Professional Documents
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General Chemistry
Laboratory Manual
Spring 2017
Dr. Martin Jones
Dr Christina Miller
Dr. Renee Beeton
GENERAL PROCEDURES
Become familiar with each laboratory experiment prior to coming to the lab. Read the lab
before the lab lecture is given and take good notes during the lab lecture so you will be able
to work efficiently in the lab. You will lose 3 points for not attending a lab lecture. Each lab
has a pre-lab assignment that must be completed in your lab notebook before coming to lab.
The instructor will check the assignment as you come to lab. You may lose up to 3 points on
a one -week lab or 4 points on a two-week lab for not doing the pre-lab assignment.
Keep your own work area (your section of the bench) and the common areas (around the
balances, sinks, and other instruments) clean and free of debris. It is your responsibility to
clean up any spills or broken glass. Paper towels, brooms, and dustpans are available in the
lab. If you spill a solid on the balance, turn off the balance and use the little paintbrush to
sweep the solid onto a paper towel. If necessary, remove the balance pan and clean that area
as well. If a liquid is spilled on the balance pan, turn off the balance and carefully remove
the balance pan and blot up the liquid with a paper towel. Replace the balance pan and turn
on the balance. Clean and put away all glassware used. Your instructor will not initial your
lab notebook at the end of the lab period until you have cleaned up.
Dispense reagents carefully. Do not take more reagent than is necessary from a common
reagent bottle. If you do happen to get more than you need, do not return excess reagent to
the common bottle. First ask your neighbors if they need any of the reagent. If not, dispose
of the reagent as instructed by the lab instructor. Some experiments will call for approximate
quantities, for example, heat up about 200 mL of water in a beaker. In this case you do not
need accuracy and you can simply fill a beaker to approximately the 200 mL line. In other
cases, you will be asked to measure out more exact quantities and you need to use the
appropriate measuring devise and take more care in using it. At times you will be asked to
accurately weigh out an approximate mass of chemical, for example, accurately weigh out
approximately 0.5 g. In this case, use a spatula to adjust the amount of chemical to within
10% or the desired amount (between 0.45 g and 0.55 g in the given example) and then write
down all figures displayed on the balance (say, 0.483 g).
Dispose of laboratory reagents as directed by the lab instructor. Most reagents used in the
general chemistry laboratory can be rinsed down the sink with large amounts of cold water.
However, on occasion, you will need to place reagents in designated waste containers. There
are three such containers in the hoods in the lab one for heavy metal waste, one for
nonhalogenated organic waste and one for halogenated organic waste. Please ask the
instructor for assistance.
WORKING IN GROUPS
Except for the first lab, you will be assigned to a group of 3 or 4 students that will work
together for the first half of the semester. At midterm, you will be assigned to work with a
new group for the rest of the semester. Sometimes you will be doing parts of the experiment
individually, but you will be turning in a summary of your lab work or a group report
together. Along with the summary report, each individual in the group will be attaching the
duplicate pages from your lab notebook (see next section for more information about the lab
notebook). Two thirds of the grade you receive on the lab will be from the group report and
one third from your individual duplicate pages. For the most part, chemists do not work
individually in industry or in research, but as part of a team. It is important that you begin to
learn how to function as a team to solve problems.
Make every good effort to work with your group as your grade, in part, depends on how well
your group functions together. It is a lot more fun if all group members take an active part in
all aspects of the process. This includes being on time since you will be holding up your
group if you are late. Instructors will deduct points for being late to lab.
Talk over what you will be doing before you start. You will be taking turns being the group
leader. When you are leader, make sure all group members participate.
When you have finished taking data, do not leave if there is still time left in the lab period.
Begin to generate your summary/report. All group members should participate in generating
the content of the summary/report, not just the person who is designated as the recorder for
that week. It is a lot easier to do this work while the material is fresh in your mind, your
entire group is already assembled, and you have an instructor or lab assistant handy to answer
questions. Sometimes you will be able to complete the summary and turn it in before you
leave instead of waiting until the following lab lecture.
Before you leave, set a time and place for your group to meet to finish the summary/report if
you did not get it done during the lab time. Everyone should have the opportunity to check
over the summary report before you turn it in as everyones grade depends on it. You will
also read the leaders participation report, add any comments to the participation report, and
sign it on the lab report cover sheet.
You will be rotating the jobs of group leader and group recorder. The leaders job is to call
the group together to work out a plan of action, to make sure all group members are carrying
out their assigned tasks, to call for additional meetings if required, fill out a participation
report, and deduct points for lack of participation. The recorders job is to fill out the group
summary or enter the report in the computer for the project labs. Everyone needs to
contribute to the content of the reports. On the next page are two group duty rosters for you
to fill out during the first period your group works together, one for the first half of the
semester and one for the second half of the semester.
If you feel that your group is not functioning, bring it to the attention of the lab instructor.
The instructor will meet briefly with your group at the end of a lab period or other arranged
time to assist you in getting on track.
Although you are working in groups, each team member is responsible for knowing how to
use all of the equipment for each lab, how to conduct all analysis, and how to do all of the
calculations. There will be two lab exams/practicals that test all of these skills individually.
Phone #
E-mail address
Local Address
DUTY ROSTER
Experiment #
2
Leader
Recorder
3
4
5
Phone #
E-mail address
Local Address
DUTY ROSTER
Experiment #
6
Leader
Recorder
7
8
9
10
Note: Make sure that the same person is not the recorder for labs 3 and 6, the two project labs.
Errors and Statistics
There are always errors associated with making measurements in the laboratory. We classify
errors as accuracy errors and precision errors. Accuracy refers to how close the measurement is
to some assumed true value or some accepted literature value. We can reduce accuracy errors
by calibrating our instruments and by using them correctly. Precision errors reflect our ability to
repeat measurements and obtain the same value. The precision is limited by the quality of the
measuring device. For example, a graduated cylinder is more precise than a beaker for
measuring volume. We can obtain an idea of our precision by repeating the measurements
several times and observing the scatter in the data.
In several experiments, each member of your lab group will be obtaining values for the same
quantity. You will be asked to average the values and find the standard deviation. The average,
x, represents your best estimate of the value and the standard deviation, n-1, is a measure of the
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scatter in the data. Standard deviation assumes that all the errors are random and distributed
according to a normal distribution or what is often referred to as a bell curve because of the
curves resemblance to a bell shape. When you report the average plus or minus the standard
deviation ( x n-1), statistics claims that the average value of many measurements has a 68%
probability of being in the range of
x + n-1 to x - n-1.
You may use your calculator to obtain values of the average and the standard deviation. Every
make and model of calculator tends to have its own unique way of doing this so we cannot give
you directions that work in all cases. You need to consult your calculator manual or with
someone that has a similar calculator and knows how to use it. You need to be able to enter a
data set and then use the correct keys to obtain the average and the standard deviation. Note that
calculators will usually have both n and n-1 functions. It is the n-1 that is appropriate for most
situations. If you cannot figure out how to calculate the values directly, there are formulas for
calculating both. Suppose you had n values: x 1, x2, .xn.
x = x1 + x2 + ..xn
n
To get n-1 you need to calculate the deviations of each value from x and square them:
d12 = ( x x1)2, d22 = (x x2)2, .. dn2 = (x xn)2
Then
=
Example: If the values are 6,8,6,and 9
Now d12 = d32 = (7.25 6)2 = 1.56,
=
= 1.50
d + d + d
1
If a value is known from a literature source or otherwise, you can report the accuracy error in
your measurement as a percent error.
%error = experimental value literature value x100
literature value
measure will be different from those reported in reference sources. You will need to adjust your
boiling points and we will show you how in the lab.
