of nitrite in solution so long as you know that there is no sulfate in the
solution.
How It Works
In acidic solution, nitrates react with sulfamic acid to give bubbles of nitrogen
and sulfate ion as described in the equation
HC
NO2 C NH2 SO3 ! N2 .g/ C SO24 C H2 O. (29.6)
The Procedure
First you need to ensure that no sulfate is in the solution before you test for
nitrite. To a few drops of the solution under test, add BaCl2 solution. If a ⌘ If you add BaCl2 and no precipitate
results, that just means you have no
BaSO4 precipitate forms, add more BaCl2 until precipitation is complete. Then contaminating sulfate present, so
continue with the test.
centrifuge the solution and transfer the solution to a new test tube.
Since your solution now contains Ba2C , add a few crystals of sulfamic acid
to the solution, and flick the bottom of the tube with your forefinger to cause
vigorous evolution of gas bubbles.
The Interpretation
The formation of both white precipitate (BaSO4 ) and gas bubbles (N2 ) indicates
the presence of nitrite.
This is an identification test for nitrate ion, NO3 . A positive IT-7 indicates the
presence of nitrate in solution.
How It Works
Ammonia gas may be detected by its action on moist red litmus because the
ammonia gas forms hydroxide when exposed to water:
The Procedure
Mix several drops of the solution under test with an equal volume of 6 M NaOH.
With a pipet, transfer this mixture to a dry test tube in such a way as not to
wet the upper walls of the tube with the basic solution. After withdrawing the
pipet, inspect the upper walls of the tube to make sure this critical requirement is
satisfied. Have a strip of red litmus ready. Add a piece of aluminum wire to the
test tube. Warm briefly in a water bath to induce a vigorous reaction. Withdraw
the tube and insert a piece of red litmus, first bending the strip into a V and
moistening the fold. The dry upper ends will support the litmus so that it does
not fall in. Allow the tube to stand for several minutes.
The Interpretation
The presence of nitrate is indicated if the bottom tip of the litmus turns uniformly
blue, indicating NH3 was formed.
Description
This is an identification test for phosphate ion, PO34 . A positive IT-8 indicates
the presence of phosphate ion in solution.
How It Works
The Procedure
Acidify a few drops of the solution under test with 6 M HNO3 , and add 2 drops
of acid in excess. Warm the solution for a minute in a hot water bath; it should
reach a temperature of 40-50ı (not too hot to hold) for fast reaction in the next
step.
Withdraw the tube from the water bath, and add 2 drops of ammonium
molybdate reagent [(NH4 )2 MoO4 ]. Allow to stand for 5 minutes.
29.4. Safety Considerations 197
The Interpretation
This test is an identification test for carbonate ion, CO23 . A positive IT-9
indicates the presence of carbonate ion in solution.
How It Works
This is where ET-2 ends. However, if the gas is absorbed in barium hydroxide
solution, a white precipitate of BaCO3 is obtained according to the equation
The Procedure
The Interpretation
Goggles
As with all laboratory experiments, you are expected to wear your goggles at all
times while in the lab. Failure to do so may result in expulsion from the lab.
Waste Disposal
All waste in this lab must be poured into the appropriate waste containers in the
hoods located in the back of the laboratory. No waste can be poured down the
drain.
Broken Glass
Do not work with any broken glassware. Dispose of broken glassware in the bins
labeled “broken glass” as shown in Figure 29.1. Do not use the normal waste
baskets for broken glass.
Figure 29.1
Broken glass container. 29.5 Experimental Procedure
Some of the tests are carried out directly on solid samples, others on solutions.
Solid samples and solutions are available on your lab bench. Use 4 inch test
tubes whenever test tubes are called for in the procedure.
Elimination Tests
Elimination Test 1 (ET-1)
⌘ Carefully record all observations in 1. Place Solution of S2 in Test Tube: Place a few drops of a solution contain-
your laboratory notebook.
ing S2 in a test tube.
2. Test pH of S2 Solutions: Dip a clean stirring rod into the solution, withdraw
it, and touch it to a piece of wide range indicator paper. Determine the pH by
comparing the color of the indicator paper to the color chart.
3. Repeat for PO34 : Repeat these steps for ET-1 on a solution containing the
phosphate anion.
4. Repeat for CO23 : Repeat these steps for ET-1 on a solution containing the
carbonate anion.
4. Observe Tube and Note Odor: Watch for the evolution of gas. Note the
odor by cautiously wafting some of the gas to your nose. Do this under a
hood and use a wafting motion to smell the gases since some of them are
obnoxious and toxic.
5. Repeat for S2 : Repeat these steps for ET-2 on a solid containing the sulfide
ion.
6. Repeat for NO2 : Repeat these steps for ET-2 on a solid sample containing
the nitrite ion.
1. Place Solution of S2 on Spot Plate: Place a few drops of a solution con- ⌘ Carefully record all observations in
your laboratory notebook.
taining S2 into a depression in a porcelain spot plate.
2. Acidify with HCl: Add a drop of concentrated HCl to the depression con-
taining the sulfide ion solution.
5. Add FeCl3 Solution to S2 Spot: Add one drop of FeCl3 solution to the
depression containing the sulfide ion solution.
6. Repeat for NO2 : Repeat these steps for ET-3 on a solution containing the
nitrite ion.
7. Repeat for I : Repeat these steps for ET-3 on a solution containing the
iodide ion.
1. Add NO2 to Test Tube: Add 5 drops of a solution containing NO2 to a test ⌘ Carefully record all observations in
your laboratory notebook.
tube.
2. Make Acidic with Sulfuric Acid: Add 6 M H2 SO4 dropwise to the test tube
until the solution is acidic.
3. Add FeSO4 to the Test Tube: Add 5 drops of freshly prepared 0.1 M
FeSO4 . Carefully observe the result, paying particular attention to whether
the solution turns brown.
4. Repeat for NO3 : Repeat the above steps for ET-4 for a solution containing
nitrate instead of nitrite. Then continue with the remaining steps for the
nitrate solution.
