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Overview for the Biofuels Unit

This set of three laboratory experiments introduces students to biofuels. These labs,
which can be run in three consecutive weeks, give students the opportunity to explore the
chemical properties of biofuels from three different perspectives. During the first week
students are introduced to toxicology, including the use and limitations of LD
50
values.
Students then make up standard dilutions of various biofuels and set up a simple
germination assay to quantify the potential ecotoxicty of each of the fuels.

The second week of the unit has the students synthesize biodiesel from soybean oil. In
addition to introducing techniques of synthetic chemistry, this lab focuses on concepts of
stoichiometry, limiting reagents, and reaction yield. The synthesis of biodiesel can be set
up in less than an hour, and the rest of the lab period is used to collect the data from the
germination experiment which has been incubating for a week.

The final lab of the unit challenges students to determine the heat of combustion of their
biodiesel using a simple soda can thermometer. This lab introduces heat transfer and asks
students to consider the relationship between the heat of combustion of a fuel and
efficiency of a fuel.

The themes of the unit are synthesized by the students in a final assignment. The students
are asked to write a short paper evaluating biodiesel and one other biofuel as alternative
transportation fuels. They are told to use data they collected along with supporting
information from scientific sources to support their conclusions. This short paper gives
students a chance to reflect on what they have learned and see how it applies to the
energy challenges facing our society.

Timeline:
Week 1- Set up germination assay
Week 2- Run biodiesel reaction
- Collect data from the germination assay
Week 3- Conduct separation and purification of biodiesel
- Determine the Heat of Combustion for biodiesel

Dose Makes the Poison: Estimating the
Relative Ecotoxicity of Various Biofuels

"All things are poison and nothing is without poison; only the dose makes a thing not a
poison."
- Paracelsus (14931541)

Chem Connections:
The central theme of green chemistry is the design of materials and processes that
are inherently safer for human health and the environment. In order to achieve this goal,
we need to be able to quantify how harmful or toxic a substance is to humans or the
environment. There are many different ways to quantify the toxicity of a chemical. The
most common is the mean lethal dose, or LD
50
. This is the amount of a chemical
substance that it takes to kill half the members of a test population for a given exposure
and amount of time. The LD
50
is usually expressed with units of amount of
chemical/weight of animal, so that values can be compared between different size
animals. For example the LD
50
for sodium cyanide is 6.3 mg/kg. This means that if you
give 6.4 mg of sodium cyanide to a 1 kg rat, it has a 50% chance of dying as a result of
that exposure. The mean lethal dose for a 60 kg human would be 6.4 mg/kg 60 kg =
380 mg. The first activity in this experiment will give you a chance to examine more of
these values for various chemical substances.
It is important to realize that the LD
50
is not the only measure of chemical
toxicity. There are many other possible outcomes from chemical exposure that are less
severe than death, but that are still of concern. These include the chemicals ability to
cause cancer, disrupt hormone function, or cause birth defects. In order to quantify these
affects one current testing method uses large numbers of laboratory animals, many years,
and millions of dollars. These methods have been criticized by many animal rights groups
and others as being wasteful and inaccurate. In response to these shortcomings many
scientists, companies, and governments are developing new methods to evaluate toxicity.
In todays lab we are going to measure how various chemicals affect the
germination of plants. We have chosen this test system because we can obtain
quantitative data over the course of a week, rather than the many weeks, months, or years
that it takes to evaluate chemical exposure in animals. We will be examining various
chemicals that have been suggested for use as alternative fuels. All of the fuels we will be
testing can be derived from plant resources, and include biodiesel, methanol, ethanol, and
2-butanol.





Prelab Activity


Often chemists rely on published safety information, rather than experiments to
determine the risks associated with chemicals. There are many sources for this
information; the most common is the Material Safety Data Sheet (MSDS). For the
following three chemicals, you will need to find safety information using a few of the
common resources available to chemists. Look up each of these chemicals in each
resource, and then answer the following questions.

Chemicals:
1) Bisphenol A (BPA) chemical name: 4,4'-dihydroxy-2,2-diphenylpropane
a. This is the chemical which has created the public concern over plastic
water bottles.
2) Lead (Pb)
a. Recently found in children toys.
3) Dioxins class of chemicals. In particular look up 2,3,7,8-tetrachlorodibenzo-p-
dioxin
a. This chemical is why you should not burn plastic, and is one of the few
chemical restricted by the EPA.