Reference Sources:
CRC Handbook of Chemistry and Physics (available in lab room, room POR 312 , ASC Library)
Lange's Handbook of Chemistry (available in ASC Library)
Merck Index (available in room POR 312, ASC Library)
Aldrich Chemical Company Catalog (available in room POR 312, ASC Library)
Possible Compounds for this experiment.
2-propanol (isopropyl alcohol)
ethanol (ethyl alcohol)
ethylene glycol
2-propanone (acetone)
2-methyl-2 propanol (t-butyl alcohol)
dodecanol
(SAFETY NOTE: All these compounds are flammable. There should be no flames in the lab.
Use a hot plate to heat samples. Dispose of extra/used samples in the waste container marked
non-halogenated organic waste).
Report
The report for this project experiment should include:
A Lab Report Cover Sheet completely filled out and signed.
A brief description of the problem you were asked to investigate. Identify the unknown by
number.
A summary of the experimental design (i.e., the plan you developed to investigate the
problem) including brief descriptions of the procedures you followed to conduct the
individual experiments in your experimental design.
The results including calculations from each group member's experiments. These should
include the physical properties your group measured experimentally and the physical
properties your group looked up in reference sources including: boiling and melting point
determinations and density determinations. You may wish to present the information in a
table. Be sure to indicate which values you measured and which were looked up and cite the
sources.
Predictions of how life on an Alien World would be affected if the liquid your group
investigated was the major liquid on that world. Be sure to provide rationale for your
predictions (i.e., why would changing the properties of the liquids affect the alien world?).
Begin your predictions with a discussion of the structure and prevalent intermolecular
attractive forces of water and how these affect its physical properties. Include both liquid and
solid forms of water. Pay special attention to how the properties of water affect the average
temperature of the earth. Comparison of your liquids physical properties to those of water
should provide the rationale for the predicted changes.
Each group members individual duplicate pages from the lab notebook. These pages should
include the procedures, data, observations, calculations, and results from the individual
experiments carried out. Attach these pages to the project lab report.
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The report should be written using a word processor (although the calculations may be handwritten if you wish).
The group report is worth 30 points and the individual duplicate pages are worth 15 points.
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Experiment 2 - Spectroscopy
Learning Objectives
Learn how to use spectroscopic techniques for both qualitative and quantitative analysis.
Improve laboratory skills for preparing solutions with molar concentrations.
Learn the typical terminology associated with absorption and emission spectroscopy.
Improve skills in experimental design and planning, group work, and data interpretation.
Pre-lab Exercise
1. Calculate the amount of CoCl26H2O required to make 25.0 mL of 0.200 M solution.
2. What is the concentration of a solution of Fe(NO)3 if the absorbance is 0.35 in a 1.0 cm
cell? The molar absorption coefficient is 1.8 x 102 L/(cm)(mol)
Background
Electromagnetic radiation is a type of energy consisting of oscillating electric and magnetic
fields that travel in wavelike fashion. The figure shown below, which is the same as a figure in
chapter 4 of your textbook, illustrates components used to describe a wave. Of most interest to
us
is the wavelength, , which is the distance between two successive crests or troughs in the wave,
and the frequency, , which is the number of full waves that pass a point in a given period of
time (generally one second). The units of are units of length, such as m, mm, and nm. The
units of frequency are cycles per second, better known as hertz (Hz). The energy of
electromagnetic radiation may be related to either the wavelength or the frequency, using
Planck's equations as shown below. As can be seen from the equations, the energy of
electromagnetic radiation is directly proportional to frequency and indirectly proportional to
wavelength.
E = h
or
E = hc/
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we'll be most interested in the visible light region, from about 350 nm (8.6 x 10 14 Hz) to 750 nm
(4.0 x 1014 Hz).
When matter encounters electromagnetic radiation of the proper frequency, absorption of the
radiation may take place. This results in some distinct change in the structure of the matter. For
example, absorption of infrared light by organic molecules can cause bonds to be bent or
stretched. Absorption of ultraviolet or visible light by organic or inorganic compounds can cause
electrons to jump from one orbital to another higher energy orbital. Loss of the excess energy
from the higher energy species often occurs via emission of light. This overall process is
illustrated below.
absorption
of light
Energy
E
emission
of light
%T =
light detected
x 100
light emitted
Another comparison that is used is absorption (A). This is a measure of the amount of light of a
specific wavelength that is absorbed by the sample. The equation for A is:
12
Procedure
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A. Emission Spectroscopy
NOTE: This part of the experiment will be done on an individual basis and the lab report for
this part of the experiment will be written only in your lab notebooks there is no summary
report for part A.
1. Obtain a looped nichrome wire, a flat toothpick and a Bunsen burner. In your 24-well plates,
place 20 drops (about one mL) of each of the following aqueous solutions: 0.1 M LiCl, 0.1
M CaCl2, 0.1 M NaCl, 0.1 M Ba(NO3)2, and 0.1 M Sr(NO3)2. Also get a few crystals of one
of the unknown powders. Record the code of the unknown in your notebook. In a separate
small test tube, place a few mL of 6 M HCl.
2. Light the Bunsen burner. Dip the loop of the nichrome wire into the tube of 6 M HCl, then
place the loop into the hottest part of the burner flame (the tip of the blue part of the flame).
Repeat this step two or three times, until the flame around the wire is nearly colorless.
3. Dip the loop of the wire into one of the known solutions (save the NaCl for the very last),
cleaning the wire after every test. Record your observations on the report sheet. After you
have completed the flame tests on the known substances, add 20 drops of water to the
unknown powder and use a toothpick to stir the mixture. Perform a flame test on the
unknown solution, and identify your unknown. Clean the nichrome wire thoroughly before
continuing. Have each group member pick a different unknown.
4. Be sure you include a procedure and a discussion/conclusion section in your notebook for
this part of the experiment.
B. Absorption Spectroscopy
NOTE: This part of the experiment will be done in your lab group. Calculation and analysis
should be done on the tear-out report sheet. If you wish, you may use one lab partners tearout for rough work, and another partners tear-out for the final version to turn in.
1. Prepare 25.0 mL of about 0.2 M CoCl26 H2O using a volumetric flask. Be sure to record
the mass of solid you actually weigh out and determine the actual concentration to the correct
number of significant figures using that mass. This will be your stock solution.
2. Dilute the stock solution by the appropriate factors to make 10 mL each of approximately
0.15 M, 0.10 M, 0.050 M and 0.020 M. Use the dilution equation (M cVc = MdVd). You can
use 10 mL volumetic cylinders, but use them very carefully to get good results. Adjust the
amount of stock solution in the cylinder with a pipette, fill to the 10 mL mark with a water
bottle and then invert several times with the cylinder stoppered to mix well.
3. You will be using an Ocean Optics spectrometer. The instrument should already be hooked
up to a lap top computer and a printer and turned on, but must be calibrated prior to use.
From the top tool bar, click on Experiment and choose Calibrate Spectrometer and
follow the directions in the dialog box and click OK when finished. Instead of using an
empty cuvette, fill a cuvette about full of DI water for calibration. The calibration box
counts down from 1 minute to warm up the lamp before you put the cuvette in the sample
compartment. Three minutes is better if you are the first group to use the instrument that lab
period. The cuvette should be inserted so that the 1 cm side is in the light path.
4. Dump out the water and add a small amount of the stock solution to the cuvette, swish
around and empty it. Fill the cuvette to about 3/4 full with the stock solution. This should
14
eliminate any dilution effects from water having been in the cuvette. Wipe off the outside
with a Kimwipe, and place the cuvette into the sample compartment making sure it is
oriented correctly. Click on the Configuration Spectrometer Data Collection icon located on
the right hand side of the toolbar. It has colored bars under a spectrum.
5. Click box on Abs vs. Concentration (under Set Collection Mode; it may already be correctly
selected). The wavelength of the maximum absorbance will be automatically selected.