200 Semimicro Qualitative Analysis of Known Anions
5. Add 18 M Sulfuric Acid: Hold the test tube in a slanted position and care-
fully (and slowly) add 5 to 10 drops of 18 M H2 SO4 , allowing it to run down
⌘ If the two solutions are mixed the inside of the tube. It should form a layer below the other solution.
together by careless addition of the 18
M H2 SO4 or by shaking, the test will
not work. 6. Observe Tube: Carefully straighten the tube to an upright position and set it
in a test tube rack or a beaker. Observe the region between the two layers.
2. Add Silver Nitrate: Add a drop of silver nitrate solution to the test tube.
4. Add Nitric Acid: Add 6 M HNO3 to the test tube a drop at a time, mixing
well after each drop is added, until the solution is acidic to litmus. Finally,
add a few drops of acid in excess.
5. Repeat for Br : Repeat these steps for ET-5 on a sample containing bromide
ion.
6. Repeat for I : Repeat these steps for ET-5 on a sample containing iodide
ion.
7. Repeat for S2 : Repeat these steps for ET-5 on a sample containing sulfide
ion.
2. Add Barium Chloride: Add barium chloride solution drop by drop until
precipitation is complete.
3. Centrifuge Test Tube: Centrifuge and draw off the solution above the pre-
cipitate and discard it.
29.5. Experimental Procedure 201
Identification Tests
Identification Test 1 (IT-1) ⌘ Test for Cl
1. Add Chloride Solution To Test Tube: Add a few drops of a chloride solu- ⌘ Carefully record all observations in
your laboratory notebook.
tion to a test tube.
2. Add Nitric Acid: Acidify the contents of the test tube by adding 6 M nitric
acid.
3. Add Silver Nitrate: Add a drop of AgNO3 solution to the test tube. ⌘ A white precipitate at this stage
may be AgCl. The remainder of the
steps are to confirm this.
4. Centrifuge Test Tube: Centrifuge the test tube and contents. Discard the
supernatant liquid.
2. Add Nitric Acid: Acidify the bromide solution with 6 M HNO3 , and then
add 4 drops of nitric acid in excess.
3. Add Petroleum Ether: Add several drops of petroleum ether. Add just
enough to clearly see two layers. ⌘ Adding too much petroleum ether
will make the color more difficult to see
if present.
4. Add Potassium Permanganate: Add 0.02 M KMnO4 drop by drop, shaking
after each addition.
⌘ Test for I
Identification Test 3 (IT-3) ⌘ Carefully record all observations in
your laboratory notebook.
1. Add Iodide Solution to Test Tube: Add a few drops of a solution containing
iodide ions to a test tube.
3. Add Sodium Nitrite and Petroleum Ether: Add a few crystals of NaNO2
and several drops of petroleum ether. Shake vigorously to extract the iodine.
3. Add Sulfamic Acid: Add a few crystals of sulfamic acid to the solution, and
flick the bottom of the tube with your forefinger to cause vigorous evolution
of gas bubbles.
2. Obtain Red Litmus Paper: Obtain a piece of red litmus paper from your
drawer. Fold it in half end to end to make a V shape.
3. Obtain Two Test Tubes: Obtain two clean and dry test tubes.
4. Add Nitrate Solution to Test Tube: Add a few drops of a solution containing
nitrate ion to one test tube.
6. Transfer Mixture to New Test Tube: With a pipet, transfer this mixture to
the other dry test tube in such a way as not to wet the upper walls of the tube
with the basic solution. After withdrawing the pipet, inspect the upper walls
of the tube to make sure this critical requirement is satisfied.
7. Add Aluminum Wire: Add a piece of aluminum wire to the test tube con-
taining the solution.
8. Warm Test Tube: Warm the test tube briefly in a water bath to induce a
vigorous reaction.
9. Add Litmus Paper to Test Tube: Withdraw the test tube from the water
bath. Moisten the bottom of the V in the litmus paper with DI water and
then insert the piece of red litmus into the test tube with the bottom of the V
pointing down into the tube. The dry upper ends will support the litmus so
that it does not fall in. Allow the tube to stand for several minutes.
29.6. Before Exiting Lab 203
1. Add Phosphate Solution to Test Tube: Add a few drops of a solution ⌘ Carefully record all observations in
your laboratory notebook.
containing phosphate to a test tube.
2. Add Nitric Acid: Acidify the phosphate solution with 6 M HNO3 . Add 2
drops of acid in excess.
3. Heat Test Tube in Water Bath: Warm the solution for a minute in a hot
water bath. It should reach a temperature of 40-50ı (not too hot to hold) for
fast reaction in the next step.
4. Add Ammonium Molybdophosphate: Withdraw the tube from the water
bath, and add 2 drops of ammonium molybdate reagent [(NH4 )2 MoO4 ].
Allow to stand for 5 minutes.
1. Place Barium Hydroxide Solution in Test Tube: Place about 10 drops of ⌘ Carefully record all observations in
your laboratory notebook.
barium hydroxide solution into a test tube and suck most of it up into a
medicine dropper (not a Pasteur pipet). Leave the medicine dropper in the
test tube until needed.
2. Add Carbonate Solid to Test Tube: Add 20-30 mg of a solid containing
the carbonate ion to a different test tube.
3. Add Sulfuric Acid: Add 1 or 2 drops of 6 M H2 SO4 to the test tube contain-
ing the carbonate solid.
4. Bring Medicine Dropper To Test Tube: After adding the acid, quickly
insert the dropper into the mouth of the test tube with carbonate. Do this
without squeezing the bulb. The drop is not to be added to the solution. Look
for cloudiness in the drop at the end of the dropper.
30.1 Introduction
In this experiment you will identify the cations present in a solution of known
identity. This experiment utilizes the principles of semimicro qualitative analysis.
The separation of AgC from Cu2C , Al3C , and Fe3C is based on the fact that
while most chlorides are soluble, AgCl is insoluble, so the formation of AgCl is
used to separate the AgC from the remaining cations.