Check that only one wavelength is selected and that it is one in the visible range. Click OK
to close the display.
6. Click on Collect icon on the tool bar at top. Next click on the Keep icon at the far right
of top tool bar. Enter the concentration of the sample in the box that comes up and click OK.
7. Empty the cuvette, add a small amount of one of your diluted samples to the cuvette, swirl it
around, then pour it out. Fill the cuvette about 3/4 full with the diluted solution and put back
in the sample compartment. The absorption value will show at the left below the tool bar.
Click on Keep and enter the concentration. Continue measuring and entering the rest of
the diluted samples.
8. Click on the Stop icon when data on all 5 solutions has been taken. Click the linear fit
icon to have the computer draw a best fit line through your data. If the plot is not scaled
correctly, you can use the auto scale icon or put the cursor on the numbers on the axis and
type in a new value. Sometimes it is difficult to get the cursor to lock on the number. When
locked the computer will place a box around the number and then you type in the new value.
9. Obtain one of the unknown solutions, put in the cuvette and the sample compartment.
Remember to rinse the cuvette with the solution before filling and wipe off outside.
10. Click on the Analyze icon in the tool bar and choose Interpolation Calculator (not
Interpolate!) from the Analyze menu. A helper box will appear, displaying the absorbance
and concentration of the unknown. Click OK
11. Make sure the printer switch box is turned to your computer and then print out the results
using the print icon.
12. After you have finished, under Experiments click on Clear last run and the X in the
boxes on the graph area. Remove your cuvette, pour out sample and rinse well with DI
water.
Your report should contain the cover sheet, the completed tear-out summary report for part B,
the Beers law plot, and individual notebook duplicate sheets for each group member.
15
16
17
Attach cover sheet, printout from the Beers law experiment and the duplicate pages from each
team members lab notebook to this summary report.
18
Experiment 3 Deicers
Learning Objectives
Learn how to make freezing point measurements.
Practice calculating molality
Practice calculating the vant Hoff factor, i.
Practice calculating freezing point depression constants.
Learn how to make a slush for low temperature work.
Learn how to do a cost analysis for product comparison.
Pre-lab Exercise
1. Calculate the molality of a solution of 2.57 g of NaCl in 25.0 mL of water.
2. What would the freezing point of the solution in question 1 be if the freezing point of pure
water is 0.00C, assuming a vant Hoff factor of 2?
Background
In chapter 11 of your textbook you learned that the freezing point of solvents is lowered by the
presence of dissolved solutes. Freezing point lowering is one of four colligative properties that
depend on the amount of dissolved substances, not on the chemical nature of the substances.
The amount of lowering of the freezing point is given by the equation Tf =- kfmi. kf is the
freezing point depression constant (1.86oC/m for water), m is the molality of the solute and i is
the van Hoff factor. Molality is defined as the moles of solute divided by the kilograms of
solvent. For molecular solutes, the molality of all dissolved solute species is equal to the
solution molality since the molecule stays intact when it dissolves. For ionic solutes, the ions
separate when they dissolve and each individual ion contributes to the total molality of dissolved
species. The molality of all species is the solution molality times the number of ions in the
chemical formula. For example, the total molality of KCl is double the solution molality while
the total molality of K2SO4 is triple the solution molality. The vant Hoff factor, i, is the number
of particles that the solute will dissolve into. However, a further complication is that ionic
substances rarely dissociate completely, so a solution of an ionic compound will contain fewer
particles than would be expected due to ion pairing. The extent of ion pairing seen is
concentration-dependent. We will be exploring three different solutes in water where we will be
using them in fairly concentrated solutions. We will be seeing how the vant Hoff factor, i,
changes under the higher concentrations we will be using.
As a pure solvent freezes, the liquid left behind is still pure solvent. It will continue to freeze at
the same temperature until it is all frozen. After all the solvent is frozen, the solid can now
decrease in temperature. Conversely, as the solid is heated, it will warm to its melting point and
begin to form some liquid. As the solid melts, it will remain at the same temperature until all of
the solid is melted. Additional heat will now warm the liquid. A graph of the warming and
melting process is shown below. In our case we will not totally freeze all the liquid and we will
quit taking temperature measurements before all of the solid is melted so we will stay on the flat
portion of the graph.
When you freeze a solution instead of a pure solvent you are removing only the solvent to form
the solid. The concentration of the solution left behind becomes more concentrated and the
19
freezing point keeps going down. Once all the solution becomes solid, it will drop in
temperature more quickly. As you heat a solid solution, the converse will occur. A graph of the
warming and melting process is shown below along with the case of the pure solvent. As with
the pure solvent, you will not totally freeze the solution so that most of your data will be taken as
the solution melts. The temperature we want to record for the freezing point of the solutions is
the temperature just before all of the solid melts.
Warming Graph for Pure Solvent
T
solid
melting
liquid
solid
melting
liquid
Scenario
Several different chemicals are or have been used as deicers, substances that lower the
freezing point of ice so that the ice can be removed or melted away more quickly. To deice
windshields, methanol is commonly used while 2-propanol (CH 3CH(OH)CH3), commonly
known as rubbing alcohol, can be used for windshields and is also used for airplanes. Rubbing
alcohol normally comes as a 70% by volume mixture of 2-propanol with water. You can
purchase it at near 100% purity but the cost is more prohibitive for commercial use due to the
amount of alcohol you get. To make calculations easier, we will use 100% 2- propanol.
For deicing roads or sidewalks, salts or concentrated solutions of salts are commonly used. The
most popular salt used for many years was sodium chloride (NaCl) because sodium chloride is
one of the cheapest salts available. For home use, calcium chloride mixed with other chloride
salts can be purchased commercially. Recently, an aqueous solution of magnesium chloride
(MgCl2) has become more popular for use on roads. This solution is used almost exclusively on
Colorado roads. You may have noticed roads where it has been used as the road appears darker
in color due to a residual film of the hydrated MgCl 2 that is left behind after the snow and ice
have melted.
Your job in this lab is to evaluate the three deicers: sodium chloride, calcium chloride and 2propanol. You will need to test their ability to lower the melting point of ice and calculate the
vant Hoff factor for each concentration of deicer used. Your group will also do a cost analysis
by calculating how much it costs for enough of each of the deicers to lower the freezing point of
1 kg of water by 10.0oC.
Procedure
To make a dry ice bath for freezing samples, each lab group has a low-cut vacuum bottle into
which you need to pour 70% rubbing alcohol until it is about 1 1/2 inches deep. Break up the
dry ice into smaller pieces by covering it with a cloth and hitting it with a hammer. Slowly add
the small pieces to the alcohol until it gets cold enough to form a slush. Wear gloves while
20
handling the dry ice so as to not get freeze burns. All persons in your group will be using the
slush to freeze their samples. If the slush begins to melt with use, a few more pieces of dry ice
can be added. If a group has used the slush in the lab period ahead of you, the bottles will
already have alcohol in them and may be partly frozen. Only a few more pieces of dry ice may
be needed, if any, to reform the slush. Dont add too much dry ice or the slush will have too
many pieces of dry ice in it and it will be harder to put the samples in it to freeze.
Each member of your group will choose one of the three deicers to test. Use a medium sized test
tube (15 cm long and 2 cm in diameter is good) and a thermometer which goes down to 20 oC.
Use a 10 mL graduated cylinder to carefully measure out 5 mL of water and pour into the test
tube. Assume that the density of water is 1.00 g/mL so that the mass of water is 5.00 g. Now
put the thermometer into the water and the test tube containing the water and thermometer into
the slush. Hold the top of the test tube with one hand and gently stir the water with the
thermometer using your other hand. Lift it out after a minute or two to see if you have frozen a
layer of ice around the inside of the test tube. If you have a layer frozen, remove the test tube;
otherwise, return the test tube to the slush bath until a layer of ice has formed. After removing
the test tube, read the thermometer occasionally as you gently continue to stir the ice-water
mixture until most of the ice has melted and only a few chunks of ice remain. The temperature
should stay nearly constant at close to zero as it is melting, but your thermometer may not read
exactly zero. Choose a value for the melting point of pure water from your data.
Warm up the water until all the ice has melted and add the first prescribed amount of de-icer
from the table. Refreeze the mixture in the slush bath. This time slush will form in the mixture
rather than an ice layer forming around the inside of the test tube. Keep cooling until the slush in
the test tube is formed throughout, but is not real stiff. Now take the test tube out and make
temperature readings as you gently stir with the thermometer and the slush melts while holding
the test tube in the air. Take the last reading when most of the ice has melted and only a few
chunks of ice remain. As the slush in your test tube melts it is changing the concentration of the
liquid solution making it more dilute. You should see the temperature of the slush change while
this is happening so you will end up with a temperature range for melting the slush. The most
accurate temperature to use for the reported melting point of the solution is when there are still a
few ice crystals left but most of the slush has melted because the original concentration of
solution has been re-established. You will now add an additional increment of deicer and repeat
the measurements and then a third increment and repeat the measurements a third time.
Deicer
NaCl
CaCl2
100% 2-propanol
In all cases, weigh or measure out precisely how much is added each time and use your data to
calculate molalities. For the 2-propanol, calculate the grams of 2-propanol added assuming 2propanol has a density of 0.785 g/mL.
21
From the total molalities of dissolved species and the freezing point lowering, calculate the vant
Hoff factor for each of the three concentrations you measured.
Report
Each group member needs to fill out their lab notebooks with their data and calculations.
Organize data into a table that includes temperature measurements, volume (mass) of water you
started with, and masses of deicer added and organize calculations into a table that includes Tf,
total mass of water, total mass of deicer, solution molality, and i. Duplicates of these should be
attached to the lab cover sheet and the tear-out group report that contains a summary of the data
from the individual reports, a cost analysis of each of the deicers (cost of deicer required to lower
the freezing point of 1 kg of water by 10.0 oC) and a discussion of the pros and cons of each of
the deicers.
A quick check of the local stores gave the following prices for deicers. Sodium chloride costs
$3.25 for a 40 lb bag. Commercial deicer consisting mostly of CaCl 2 costs $3.00 for a 20 lb bag.
70% rubbing alcohol costs $.44 per pint (430 mL) so the equivalent of 100% 2-propanol would
cost $.63 per 430 mL (use this value for the 2-propanol calculation). In your discussion,
consider the uses of each deicer for deicing windows and roads/sidewalks and why one might be
desirable over the other for a particular use. Consider your cost analysis results and any
environmental factors you can think of. Report whether the apparent k f stays constant as the
concentration of each of the deicers increases and whether the apparent k f is the same for all
three deicers.
Example cost analysis:
Suppose that your data for deicer X indicated that the vant Hoff factor was equal to 4.2 The
molar mass of X is 100 g/mole. Furthermore, X costs $5.00 per pound. What is the cost of
enough deicer X to lower one kg of ice by 10.0 oC?
From the formula, Tf = -kfmi , mi = -Tf -/kfi
so m = (-10.0oC)/(-1.86oC/m)(4.2) = 1.28m
Now we want the amount of deicer X in 1 kg of water so (1.28 mol/kg)x(1kg) = 1.28 moles of
deicer.
We need the mass of deicer X : (1.28 moles of X) x (100 g of X)/(1 mole of X) = 128 g.
Finally, we need to convert from grams to lbs and lbs to dollars.
(128 g of X) x (1 lb)/(453.6 g) x ($5.00) / (1 lb) = $1.40
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Total molality
NaCl
CaCl2
Isopropanol
23
3. Discussion of the advantages and disadvantages of each deicer for use in de-icing
windows or roads and sidewalks. Discuss the results as indicated in the report section of
the write-up.
24
(1)
You will follow the reaction by measuring the volume of O 2 as it displaces water in a buret at
constant pressure. The rate of a chemical reaction is a measure of how rapidly the products form
or the reactants disappear. To put all reactants and products on an equal footing, we divide by
the stoichiometric coefficient in the balanced reaction. Rate = (-1/a)(Reactant / time) =
(+1/b)( Product / time) with a and b being the coefficients of reactant and product
respectively. Since the coefficient of O2 is one, the rate for the decomposition of H 2O2 can be
expressed in terms of the production of O2 by Rate = mole of O2/ t. moles of O2 is the
change in the moles of oxygen gas and t is the time interval of the change in moles of oxygen.
If we plot the moles of O2 as a function of time in seconds, the rate is also given by the slope of
the line. As the reaction proceeds, the amount of H 2O2 continuously decreases so that the rate
decreases. If we choose to measure the rate at the very beginning of the reaction before much of
the H2O2 has decomposed, we know how much H 2O2 is present. This is called the initial rate.
25
The initial rates will allow us to determine the rate law, the rate constant and the activation
energy.
In order to calculate the initial rates, you will need the rate of production of moles of O 2. What
you will measure in lab is the rate of production of milliliters of O 2. If we assume O2 is an ideal
gas, we can use the ideal gas law to convert from milliliters to moles.
PV = nRT
(2)
= Rate in moles/s
= Rate in moles/s
X mL/s is the value of the initial rate in mL of O2 per second obtained from the slopes of the data
plots.
B. Rate Law
The rate law for a reaction gives the mathematical dependence of rate of the reaction upon the
concentrations of all species involved in the reaction. So called simple rate laws are products
of powers of the concentrations of reacting species. For the catalytic decomposition of H 2O2,
only H2O2 and the catalyst, I-, participate in the rate law. The simple rate law for the
decomposition of hydrogen peroxide is Rate = k[H2O2]x[I-]y. k is called the rate constant. x
and y are most often whole numbers and are referred to as the orders of the reaction. As stated
above, x is well established as 1, that is, the order with respect to the hydrogen peroxide
concentration is 1 or we say the reaction is first order in H2O2. The overall order of the rate law
is the sum of all the individual orders. Your job will be to establish the value of y, i.e. the
order with respect to the catalyst, I-.
Catalysts are involved in the rate law, but they do not appear in the overall chemical reaction.
The reason is that they are consumed in an early step in the reaction but are then regenerated in a
later step. In the net reaction, the catalyst cancels out. The result is that the concentration of the
catalyst remains constant during the course of any one kinetic run. If we now measure the initial
rates for the reaction at two different concentrations of I- but with the same concentration of
H2O2, we can determine the order with respect to [I-]. Putting in the known value of 1 for the
order of [H2O2]:
Rate1 = k[H2O2][I-]1y and Rate2 = k[H2O2][I-]2y
26
[H2O2] values are equal and constant because of the initial rate conditions
[I-] concentrations stay the same during the course of the kinetic run, but may be different
between two different kinetic runs.
We can divide Rate2 by Rate1. k[H2O2] cancels giving
Rate2/Rate1 = {[I-]2/[I-]1}y
Taking the natural log of both sides and solving for y gives
y = {ln(Rate2/Rate1)}/{ln([I-]2/[I-]1}
(3)
After establishing the orders in the rate law and measuring the initial rate of the reaction for a
given concentration of all species in the rate law, we can solve for the value of the rate constant.
In our case,
k = Rate/[H2O2][I-]y
(4)
We measured the rate in moles per second rather than as a concentration. To get the units to
come out right, we should enter [H2O2] in as moles rather than molar. You will be using 5 mL of
3% H2O2 in all cases. 3% of 5 mL means you have 0.03 x 5mL = 0.15 mL of H 2O2. The density
of H2O2 is 1.44 g/mL and its molar mass is 34.0 g/mol. We can calculate the moles of H 2O2.