While AgCl is insoluble, AgC forms the complex ion Ag(NH3 )C 2 in the presence
of excess NH3 . This shifts the equilibrium away from the formation of AgCl to
the more stable complex ion, thus dissolving the precipitate. Addition of more
HCl protonates the NH3 causing equilibrium to shift away from the complex ion,
allowing the AgCl precipitate to reform.
Dissolution of the AgCl precipitate by formation of the Ag(NH3 )C2 complex
ion followed by reformation of the AgCl precipitate confirms the presence of
AgC .
Separation of Copper(II)
The separation of Cu2C from Al3C and Fe3C is based on the fact that in the
presence of NH3 , Cu2C forms the complex ion Cu(NH3 )2C 4 while Al
3C and
205
206 Semimicro Qualitative Analysis of Known Cations
Confirmation of Copper(II)
The deep blue of the Cu(NH3 )2C 4 complex ion is strongly indicative of the
presence of Cu2C . The addition of HCl causes the protonation of the NH3 ,
resulting in the dissociation of the Cu(NH3 )2C
4 complex ion and the subsequent
formation of CuCl24 . This complex ion readily dissociates in the presence of
Fe(CN)46 as Cu2C reacts to form Cu2 Fe(CN)6 , a blood red precipitate. This
precipitate confirms the presence of Cu2C . Formation of the Cu2 Fe(CN)6 , a
deep red precipitate, confirms the presence of Cu2C .
Separation of Aluminum(III)
The basis for the separation of Al3C from Fe3C is that Fe(OH)3 is a basic
hydroxide (reacts with acid, but not base) while Al(OH)3 is an amphoteric
hydroxide (reacts with acid or base). In the presence of excess hydroxide,
Fe(OH)3 does not react, but Al(OH)3 reacts to form the complex ion Al(OH)4 .
So the formation of the complex ion Al(OH)4 puts the Al3C in a soluble form,
allowing it to be separated from the Fe(OH)3 precipitate.
Confirmation of Iron(III)
Confirmation of Aluminum(III)
The addition of HCl to Al(OH)4 will initially cause one hydroxide of the col-
orless complex ion to react, forming water and the white precipitate Al(OH)3 .
The addition of more HCl will cause the remaining hydroxide to react, freeing
Al3C from the precipitate. Note that if sufficient HCl is added initially, all the
hydroxides can react, allowing the formation of Al3C from Al(OH)4 without the
intermediate formation of Al(OH)3 . The free Al3C can then react with PO34 to
form AlPO4 , a white precipitate. This confirms the presence of Al3C . Note that
if the solution is strongly acidic, the PO34 can be protonated (forming HPO24 ,
H2 PO4 , and H3 PO4 ), thus preventing it from reacting with the Al3C . In such
a case, the addition of excess PO34 can still result in the formation of AlPO4 .
Formation of a white AlPO4 precipitate confirms the presence of Al3C .
30.2. Safety Considerations 207
Goggles
As with all laboratory experiments, you are expected to wear your goggles at all
times while in the lab. Failure to do so may result in expulsion from the lab.
Waste Disposal
All waste in this lab must be poured into the appropriate waste containers in the
hoods located in the back of the laboratory. No waste can be poured down the
drain.
Broken Glass
Do not work with any broken glassware. Dispose of broken glassware in the bins
labeled “broken glass” as shown in Figure 30.1. Do not use the normal waste
baskets for broken glass.
Figure 30.1
30.3 Experimental Procedure Broken glass container.
The known solution you will be testing contains AgC , Cu2C , Al3C , and Fe3C .
2. Add HCl: Add 4 drops of 6 M HCl. Mix and allow to stand 3 minutes.
5. Wash Precipitate: Wash the precipitate with 10 drops of cold water. Cen-
trifuge and add the wash to the decantate (the decanted solution) from the
previous step.
3. Discard Mixture: After you have performed these tests on the silver precipi-
tate, you may discard the mixture.
4. Wash Precipitate: Wash the precipitate with 10-15 drops of water. Cen-
trifuge the test tube and add the wash to the decantate from the previous
step.
5. Wash Precipitate Again: Wash the precipitate a second time with 10-15
drops of water. Centrifuge and discard this supernatant.
6. Discard Nothing: The precipitate you have collected in this procedure will
be used in further separation tests. The decantate will be used in confirmation
tests for copper(II) ions. Therefore, discard nothing at this stage.
2. Add KSCN: Add 3 drops of 0.2 M KSCN to this solution. ⌘ What observation confirms the
presence of iron(III)?
2. Add Sodium Phosphate: Add about 20 drops of 0.5 M Na3 PO4 to this ⌘ What observation confirms the
presence of aluminum(III) ion?
solution. You may need to add more if the solution was strongly acidic.
2 Draw a line at the end of your experimental work for the day. Sign your
notebook at the line.
2 Have your instructor sign your lab notebook before you leave the lab. This
helps verify where you stopped lab work for the week.
31.1 Introduction
In this experiment you will identify the anion and cation present in a sample
of unknown identity. This lab requires that you already be familiar with the
techniques of semimicro qualitative analysis for anions and cations.
Goggles
As with all laboratory experiments, you are expected to wear your goggles at all
times while in the lab. Failure to do so may result in expulsion from the lab.
Waste Disposal
All waste in this lab must be poured into the appropriate waste containers in the
hoods located in the back of the laboratory. No waste can be poured down the
drain.
Broken Glass
Do not work with any broken glassware. Dispose of broken glassware in the bins
labeled “broken glass” as shown in Figure 31.1. Do not use the normal waste
baskets for broken glass.
Figure 31.1
Broken glass container.
211
212 Semimicro Qualitative Analysis of Unknown Ions
1. Record Anion Unknown Number: At your desk will be a 4-inch test tube
which contains a solid salt sample. Record the number of your anion unknown
in your lab notebook.
Cation Identification
Your unknown solution contains from one to four of the following cations: AgC ,
Cu2C , Al3C , Fe3C . Thus, you may not stop testing once you have found one
ion in solution. You must continue until you have exhausted all possibilities.