(0.15 mL)(1.44 g/mL)(1mol/34.0g) = .00635 moles of H2O2
(5)
Now [I-] should be put into the equation for the rate constant in units of molar concentration.
Remember to apply a dilution factor to input the concentration in the reacting mixture. Recall
that Rate has units of moles/s. k will then have the units of
s-1M-y. You will have two values of k at room temperature which should be nearly equal. Take
an average of the two values. You will have a different value of k for the elevated temperature.
C. Activation energy
The temperature dependence of the reaction is expressed in the value of the rate constant, k.
Arrhenius determined that the temperature dependence can be expressed by
k = Ae-Ea/RT
where A is the pre-exponential factor, Ea is the activation energy, and R and T are the usual
gas constant in J/mol K and temperature in Kelvin. A discussion of this equation and the
activation energy are given in your textbook and is not included here. In brief, the activation
energy is a barrier that must be overcome in order to get from reactants to products. The higher
the temperature is, the larger the fraction of molecules that have sufficient energy to go over the
barrier and form products. The ratio of the rate constants at two different temperatures is:
27
(6)
You can use this equation along with your two values of k at different temperatures to calculate
the activation energy.
Experimental Details
A diagram of the apparatus is shown.
Before you begin taking kinetic data,
you will need the atmospheric pressure
and the room temperature so you can
convert mL of O2 to moles of O2.
Read the barometer and a thermometer
left out in the room.
Fill the tray with tap water at about
room temperature. Make sure the
buret is nearly full of water, the
funnel is nearly empty and at the
top, and the stopcock on the buret
is open. Put about 10 glass beads into
the Erlenmeyer flask. Measure out 5 mL
of 3% H2O2 and put into the flask.
Measure out 5 mL of 0.10 M KI and
put it into a small beaker. Hold the
flask and beaker in the tray with the
water for about a minute so they can
thermalize with the water. Clear a
stop watch so it reads zero
funnel
tubing
50 mL
buret
tubing
25 mL
Erlenmeyer
Your group will need to assign jobs for performing a kinetic run. One persons task will be to
pour the KI solution into the flask containing the H2O2, place the stopper connected to the tubing
into the top of the flask and then begin swirling the flask while holding it in the water. A
thermometer should also be in the water in the tray and the temperature taken just before and just
after each kinetic run. A second persons job will be to follow the volume of O 2 as it is evolved.
To keep the pressure equal to the atmospheric pressure, the person will need to lower the funnel
as the O2 is evolved so the water level in the funnel stays close to the same as the level in the
buret. Let 1 to 2 mL of O2 be evolved to allow the system to stabilize. Then start calling out
28
every time the level drops to a mL mark on the buret. The buret is inverted so the mL marks are
just above each of the inverted number. You can stop after 10 mL past the original 1 to 2 mL
have been evolved. The third persons job will be to time and record the evolution of each mL.
The stopwatch should be started at the first instant the follower of the O 2 evolution calls out.
Each following mL that is evolved needs to be timed and recorded. If you have 4 people in your
group the 4th person can supervise and make sure all is being done correctly. It is recommended
you rotate through the jobs for the 3 runs.
After the first run, disconnect the reaction flask and pour out the reaction mixture in the sink.
You can hold back the glass beads with a wire gauze. Rinse out the flask and beads several
times with water and shake out the excess water. Now you are ready to repeat a kinetics run.
You will again use 5.00 mL of H2O2 solution in the Erlenmeyer flask, but this time add 2.50 mL
of KI instead of 5.00 mL to the beaker. To give the same total volume and concentration of ions
add 2.50 mL of 0.10 M KCl to the beaker containing the KI.
For the third run, you will need to throw out the room temperature water in the tray and replace it
with warm water obtained in the sink. You may have to run the hot water a few minutes for it to
warm up. Adjust the temperature in the tray to where it is anywhere from 10 to 15 degrees
warmer than your previous two runs. For this run, go back to 5 mL of KI and no KCl like the
first run. Otherwise, everything will be the same as the first run.
If you have problems with any of the three kinetics runs, you should have time to rerun it.
Treatment of Data
A. Obtaining the rates
Convert all of the times for the three data runs to total elapsed seconds. Now you will need to
graph the volume of O2 as a function of the total time in seconds. Use a spreadsheet to do this.
In the second lab of the year you made a graph using Excel. Create a graph for each kinetics
experiment you ran. And use linear least squares to find the initial rates of reaction. If you find
that your data is not very linear, favor the first few points. The units of the slopes should be
mL/s.
Now convert the slopes to units of moles of O2 per second. The instructions for this calculation
are in the background information, equation (2). You will need to use the atmospheric pressure
you have measured and subtract the vapor pressure of water at the temperature of the experiment.
It will have to be converted from units of torr to atm. You will also need to use the room
temperature you have measured for further calculations. Do not use the tray water temperature
for this calculation. Most of the O2 gas will be at room temperature rather than the water
temperature. The slopes you have just calculated are the initial rates of the reaction under the
three different conditions.
29
30
31
32
(1)
This reaction, an equilibrium reaction, proceeds both in the forward and reverse directions. At
the start of the reaction, there are no products and so the reaction proceeds only in the forward
direction, but as products are formed, the reverse occurs as well. Eventually, at equilibrium, the
rate of the forward and reverse reactions are equal, so the concentrations of product and reactants
no longer change.
It is possible to perturb an equilibrium causing a shift in the equilibrium concentrations.
Le
Chateliers principle tells us that an equilibrium reaction will shift to alleviate a stress put upon
the system. If a species in the equation is added, the equilibrium will shift away from the
species to reduce its concentration. If a species in the equation is removed, the species will shift
toward that species to increase its concentration. This includes the addition or removal of heat;
for an endothermic reaction heat is a reactant, for an exothermic reaction heat is a product.
You decide that a good place to start is to probe this equilibrium reaction and see if it can be
shifted towards the creation of more product.
33
Finding the equilibrium concentration of Fe(SCN)2+. You know that SCN- is clear and
colorless, this is what makes it so hard to test for. The product of our equilibrium reaction,
Fe(SCN)2+, however, is colored. By finding the equilibrium concentration of the product, the
concentration of the reactants may be found. You suspect that we can find the concentration of
this product by absorption spectroscopy, but we need to find the molar extinction coefficient for
this substance to do so.
You remember from the lab on absorption spectroscopy that Beers Law is:
A = bc
(2)
Where A = absorption (no units) , = molar extinction coefficient (L/mol cm, b = path length of
the absorption cell (1.00 cm) and c = concentration of the species (M). To find you and your
team decide to create a series of SCN- standards, pair them with a known and constant
concentration of Fe3+, measure the absorbance of the Fe(SCN)2+ complex and create a graph of
SCN- vs complex absorbance where the slope of the line is .
Finding the equilibrium constant for this equilibrium equation.
Now that you have , you can use this value to find the equilibrium concentration of Fe(SCN) 2+.
Once you know the equilibrium concentration of Fe(SCN) 2+, you can use that concentration to
find the equilibrium concentration of the reactants, including SCN -.
The first step is writing the equilibrium expression. In the equation below
cC + dD
aA + bB
The equilibrium expression is:
[C]c [D]d = K
[A]a[B]b
(3)
Where K is the equilibrium constant. The value of K will allow us to calculate equilibrium
concentrations of our substances, but it also gives us information about our equilibrium reaction.
If the value of K is greater than one, then the products are favored, if the value of K is less than
one then the reactants are favored. If the value of K is equal to one, then neither is favored.
(Really we say that neither is favored very much if 1 x 103 Kc 1 x 10-3.)
Experimental Details
Part One. Exploring the Equilibrium Equation and how to shift it.
Set up 5 medium test tubes in a rack and label them 1-5. To each test tube, add 20 drops of
0.0075M Fe(NO3)3 and 20 drops of 0.0075M KSCN. This should be the reaction at equilibrium.
Dont do anything to test tube 1- this is the undisturbed equilibrium reaction and is your control.
Add 10 drops of 0.1M Fe(NO3)3 to test tube 2 and mix the contents. Add 10 drops of
0.1MKSCN to test tube 3 and mix the contents. Place the 4 th test tube in a boiling water bath on
a hotplate. Place the 5th test tube in an ice bath. Make observations.
34
mL 0.20M Fe(NO3)3
5
5
5
5
5
mL 0.0020M KSCN
0
1
2
2.5
3
mL 0.10M HNO3
25
24
23
22.5
22
Mix the samples using a glass rod, careful not to cross contaminate. Use the Ocean Optics
spectrometers to read the samples:
1.
2.
3.
4.
5.
6.
7.
The instrument should already be hooked up to a lap top computer and a printer and turned on, but must be
calibrated prior to use. From the top tool bar, click on Experiment and choose Calibrate Spectrometer and
follow the directions in the dialog box and click OK when finished. Instead of using an empty cuvette, fill a
cuvette about full of DI water for calibration. The calibration box counts down from 1 minute to warm up the
lamp before you put the cuvette in the sample compartment. Three minutes is better if you are the first group to
use the instrument that lab period. The cuvette should be inserted so that the 1 cm side is in the light path.
Dump out the water and add a small amount of the stock solution to the cuvette, swish around and empty it. Fill
the cuvette to about 3/4 full with the stock solution. This should eliminate any dilution effects from water
having been in the cuvette. Wipe off the outside with a Kimwipe, and place the cuvette into the sample
compartment making sure it is oriented correctly. Click on the Configuration Spectrometer Data Collection
icon located on the right hand side of the toolbar. It has colored bars under a spectrum.
Click box on Abs vs. Concentration (under Set Collection Mode; it may already be correctly selected). The
wavelength of the maximum absorbance will not be automatically selected. Check the box at 447 nm. Click
OK to close the display.
Click on Collect icon on the tool bar at top. Next click on the Keep icon at the far right of top tool bar.
Enter the concentration of the sample in the box that comes up and click OK.
Empty the cuvette, add a small amount of one of your diluted samples to the cuvette, swirl it around, then pour
it out. Fill the cuvette about 3/4 full with the diluted solution and put back in the sample compartment. The
absorption value will show at the left below the tool bar. Click on Keep and enter the concentration of the
initial KSCN in your solution. Continue measuring and entering the rest of the diluted samples.
Click on the Stop icon when data on all 5 solutions has been taken. Click the linear fit icon to have the
computer draw a best fit line through your data. If the plot is not scaled correctly, you can use the auto scale
icon or put the cursor on the numbers on the axis and type in a new value. Sometimes it is difficult to get the
cursor to lock on the number. When locked the computer will place a box around the number and then you type
in the new value.
The slope of the line is our value. Print your graph to include with your report.
How do you calculate the KSCN concentration for each sample for your graph? Lets calculate
the Fe(NO3)3 concentration instead as an example using the dilution factor:
0.20M X 5mL = 0.033M
30mL
(4)
35
mL 0.0020M KSCN
9
8
7
Mix the samples, careful to avoid cross contamination. Use the Ocean Optics Spectrometers to
read the samples.
1.
2.
3.
4.
Now you need to calculate the value for K. First, using Beers law and the molar extinction
coefficient you calculated, calculate your equilibrium value for Fe(SCN) 2+ by rearranging
equation 2:
c = A/b
Next you need to find the equilibrium Fe3+ concentration:
[Fe3+]eq = [Fe3+]in [Fe(SCN)2+]eq
(6)
Where eq = equilibrium concentrations and in = initial concentration. Next you need to find the
equilibrium SCN- concentration, which is found the same way as the Fe3+ concentration, just
with the initial concentration of SCN- instead. Remember to use your dilution factors as in
equation 4. Now plug all three numbers into equation number 3 and solve for K. Do this for
each of the three solutions, calculate an average and standard deviation for K and report these.
36
How could your team use this knowledge to design a test for SCN - in water?
37
[Fe(SCN)2+] [Fe3+]eq
(M)
(M)
F
G
38
[SCN-]eq
(M)
K (M-1)
The primary buffering agent in the blood is the carbonate system. There are two equilibria
required to describe this buffer system:
CO2 + H2O
H2CO3 + H2O
H2CO3
H3O+ HCO3-
The buffering action derives from the second equilibrium but the first equilibrium governs how
much carbonic acid is present. The carbonic acid concentration is a function of the amount of
dissolved CO2 from the respiration process. Without the first equilibrium replacing H 2CO3 as it
is neutralized by a base, the system would not have much buffering capacity against bases.
When you test this buffering system in the lab, you will not have the source of CO 2 to replace the
H2CO3 and you should find it to have a low base buffering capacity.
The most important buffering agent for intracellular fluid is the phosphate system. The buffer
mixture functions through the equilibrium:
(OH)2PO2- + H2O
(OH)PO32- + H3O+
The total concentration of phosphate species in the cells is about 0.02 M. Histidine also helps
buffer the intracellular fluid although you will not be testing that system.
Scenario
You are working as an assistant for the biology program and have been asked to come up with a
recipe for making 1 liter of buffer solutions to model those of the human body for use in a
physiology lab. The pH is to be 7.4. The buffering capacity of the buffers is needed as well to
make sure they will work for the experiment they are to be used for. You have decided to make
up 100.0 mL of both the carbonate buffer system and the phosphate buffer system at
concentrations of 0.020 M which is close to concentrations found in the body. The recipe can
then be multiplied by 10 for liter portions. You will split each of the buffers you make into two
50.0 mL portions and then test the buffering capacity against addition of acids with one of the
50.0 mL portions and against bases with the other 50.0 mL portion. Standardized 0.10 M HCl
and 0.10 M NaOH are available in the lab to use for adjusting buffer pH and as the source of acid
and base to test the buffer capacities.
A check of the stockroom indicates you have KH 2PO4 and K2HPO4 from which to make up the
phosphate buffer system. You know that the total phosphate concentration should be 0.020 M.
You will need to look up the pKa2 of phosphoric acid and use the Henderson-Hasselbalch
equation to calculate what concentrations of KH2PO4 and K2HPO4 you will need to make up your
buffer having the sum of the concentrations of H2PO4- and HPO42- add up to a value of 0.020 M.
You will prepare the buffer using tap water and test its pH. Theory and experiment dont always
agree as contaminants in the water or in the reagents may prevent the buffer from giving the pH
calculated by the Henderson-Hasselbalch equation. You will need to adjust the buffer to the
correct pH by addition of HCl or NaOH which will shift the equilibrium between the H 2PO4- and
40
HPO42- without changing the total amount of phosphate species present. Your final recipe will
include masses of KH2PO4 and K2HPO4 and volume of either 0.10 M HCl or 0.10 M NaOH to
bring the liter of tap water to the correct pH. After making up the buffer, take 50 mL samples
and test the buffering capacity, one with 0.10 M HCl and one with 0.10 M NaOH.
The stockroom does not have carbonic acid, but you find plenty of NaHCO 3. A little thought
(and a visit to your general chemistry textbook) gives you the idea that you can start by making
100 mL of 0.02 M NaHCO3 and then partially neutralize it with 0.10 M HCl to make H 2CO3
until you have the desired pH of the buffer. You must record how much of the HCl is required
for your buffer recipe. After addition of HCl to make the buffer, you will take two 50 mL
portions and test each for its buffering capacity against 0.10 M HCl and 0.10 M NaOH.