1. Record Unknown Number: At your desk will be a 4-inch test tube which
contains a solution of unknown cation(s). Record the number of your cation
unknown in your lab notebook.
3. Carry Out Cation Tests: Carry out the same cation tests that you did while
testing the known ions.
2 Draw a line at the end of your experimental work for the day. Sign your
notebook at the line.
31.5. Post-Lab Assignments 213
2 Have your instructor sign your lab notebook before you leave the lab. This
helps verify where you stopped lab work for the week.
2. State, in brief, your reasoning for your identification of the unknown anion.
3. Clearly indicate in your lab notebook what you think the identity of your
unknown cation is.
4. State, in brief, your reasoning for your identification of the unknown cation.
Chapter 32
Synthesis of Cobalt(III) Coordination Compounds
32.1 Introduction
eg
The bonding between ligands and the metal in coordination compounds is often
discussed in terms of crystal field theory. As ligands approach the metal, the d
orbitals are perturbed, causing all of them to go up in energy. Because of the
differing spatial orientation of the five d orbitals, some go up in energy more t2g
than others. For octahedral complexes, this leads to the energetic splitting pattern
illustrated in Figure 32.1.
The difference in energy between the group of orbitals labeled t2g and Figure 32.1
that labeled eg in Figure 32.1 is called the crystal field splitting energy. It is Splitting pattern expected
given the symbol 0 . The magnitude of 0 depends on the oxidation state for the metal d orbitals in an
and size of the metal as well as the identity of ligand. Some ligands can make octahedral complex ion. The
0 small, and these are called weak field ligands. Some ligands can make three d orbitals lower in en-
0 large, and these are called strong field ligands. The magnitude of 0 can ergy are called t2g orbitals,
be measured spectroscopically, providing an experimental way to determine and the two d orbitals higher
the relative crystal field strength of ligands. This, in turn, can sometimes be in energy are called eg or-
correlated with reactivity of the ligands, making this a particularly important bitals. The energy difference
quantity to determine. between the t2g and eg or-
If several coordination compounds are synthesized with the same metal in bitals is given the symbol
the same oxidation state and with all ligands the same except one, all changes 0
in spectral properties can be attributed to the one ligand that changed. This
makes it possible to spectroscopically distinguish weak field from strong field
ligands. In this project your laboratory section will synthesize two coordination
compounds that differ only by one ligand. You will spectroscopically analyze
these complexes in a future project to determine relative ligand strength.
Coordination compounds of cobalt(III) are relatively stable in water, under-
going ligand exchange with water very slowly. This makes them easier to study
than complexes of other metal ions, such as nickel(II). For instance, Ni.NH3 /2C 6
215
216 Synthesis of Cobalt(III) Coordination Compounds
undergoes nearly instantaneous reaction with water to form Ni.H2 O/2C 6 , making
the ammonia complex ion of nickel(II) difficult to study. Thus, in this project we
will synthesize two coordination compounds of cobalt(III).
The two complex ions your laboratory section will synthesize are shown in
Figure 32.2. For complex ion A, the counter ion is nitrate. For complex ion B,
the counter ion is chloride.
+ 3+
Figure 32.2 NH 3 NH 3
Both coordination com-
H 3N O H 3N NH3
plexes to be synthesized
Co C O Co
possess cobalt in the C3
oxidation state. Complex H 3N O H 3N NH 3
ion A has nitrate as the NH 3 NH 3
counter ion. Complex
ion B has chloride as the
counter ion. A B
The synthesis of complex ion A will be carried out according to the unbal-
anced equation
and the synthesis of complex ion B will be carried out according to the unbal-
anced equation
Goggles
You are expected to wear your goggles at all times while in the lab. Failure to do
so may result in expulsion from the lab.
Waste Disposal
All waste in this lab must be poured into the appropriate waste containers. No
waste can be poured down the drain.
Broken Glass
Do not work with any broken glassware. Dispose of broken glassware in the bins
labeled “broken glass” as shown in Figure 32.3. Do not use the normal waste
baskets for broken glass.
Figure 32.3
32.3 Experimental Procedure Broken glass container.
3. Prepare Chilled Water: Place about 20 mL of DI water into a small beaker. Figure 32.4
Place the beaker in the ice bath. You will need this chilled water later. Complex ion A.
6. Add Ammonia: Remove the beaker from the hot plate and add 10 mL con-
centrated aqueous ammonia to the mixture. Be sure to do this under the fume
hood.
8. Mix Solutions: Add all of the ammonium carbonate solution to the Co(II)
solution with stirring.
⌘ Do not allow the bulb of your 10. Evaporate Solution: Place the 250 mL beaker on the hot plate and set the
thermometer to touch the bottom of the dial to obtain a solution temperature as close to 75ı C as you can without
beaker. Use your split rubber stopper
and a ring stand to suspend your exceeding 75ı C. Never let the solution boil. Keep the beaker on the hot plate
thermometer in the solution.
until the solution volume has been reduced to between 15 mL and 20 mL.
15. Dry Crystals: Dry the crystals by pulling air through them for about 10
minutes.
16. Weigh Collected Product: Weigh the collected product on the filter paper
and determine the total mass of product collected.
17. Store Crystals: Place the dried crystals and filter paper onto a watch glass
and then place the watch glass in a large beaker. Store this in your drawer
until needed.
7. Add Activated Charcoal: Under a hood, add 0:50 g of activated charcoal to ⌘ Activated charcoal is carbon that
has been processed to have lots of
the reaction mixture. This will not dissolve. pores, greatly increasing its surface
area. Its use in this reaction probably
means part of the reaction takes place
8. Add Ammonia: Add 25 mL concentrated aqueous ammonia to the reaction on the surface of the carbon.
mixture. Be sure to do this under a hood. ⌘ After adding the ammonia, the
mixture should be a brown slurry.
9. Cool Mixture in Ice Bath: Place the flask containing the reaction mixture
into an ice bath and cool the mixture to 0ı C.
10. Add Hydrogen Peroxide: With the flask still in the ice bath, slowly add
2:0 mL of a 30% hydrogen peroxide solution. Be sure to add the hydrogen
peroxide drop-by-drop, leaving plenty of time between drops to allow the
reaction mixture to cool. Be sure the reaction mixture never goes above 10ı C.
11. Heat Reaction Mixture: After all hydrogen peroxide has been added, re- ⌘ This heating step helps facilitate the
dissociation of all water molecules from
move the flask from the ice bath, dry the flask, and then place it on a hot the metal ion.
plate to heat the mixture to 60ı C. Keep the solution on the hot plate at this
temperature for 30 minutes.
12. Cool Mixture in Ice Bath: Place the flask with the reaction mixture into an
ice bath. Look for product precipitating from solution.
13. Suction Filter Product Mixture: Suction filter the solid out of the reaction
mixture. Note that the solid will contain both the product and charcoal.
14. Place Solid in Flask: Transfer the solid collected in the suction filtration to
a 125 mL Erlenmeyer flask.
15. Prepare Hot Water: Add about 20 mL DI water to a small beaker and heat
it on a hot plate until the temperature is about 70ı C.
16. Dissolve Product Crystals: Add the hot water to the flask containing the
collected solid, which contains product crystals and charcoal. Also add
1:0 mL concentrated HCl.
17. Heat Mixture: Heat the flask to 70ı C on a hot plate. This should dissolve
the product, leaving the charcoal as the only solid.
18. Suction Filter Mixture: Suction filter the mixture to remove the charcoal. ⌘ Make sure the filter flask is clean
and dry before this filtration since it is
Be sure you carry out the filtration while the solution is still warm. Note that the liquid that should be saved.
it is the liquid filtrate that you want to save.
19. Chill Filtrate: Transfer the filtrate to a beaker and place the beaker in an ice
bath. Also add 1:0 mL HCl. Crystals should form. If they do not, scratch the
bottom of the beaker with a glass stirring rod.
220 Synthesis of Cobalt(III) Coordination Compounds
20. Suction Filter Crystals: Suction filter the product crystals onto a piece of
⌘ It is important that you only wash weighed filter paper. Wash them in the filter funnel with a few milliliters of
the product crystals with chilled water
and chilled ethanol. the chilled DI water you prepared earlier and then with a few milliliters of
the chilled ethanol.
21. Dry Crystals: Dry the crystals by pulling air through them for about 10
minutes.
22. Weigh Collected Product: Weigh the collected product on the filter paper
and determine the total mass of product collected.
23. Store Crystals: Place the dried crystals and filter paper onto a watch glass
and then place the watch glass in a large beaker. Store this in your drawer
until needed.
2 Turn off and unplug your hot plate; return it to the location from which you
retrieved it.
2 Draw a line at the end of your experimental work for the day. Sign your name
on the line.
2 Have your instructor sign your lab notebook before you leave the lab.
33.1 Introduction
As has been emphasized before, chemists are good at two broad categories of
things: synthesis and analysis. Synthesis is the making of new molecules or
materials. Analysis is the determination of the identity and quantity of substance
present in a sample. In this lab you will carry out an analysis of a coordination
compound that has already been synthesized. Specifically, you will analyze a
coordination compound to determine its wavelength of maximum absorbance,
max , and its molar absorptivity, ✏, which is a measure of how strongly a
substance absorbs light.
The absorbance observed for any given solution depends mainly on these three
things: the nature of the absorbing molecules, the number of molecules located
in the path of the light beam (concentration), and the wavelength of the light
being absorbed. Beer’s Law expresses this mathematically as
A D abc (33.2)
221
222 Analysis of Synthesized Cobalt(III) Coordination Compounds
Chemical Hazards
There are no substantial chemical hazards in this lab. You should treat all
solutions with respect and wash them off immediately if you happen to spill any
of them on yourself.
Goggles
As with all laboratory experiments, you are expected to wear your goggles at all
times while in the lab. Failure to do so may result in expulsion from the lab.
Waste Disposal
All waste in this lab must be poured into the appropriate waste containers in the
hoods located in the back of the laboratory. No waste can be poured down the
drain.
33.3. Experimental Procedure 223
Broken Glass
Do not work with any broken glassware. Dispose of broken glassware in the bins
labeled “broken glass” as shown in Figure 33.1. Do not use the normal waste
baskets for broken glass.
Determine ✏ of Product
1. Prepare Dilution of Product Solution: Using a 10.00 mL pipet, dilute 10.00
mL of the product solution you prepared above with 10.00 mL of distilled
water. Do this as accurately as you can with the equipment you have.
2 Draw a line at the end of your experimental work for the day. Sign your
notebook at the line.
2 Have your instructor sign your lab notebook before you leave the lab. This
helps verify where you stopped lab work for the week.
3. Report the wavelength of maximum absorbance, max , for the reactant coordi-
nation compound and the product coordination compound in water solutions.
4. Rationalize (explain) the color of the two compounds based on their measured
max values. You should be able to do this based on a simple color wheel
argument as you have learned in class.
5. In some computer program such as Excel, plot the absorbance of your product
coordination compound solutions as a function of concentration (absorbance
on the y axis and concentration on the x axis). Be sure to follow guidelines
for plotting graphs electronically.
6. Fit the data in the plot to a straight line using some linear regression tool.
Excel’s “trendline” functionality will be sufficient. Make sure you show the
best fit line on the plot of your data points.
7. Determine the value of the molar absorptivity constant, ✏, for the product
coordination compound in water solution. You can do this from the fit of your
data points to a straight line as you did in the previous problem. Be sure to
include appropriate units.
Chapter 34
Synthesis of a Cross-Linked Silicone Polymer
In this project you will synthesize a cross-linked polymer that should bounce F F
like the commercial product sold under the trademarked name Silly Putty.