Instructions
Before coming to lab, work out and write down in your lab notebook the moles and grams
required of KH2PO4 and K2HPO4 to make up the phosphate buffer system. Check this with your
group members to see if you agree before proceeding to weigh out samples. Likewise, calculate
how many grams NaHCO3 are required to make up 100 mL of 0.020 M solution of NaHCO 3 and
check with your group.
When you get to lab you will have several tasks to do. Meet together and make assignments.
The KH2PO4 and K2HPO4 need to be weighed out and added to 90 mL of tap water to make up
the phosphate buffer system in a beaker. NaHCO3 needs to be weighed out and added to 90 mL
of tap water to make up the carbonate buffer system in another beaker. (Label each so you dont
get them confused). In both cases, using your graduated cylinder to measure out the tap water
should be accurate enough. Try to make the masses close to what you calculated, but dont
spend too much time with this. Record actual masses weighed out for use in calculating your
recipes in your lab notebooks. Your group will need two burets and a buret clamp. Check the
burets for cleanliness, rinse and fill one with 0.10 M HCl and rinse and fill the other with 0.10 M
NaOH. Make sure you pass some solution out of each of the two burets to rinse the tips and
remove the air in the tips. You need to turn on and calibrate your pH meter so it is ready to make
pH measurements. You will need a wash bottle filled with de-ionized water for washing the pH
electrode and a beaker to catch the water used for washing.
You will get instruction on use of the pH meters during lab. Every time you add acid or base to
the mixture, you need to stir the solution with a magnetic stir bar. Stir carefully, keeping the bar
away from the electrode. Be very careful with the electrode; it is made of very thin glass and is
rather expensive.
After you have your preliminary buffers made, your pH meter set up and calibrated and your
burets filled, you are ready to make measurements. With the phosphate buffer, take its pH. If it
is not in the range of 7.35 to 7.45, slowly add HCl or NaOH to adjust the pH to the correct value.
You will need to measure the volume of acid or base added by reading the buret before and after
each addition. If you overshoot, you can back-titrate to the correct value but you must then
adjust to the correct value for your report. For example, if you are adding base and you
overshoot to pH of 7.5, you can add HCl to bring the pH back down to pH of 7.4. Suppose it
took 0.05 mL of acid to do this. Then the volume of base for your recipe calculations should be
41
reduced by the 0.05 mL. You can use volumes to correct because the concentrations of the acid
and base are equal. When the pH is in the correct range carefully pour your buffer into a 100
mL volumetric flask. Fill up to the mark the tap water.
Split the buffer into two 50 mL portions. To one, add small portions of 0.10 M HCl. Read the
buret and take the pH with each addition until you have dropped a pH unit. Do the same with the
other portion adding 0.10 M NaOH until the pH has gone up one unit. Make additions slowly as
you approach the desired pHs as the electrode is slow to respond. If you go over, record the
amounts of acid or base added and the pH. Using the values of volume and pH before and after
exceeding the correct amount, you can estimate the amount of acid or base that would have
changed the pH to the correct value. Calculate the moles of acid and base to change 1 liter of the
buffer by one pH unit.
To the solution of NaHCO3, add small portions of 0.10 M HCl until the pH drops to the desired
range of 7.35 to 7.45. This should take only about 2 mL so be careful not to exceed the desired
amount. If you overshoot, you can back-titrate as with the phosphate buffer and make the
corrections for your recipe. Now split this buffer into two equal portions and run the same buffer
capacity experiments with HCl and NaOH that you did with the phosphate buffer. Calculate
quantities to make up 1 liter of buffer and moles of acid and base to change 1 liter of buffer by
one pH unit. Can you see any bubbles form in this buffer, particularly when you test its buffer
capacity against addition of an acid? What do you think the bubbles are? How might this effect
the stability of the carbonate buffer?
All leftover solutions can be disposed of down the sink.
Report
Generate a brief report addressed to the Biology Department that includes the following:
1. The lab cover page.
2. Final recipe for 1 liter of the phosphate buffer that reflects masses and volumes measured.
3. Final recipe for 1 liter of the carbonate buffer that reflects masses and volumes measured.
4. Acid and base buffer capacities for 1 liter of both buffers.
5. Make a recommendation as to which buffer system is best based on buffer capacity and
stability of the buffer.
Make sure your recipes are complete enough that a non-chemist could follow them.
Attach duplicate lab notebook pages. The notebooks should contain the pre-lab exercises on the
calculations for making the 0.020 M phosphate buffer and the 0.020 M NaHCO 3 solution, data
and observations on making up the phosphate buffer, procedure for using the pH meter, data and
observations on making up the carbonate buffer and data on the buffer capacity measurements.
42
43
44
c. Calculate the percent difference between the two values. Show the calculation below:
45
c. What is the pH of the equivalence point from your graph? Circle it on your graph and
report it here.
d. Calculate the percent difference between the two values. Show the calculation below:
46
47
is abbreviated Ksp, the solubility product constant. For example, for barium phosphate, the
equilibrium is written as:
Ba3(PO4)2(s)
3 Ba2+(aq)
2 PO43-(aq)
Procedure
WEEK ONE
A. Preparation of necessary solutions
1. The calcium oxalate will be prepared from calcium chloride(aq) and potassium
oxalate(aq). A stock solution of 0.10 M CaCl2(aq) will be available in the lab. You
should prepare 250 mL of 0.010 M CaCl2(aq) from this stock solution, using a 250 mL
volumetric flask. (Remember the dilution equation: M cVc = MdVd ; solve for Vc to
determine how much of the 0.10 M CaCl2 solution you need) A stock solution of 0.10 M
K2C2O4(aq) will also be available in the lab. Use the stock potassium oxalate solution
48
49
5. Repeat for the other kidney stone salt labeled chelating effect.
6. For each titration, calculate the moles of titrant added. Does this agree with what you
would predict based on the stoichiometry of the reaction between the titrant and the
reactant? Note that one mole of Na4EDTA will complex one mole of Ca2+.
C. Effect of solubility in water.
1. Use a medicine dropper to pull off a few milliliters of the clear liquid above the
precipitate in the sample labeled Ca3(PO4)2 for solubility. Put the liquid in a small test
tube and then add a few drops of concentrated Na 3PO4 solution. What do you observe?
Was there still some Ca2+ ion remaining in solution?
2. Using the Ksp values you measured last week, calculate the amount of water you need to
add to the 0.25 g sample of Ca3(PO4)2 precipitate to dissolve it. Do not attempt to add
the water and actually dissolve it.
3. Repeat steps 1 2 with the sample labeled CaC 2O4 for solubility adding concentrated
K2C2O4 to test the solution in step 1.
REPORT
The report should be typed and include the following information, written in sentence format
where appropriate (calculations can be handwritten if you wish).
Completed lab cover sheet.
Statement of problems addressed and methods used to solve them.
Solubility equilibria and Ksp expressions for each kidney stone salt.
Values of Ksp determined for each salt.
Predictions of effect of pH, Na4EDTA, and large volumes of water on the solubility of
kidney stone salts, using solubility equilibria as the focus of the discussion.
Discuss whether your predictions were in fact borne out by the experimental data and
calculations.
Discuss whether you could use the results from this experiment for in vivo (in the body)
dissolution of kidney stones.
Look up at least one site on the Internet on kidney stones, reference it by giving the full URL
and the date accessed, and briefly indicate whether your conclusions are supported by the
reference.
Duplicate pages from lab notebooks should be stapled to the back of the report. These
should include: (Make sure everything is well labeled)
I. Week One
Pre-lab exercise.
Data and calculations for preparation of solutions.
Data for preparation of kidney stone salts for Ksp calculation.
Calculations of Ksp for each kidney stone salt.
Calculations and data for preparation of 0.25 g of each kidney stone salt.
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Another factor is that of S, entropy. We have described entropy before as the change in
randomness. I think you would agree, that when a solid dissolves that the entropy of the system
should increase as the ions flying around in solution are more random than the solid sitting in the
bottom of the beaker.
To calculate the thermodynamic factors we will use two equations. For each Ksp you calculate,
we can calculate G from it:
G = -RTln(Ksp)
G is Gibbs free energy. This is the energy available to do work. When G is negative, the
process is said to be spontaneous and the free energy generated can be harnessed to do work.
When G is positive the process is said to be non-spontaneous and energy must be added for the
process to run.
If we now graph our G values vs the T (temperature, in what units?) at which we ran the
process, we can find our other thermodynamic parameters:
G = H TS
The slope of our line is equal to S and the y-intercept is H.
What is the significance of all this information to your Facebook friend? Your call!
Procedure
Add 100.0 mL of DI water to a beaker and about 2 g of Ca(OH) 2 (report how much you added)
and take the temperature of the water to 0.1C. Stir with a magnetic stir bar for 5 minutes. If
the solid is gone, or almost all gone, add another 2 g of Ca(OH)2 and stir for another 5 minutes.
Repeat until no more goes into solution. Suction filter the solution to remove the solid. (The
clear filtrate will be titratedis it clear? If not, filter again.) Use a pipet to remove 10 mL of
this filtrate into a 125 mL Erlenmeyer flask. Add 25 mL of DI water, 10 drops of bromothymol
blue indicator (why did we choose this indicator?) and the stir bar. Titrate this solution to the
yellow endpoint with 0.050M HCl. Repeat this titration with a second aliquot of filtrate.
You are going to repeat this process, but at a different temperature. Your instructor will tell your
group which temperature range your group will use. You will be pooling your lab data.
For 0-5C you will have your Ca(OH)2 dissolving with magnetic stirring in water in a beaker
inside of an ice bath. Measure the temperature of this solution to 0.1C, but make sure that it is
in the desired range. Quickly filter the solution and continue as above.
For 10-20C you will need to use the ice bath as above, but will need to adjust the water/ice
mixture so that the temperature is within the desired range (More water than ice). Quickly
filter the solution and continue as above.
For 40 - 50C you will need to heat your water on a stirring hotplate, add the Ca(OH) 2, and
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maintain the temperature throughout the dissolving process. At the end, just before you filter,
record the temperature to 0.1C, making sure that it is in the desired range. Quickly filter the
solution, but then let it cool to room temperature before titrating.
For 60-70C, proceed as above, but at this elevated temperature range.
For 80-90C, proceed as above, but at this elevated temperature range.
Calculate the OH- concentrations from your titrations and from that, calculate the Ca 2+
concentrations. Use these to calculate Ksp at the four different temperatures. Ksp will allow
you to calculate G and a graph of G on the Y-axis and corresponding T values on the X-axis
will allow you to report S and H.
Report
Type a note to your friend explaining why Ca(OH)2 dissolves. Include the following:
1. Describe to your clueless Facebook friend what happens when an ionic compound
dissolves in water.
2. Explain what Ksp is and tell him your findings. What does the value of Ksp at the
different temperatures tell you about how soluble Ca(OH)2 is in general and at different
temperatures.
3. Explain what S, H, and G are and what you found. How does the thermodynamic
data explain the solubility of Ca(OH)2? Is it exothermic or endothermic? Spontaneous
or non-spontaneous? Does entropy increase or decrease?
4. Extort your friend for money
5. Include the yellow sheets for all group members and the graph.
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Experiment 10 - Electrochemistry
Learning Objectives
To learn about electrochemical cells
To be able to predict cell potentials
Learn how to use a voltmeter
To explore how temperature effects cell potential
To calculate G, K, H, and S for a redox reaction
Pre-lab Exercise
1. Using Table 19.1 in your textbook, write the standard reduction half-reactions and find
the standard reduction potentials for the following metals. Assume complete reduction of
the metals to solid. Metals: Fe2+, Cu2+, Mg2+, Al3+
2. Calculate the total cell potentials for the six possible Galvanic cell combinations using
the metals in the questions above.
Scenerio
Electrochemistry is the study of the conversion between chemical energy and electrical energy.
Reactions of this sort are also called redox reactions as they utilize oxidation and reduction of
elements to transfer electrons. Our bodies run on electrochemical reactions. Adenosine
triphosphate (ATP) is the energy molecule used by the body to fuel cellular reactions. The
chemical processes used to produce ATP are oxidation-reduction reactions and are known as the
electron transport chain.
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Background
Electrochemical Cells
When an oxidation and a reduction reaction are paired together in a redox reaction, electrons can
flow from the oxidized species to the reduced species. The flow of electrons can be observed
when an electrochemical cell is constructed. A galvanic cell contains a spontaneous reaction that
drives the electron flow. An electrolytic cell needs an outside source of current to drive a nonspontaneous reaction. We will be measuring the potentials of spontaneous reactions using a
Galvanic cell.
An electrochemical cell is composed of two parts commonly referred to as half cells. A half-cell
is the part of the electrochemical cell that houses the electrode. The electrode can be either an
anode (where oxidation occurs) or a cathode (where reduction occurs). Connecting the two halfcells is a salt bridge that allows charge to flow through the system.
An important concept related to electrochemistry is the standard reduction potential (E), which
is a quantitative measure (in volts) of a particular substances tendency to accept electrons under
the standard condition of 1.0 atm and 1.0 M. A table of standard reduction potentials is found as
Table 19.1 in your textbook. Observing the table, you will notice that the series of half-reactions
is listed in descending order from the most positive value to the most negative value. In general,
the more positive the standard reduction potential is for a particular substance, the stronger its
tendency is to be reduced. In a Galvanic cell, the metal with the more positive potential will be
the cathode (be reduced).
A measure of how much energy flow we get from a cell can be calculated as the overall cell
potential (Ecell). The overall cell potential is expressed as:
Ecell = Ecathode - Eanode
The theoretical cell potential can be calculated using the reduction potentials found in your
textbook. The actual reading on the voltmeter should be close to the value you calculate,
although remember you will not be working at exactly standard conditions. Even so, most of the
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error can be explained by other sources such as resistance in the salt bridge or lack of calibration
of the voltmeter.
Free Energy and the Nernst Equation
The value of G for a reaction at any moment in time tells us two things: (1) the sign of G tells
us whether a reaction is spontaneous or not as written; and (2) the magnitude of G is a measure
of the spontaneity of the process and is defined mathematically by the equation:
G = -nFEcell
In this equation, the variables are as follows: n is the number of moles of electrons transferred; F
is Faradays constant (96,500
); and Ecell is the observed overall cell potential.
Procedure
A. Construction of a Salt Bridge
1. Place 50 mL of 0.1 M KNO3 in a 250 mL beaker. Use a hot plate and bring it to a boil.
2. Remove the solution from the heat and add 0.50 g of agar while constantly stirring.
3. Use a disposable plastic pipet to transfer the agar-KNO3 gel into an inverted U-tube until
the gel fills all but 2.5 cm at the end of the tubes.
4. Place the U-tube open-end up in a beaker filled with ice and allow to cool for 15 minutes.
5. Fill the spaces on each end of the U-tube with cotton plugs. Make sure the cotton contacts
the agar gel and also protrudes from the tubes.
6. Label each side of the tube, near the bend, with the name of the metal for which it will be
used.
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Part C: Data and Calculations for Temperature Effects on Potential (your data only)
Temperature
Cell
G
K
Potential
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Discuss the relationship between the experiment cell potential and temperature:
What do the G, H, and S values for each cell tell you about the reaction(s) taking place
in the cells?
What does the sign and magnitude of E tell you about the cell?
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