C C
34.1 Introduction
F F
Polymers are molecules constructed from a large number of smaller molecules, Figure 34.1
called monomers, that are joined together with the same type of linkage. Nature Tetrafluoroethylene, the
has been making polymers for millions of years. Because they appear in nature monomer used to synthesize
without any human intervention, these are called natural polymers. Examples the polymer with the trade
include silk, wool, cotton, DNA, rubber, starch, cellulose, and proteins. Humans name of Teflon.
learned to make polymers in the late 1830s, and our understanding of how to craft
polymers with specific properties has been growing ever since. Polymers that F F
humans synthesize are called synthetic. Some examples of synthetic polymers
include vinyl, neoprene, polystyrene, Nylon, Teflon, Kevlar, and Mylar. C C
One example of a synthetic polymer is Teflon, the trademarked name for
polytetrafluoroethylene (PTFE). This polymer is formed by connecting thousands F F n
of tetrafluoroethylene monomers end-to-end to form a chain with a molecular
weight between 106 and 107 g=mol. The monomer is shown in Figure 34.1, Figure 34.2
and a representation of the PTFE polymer chain with n monomers is shown in Representation of a polymer
Figure 34.2. A single Teflon polymer molecule may have a value of n between chain in Teflon indicating
104 and 105 . To be more explicit, a Teflon polymer chain is a long chain of the monomer unit repeating
carbon and fluorine atoms, which is better depicted in Figure 34.3. n times.
Figure 34.3
F F F F F F A portion of a polymer chain of Teflon. A single
polymer chain will be about 104 carbon atoms
C C C C C C in length. The parentheses indicate that this is
just a portion of the full polymer chain, which
will extend on both sides of the parentheses for
F F F F F F
thousands of carbon atoms.
225
226 Synthesis of a Cross-Linked Silicone Polymer
Figure 34.4
The reaction to form the Teflon polymer F F F F
is depicted as n monomers of tetrafluo-
roethylene linking end-to-end to form a
polytetrafluoroethylene chain that is n
n C C C C
The reaction to form the Teflon polymer is simple to depict and is shown in
Figure 34.4. Note that no product other than the polymer is produced. When
a polymer is formed in a reaction in which there is no loss of any atoms or
molecules, it is referred to as an addition polymer to indicate that the polymer
is formed literally by adding monomers together. Other examples of addition
polymers include polypropylene, PVC, polystyrene, and Saran wrap.
Another type of polymer is a condensation polymer. This is one that forms
with the loss of a small molecule, usually water. One example of a general
class of condensation polymerization reactions is shown in Figure 34.5. In this
reaction, a di-carboxylic acid reacts with a di-amine to produce the polymer
and water. The R and R0 can be a wide range of chemical species consisting of
carbon and hydrogen. If R is the alkane C4 H8 and R0 is the alkane C6 H12 , the
polymer is called nylon 6,6. If both R and R0 are benzene rings, the polymer is
Kevlar. Other examples of condensation polymers include all proteins, which
are condensation polymers made from amino acid monomers.
O O O O
n C R C + n NH 2 R' NH 2
C R C
H
N R'
H
N + (n-1) H2O
OH
HO
n
di-carboxylic acid di-amine
Figure 34.5
The formation of a condensation polymer is illustrated by the reaction of a di-carboxylic acid monomer with
a di-amine monomer. Note that water is also formed in the reaction. The R and R0 can be a wide range of
species with carbon and hydrogen.
The properties of polymers can vary widely as the length of the polymer
chain is varied. For instance, Teflon is waxy and brittle when the chain length is
short, but as the chain length increases it becomes more mechanically hard and
viscous. Teflon with a chain length of 104 to 105 monomers is so viscous that it
does not flow when melted.
The properties of polymers can also be altered by interactions between
different polymer chains. In some cases, bonds can be formed between different
polymer chains. This is known as cross-linking. One of the more famous
34.2. Safety Considerations 227
examples of cross-linking is the vulcanization of rubber. Natural rubber (a ⌘ The discovery of vulcanization is
attributed to Charles Goodyear in 1839.
polymer) is sticky, deforms easily when warm, and is brittle when cold. It does The production of vulcanized rubber
revolutionized industry because it
not have a high degree of elasticity. If natural rubber is heated in the presence of provided a sealing material much
sulfur, the sulfur will form bonds to two different polymer chains, forming a link better than the oil-soaked leather that
had been used previously.
between them. This process is called vulcanization. This changes the physical
properties of the rubber so that it is more elastic. If too many cross-links are
formed, the rubber becomes too hard to be useful.
In this laboratory project you will synthesize a silicone polymer and then
cross-link the polymer chains to obtain a material that bounces much like the
product sold under the trademarked name Silly Putty. Molecules called silicones
are polymers that consist of alternating silicon-oxygen bonds with two organic
alkyl groups, such as CH3 , bonded to each silicon atom. The polymer you will
synthesize is called polydimethylsiloxane and is shown in Figure 34.6.
CH 3 CH 3 CH 3
Figure 34.6
Polydimethylsiloxane is the silicone polymer you
O Si O Si O Si will synthesize in this project. The parentheses
indicate that this is just a portion of the polymer
CH 3 CH 3 CH 3 chain. No cross-linking is shown.
Silanol molecules then react in a condensation reaction to form the polymer and
water. Since silanol has two OH groups, every condensation reaction that adds
another monomer to the chain will leave the ends of the chain with an OH group.
Boric acid, H3 BO3 , can be used to cross link the chains. It is thought that
boric acid undergoes a condensation reaction with the ends of the polydimethyl-
siloxane chains (which have an OH group attached) to cross-link the chains and
to release water. This will make the silicone polymer more viscous and elastic.
Equipment Hazards
You will use a separatory funnel in this project. A separatory funnel has a
stopcock at one end and a stopper at the other. If you are not attentive, it is easy
228 Synthesis of a Cross-Linked Silicone Polymer
to close both ends, creating a sealed container. This presents a hazard, especially
when the funnel contains a liquid with a low boiling point (like diethyl ether) or
when a reaction evolving a gas takes place in the funnel. Only a slight increase in
⌘ Diethyl ether has a boiling point
below human body temperature. It pressure over atmospheric will be sufficient to force open the stopper, allowing
develops a significant vapor pressure
in a closed container just by touching the contents of the funnel to be blown all over you, your work area, and your
the container. neighbors. Pay attention to your instructor when she describes how to use the
separatory funnel.
Goggles
You are expected to wear your goggles at all times while in the lab. Failure to do
so may result in expulsion from the lab.
Waste Disposal
You will generate waste in this lab that cannot be thrown down the drains or into
the trash can. Please adhere to all disposal policies. When in doubt, ask your lab
instructor. All aqueous waste can be poured down the drain with lots of water.
Broken Glass
Do not work with any broken glassware. Dispose of broken glassware in the bins
labeled “broken glass” as shown in Figure 34.7. Do not use the normal waste
baskets for broken glass.
Figure 34.7
Broken glass container. 34.3 Experimental Procedure
Prepare Silicone Oil
1. Prepare Clean and Dry 250 mL Erlenmeyer Flask: Obtain a 250 mL Er-
lenmeyer flask from your drawer and carefully clean it. Dry it completely
with paper towels.
2. Obtain Stopper for Flask: Obtain a cork stopper for the Erlenmeyer flask.
3. Obtain Dimethyldichlorosilane: With the assistance of your laboratory
instructor or teaching assistant, place 15 mL of dimethyldichlorosilane in the
Erlenmeyer flask and quickly put the stopper back on.
⌘ The diethyl ether acts as a solvent 4. Add Diethyl Ether: Add 30 mL of diethyl ether to the flask. Swirl the
for the dimethyldichlorosilane.
solution in the flask to mix the contents.
5. Add DI Water: Obtain 30 mL DI water and add it dropwise to the solution
in the flask. Swirl the solution in the flask to mix well after adding every
three drops of water.
6. Swirl Until Reaction Ceases: There should be some evidence that a reaction
is taking place. Gently swirl the contents of the flask until all evidence of
reaction has ceased.
34.3. Experimental Procedure 229
7. Transfer Flask Contents to Separatory Funnel: Close the stopcock on the ⌘ Make sure the stopcock works
before using the separatory funnel. If it
separatory funnel and then pour the contents of the flask into the separatory is too loose or tight, ask your instructor
for help.
funnel.
8. Separate Layers: Separate the two layers, saving the diethyl ether layer and
discarding the aqueous layer.
9. Wash Ether Layer with Sodium Bicarbonate Solution: Wash the diethyl ⌘ This will involve inverting the funnel
and swirling the contents while venting
ether layer twice with 20 mL portions of an aqueous solution that is 10% through the stopcock. Your instructor
will provide guidance on how to do this.
sodium bicarbonate.
10. Wash Ether Layer Until Aqueous Layer is Basic: Continue washing the ⌘ All aqueous washes can be
discarded down the drain with plenty of
ether layer with sodium bicarbonate solution until the discarded aqueous layer water.
is no longer acidic. You can test the discarded aqueous layer with long range
pH paper.
11. Wash Ether Layer with DI Water: Wash the ether layer with two 20 mL
portions of DI water.
12. Dry Ether Solution: Transfer the ether solution to a clean and dry Erlen- ⌘ Magnesium sulfate is a drying
agent that will help remove remaining
meyer flask. Add 2 g of anhydrous magnesium sulfate. Allow this solution to traces of water.
sit for 30 minutes with occasional swirling.
13. Weigh Beaker: Clean and dry a 150 mL beaker and then weigh it.
14. Filter Ether Solution: Gravity filter the ether solution using a conical funnel ⌘ This removes the magnesium
sulfate drying agent.
and filter paper. Collect the solution in the clean and dry 150 mL beaker.
15. Evaporate Remaining Ether: Fill a 400 mL beaker half full with hot water ⌘ The taps may run out of hot water.
If so, you will have to heat water on a
(60ı C to 70ı C) from the tap. Place the 150 mL beaker with the ether solution hot plate.
into the hot water. Periodically smell the contents of the 150 mL beaker using ⌘ Silicone oil will have a bitter and
biting odor.
a wafting motion to test whether any ether remains. When no ether remains,
remove the beaker from the hot water.
16. Weigh Beaker with Silicone Oil: Dry the outside of the 150 mL beaker and
then weigh it to determine the mass of the silicone oil you have synthesized.
17. Transfer Silicone Oil to Test Tube: Transfer the silicone oil to an 8-inch
Pyrex test tube. Note that an 8-inch test tube is larger than any test tube you
have in your drawer.
2. Add Boric Acid to Silicone Oil: Add the boric acid to the silicone oil in the
8-inch test tube and stir for several minutes.
⌘ Oil baths should already be set up 3. Heat Test Tube in Oil Bath: Suspend the 8-inch test tube in an oil bath that
around the laboratory.
is at a temperature between 130ı C and 160ı C. Be sure the test tube does not
touch the bottom of the beaker. Leave the test tube in the oil bath for 15 to 20
minutes or until the mixture becomes gooey.
⌘ If you heat the silicone oil too long, 4. Remove Test Tube from Oil Bath: When the silicone oil has reached the
it will become brittle due to excessive
cross-linking. desired consistency, remove the test tube from the oil bath and allow it to
cool. If the contents of the test tube remain too gooey, put the test tube back
in the oil bath.
5. Remove Polymer from Test Tube: Remove the cross-linked polymer from
the test tube using a spatula. You can add talc to make the polymer less sticky.
6. Store Polymer in Plastic Egg: Obtain a polymer egg in which to store your
synthesized polymer.
2 Clean your work area with abrasive cleaner and warm water. There should be
no trace of silicone oil on your bench.
2 Draw a line in your notebook where your experimental work ends. Sign on
this line.
2 Have your instructor sign your notebook on the line at the end of your
experimental section.
1A
(1)
Chemical Periodic Table 8A
(18)
1 2
1 H 2A 3A 4A 5A 6A 7A
He
(2) (13) (14) (15) (16) (17)
1.008 4.003
3 4 5 6 7 8 9 10
2 Li Be B C N O F Ne
6.941 9.012 10.81 12.01 14.01 16.00 19.00 20.18
11 12 13 14 15 16 17 18
3B 4B 5B 6B 7B 8B 8B 8B 1B 2B
3 Na Mg Al Si P S Cl Ar
(3) (4) (5) (6) (7) (8) (9) (10) (11) (12)
22.99 24.31 26.98 28.09 30.97 32.07 35.45 39.95
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
4 K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
39.10 40.08 44.96 47.88 50.94 52.00 54.94 55.85 58.93 58.69 63.55 65.39 69.72 72.61 74.92 78.96 79.90 83.80
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
5 Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
85.47 87.62 88.91 91.22 92.91 95.94 98 101.1 102.9 106.4 107.9 112.4 114.8 118.7 121.8 127.6 126.9 131.3
55 56 57 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
6 Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
132.9 137.3 138.9 178.5 180.9 183.9 186.2 190.2 192.2 195.1 197.0 200.6 204.4 207.2 209.0 209 210 222
87 88 89 104 105 106 107 108 109 110 111 112 114 116
7 Fr Ra Ac Rf Db Sg Bh Hs Mt Ds Uuu Uub Uuq Uuh
223 226 227 261 262 266 264 269 268 271 272 285 289 292
58 59 60 61 62 63 64 65 66 67 68 69 70 71
6 Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
140.1 140.9 144.2 145 150.4 152.0 157.3 158.9 162.5 164.9 167.3 168.9 173.0 175.0
90 91 92 93 94 95 96 97 98 99 100 101 102 103
7 Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
232.0 231 238.0 237 242 243 247 247 251 252 257 258 259 260
231
Amusement
233
Colophon
This document was typeset using the LATEX typesetting system created by Leslie
Lamport and the memoir class written by Peter Wilson. The text was prepared
in Sublime Text 2 running on Apple computer hardware (iMac, Macbook Air,
and Macbook Pro). Photographs were taken with a Canon 20D digital SLR and
then prepared for inclusion using Adobe Photoshop. Illustrations were prepared
using Adobe Illustrator. Illustrations that actually look good were prepared by
Kate Ball. All files were version controlled with Git.
235
1A 8A
(1) (18)
1 2
1 2A 3A 4A 5A 6A 7A
H Chemical Periodic Table He
(2) (13) (14) (15) (16) (17)
1.008 4.003
3 4 5 6 7 8 9 10
2 Li Be B C N O F Ne
6.941 9.012 10.81 12.01 14.01 16.00 19.00 20.18
11 12 13 14 15 16 17 18
3B 4B 5B 6B 7B 8B 8B 8B 1B 2B
3 Na Mg Al Si P S Cl Ar
(3) (4) (5) (6) (7) (8) (9) (10) (11) (12)
22.99 24.31 26.98 28.09 30.97 32.07 35.45 39.95
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
4 K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
39.10 40.08 44.96 47.88 50.94 52.00 54.94 55.85 58.93 58.69 63.55 65.39 69.72 72.61 74.92 78.96 79.90 83.80
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
5 Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
85.47 87.62 88.91 91.22 92.91 95.94 98 101.1 102.9 106.4 107.9 112.4 114.8 118.7 121.8 127.6 126.9 131.3
55 56 57 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
6 Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
132.9 137.3 138.9 178.5 180.9 183.9 186.2 190.2 192.2 195.1 197.0 200.6 204.4 207.2 209.0 209 210 222
87 88 89 104 105 106 107 108 109 110 111 112 114 116
7 Fr Ra Ac Rf Db Sg Bh Hs Mt Ds Uuu Uub Uuq Uuh
223 226 227 261 262 266 264 269 268 271 272 285 289 292
58 59 60 61 62 63 64 65 66 67 68 69 70 71
6 Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
140.1 140.9 144.2 145 150.4 152.0 157.3 158.9 162.5 164.9 167.3 168.9 173.0 175.0
90 91 92 93 94 95 96 97 98 99 100 101 102 103
7 Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
232.0 231 238.0 237 242 243 247 247 251 252 257 258 259 260
1A 8A
(1) (18)
1 2
1 2A 3A 4A 5A 6A 7A
H Chemical Periodic Table He
(2) (13) (14) (15) (16) (17)
1.008 4.003
3 4 5 6 7 8 9 10
2 Li Be B C N O F Ne
6.941 9.012 10.81 12.01 14.01 16.00 19.00 20.18
11 12 13 14 15 16 17 18
3B 4B 5B 6B 7B 8B 8B 8B 1B 2B
3 Na Mg Al Si P S Cl Ar
(3) (4) (5) (6) (7) (8) (9) (10) (11) (12)
22.99 24.31 26.98 28.09 30.97 32.07 35.45 39.95
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
4 K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
39.10 40.08 44.96 47.88 50.94 52.00 54.94 55.85 58.93 58.69 63.55 65.39 69.72 72.61 74.92 78.96 79.90 83.80
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
5 Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
85.47 87.62 88.91 91.22 92.91 95.94 98 101.1 102.9 106.4 107.9 112.4 114.8 118.7 121.8 127.6 126.9 131.3
55 56 57 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
6 Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
132.9 137.3 138.9 178.5 180.9 183.9 186.2 190.2 192.2 195.1 197.0 200.6 204.4 207.2 209.0 209 210 222
87 88 89 104 105 106 107 108 109 110 111 112 114 116
7 Fr Ra Ac Rf Db Sg Bh Hs Mt Ds Uuu Uub Uuq Uuh
223 226 227 261 262 266 264 269 268 271 272 285 289 292
58 59 60 61 62 63 64 65 66 67 68 69 70 71
6 Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
140.1 140.9 144.2 145 150.4 152.0 157.3 158.9 162.5 164.9 167.3 168.9 173.0 175.0
90 91 92 93 94 95 96 97 98 99 100 101 102 103
7 Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
232.0 231 238.0 237 242 243 247 247 251 252 257 258 259 260