For each of these chemicals find safety information using the following resources:

1) MSDS: From any UC campus computer you can search the UC database at
www.ucmsds.com. Another way to quickly find a MSDS is to do a google search
for: msds chemical name.
2) Wikipedia, yes I want you to use Wikipedia. http://www.wikipedia.org/
3) ChemSpider: This is a website hosted by the Royal Chemical Society:
http://www.chemspider.com/

Questions:

1) Which of the three chemicals would you consider most hazardous? Why?

2) What precautions should you take, if you were using each of these chemicals?
Which resource gave you this safety information?

3) Is there safety information that is missing from these resources that you would
like to have before working with these chemicals? Is so, what information would
you like?

4) Which sources of information are you most likely to use in the future? Why?

Experimental Procedure

Exercise 1: Become familiar with LD
50

Chemicals with large LD
50
values are less likely to harm animals than chemicals with
small LD
50
values. LD
50
values are expressed as the amount of chemical administered
(usually expressed in mg) divided by the mass of the animal (usually expressed in kg).
For example the LD
50
value for the sodium cyanide is 6.4 mg/kg, while the value for
vitamin C is 11,900 mg/kg. So we would expect that it would take less than a gram of
sodium cyanide to kill a 150 lb human, while it would take more than 1.5 lbs of vitamin
C to kill a human.

For the following table fill in the missing values, and then answer the questions below:
Chemical Name Structure LD
50

(mg/kg)
Estimated Lethal Dose for a
60 kg human
Sodium Nitrite (NaNO
2
)

180
Arsenous Acid
(As(OH)
3
)

14
Aspirin (acetylsalicylic
acid)

200 12 g
Sodium Cyanide
(NaCN)

380 mg
Polonium-210

0.00001
Mercury (II) Chloride
(HgCl
2
)

60 mg
Tylenol
(acetaminophen)

1944


1) Rank the substances from most to least acutely toxic.

2) Guess which substance claims the most human lives every year? Explain your
reasoning.

3) Doctors have recommended against giving children aspirin, and instead
recommend acetaminophen. How many 500 mg tablets of aspirin would it take to
reach the LD
50
threshold for a 22 lb (10 kg) child? How many 500 mg tablets of
acetaminophen?

Exercise 2:
Estimate the Ecotoxicity of biofuels using a seed germination assay. This Exercise will
take place over 2 lab sessions. During the first you will prepare your samples and
solutions. The data collection and analysis will then occur during the second lab period
after you set up the biodiesel synthesis.

The Approach
Work in groups of 2.

Equipment needed:
6 plastic petri dishes with covers
12 filter papers large enough to cover bottom of petri dishes
300 Lettuce or Radish seeds
Parafilm to seal each petri dish (6 pieces, 2-2.5 squares in length)
Scissors to cut filter paper
Ruler with mm (needed for day two)

Chemicals Needed:
Deionized Water
Biofuels of interest
Ethanol
Biodiesel (Methyl Linoleate)
2-Butanol
Methanol

Biofuel Structure
Molar
Mass
(g/mol)
Density of
pure biofuel
(g/mL)
Ethanol


46.07 0.789
Biodiesel
(Methyl
Linoleate)

294.47 0.889
2-butanol

74.12 0.808
Methanol

32.03 0.791



Part 1- Sample preparation
1. Obtain six plastic petri dishes, 12 filter papers, and 300 radish seeds. (300 radish seeds
should weigh about 2 grams.)

2. Prepare the dishes by putting a piece of filter paper and 50 seeds into each dish. If
necessary, cut the filter paper to completely cover the bottom of the petri dish. The seeds
should be evenly distributed on the filter paper then cover the seeds with a second piece
filter paper.

3. Make a 10% solution of your fuel of interest. In a
graduated cylinder, place 2 mL of fuel and dilute with 18
mL of water. Transfer this solution to a 50 mL beaker.

(Note: Some residual fuel will remain in the graduated cylinder if you are using
biodiesel. Get as much as possible into your beaker and put it on a stir plate and stir very
rapidly to make an emulsion. The emulsion should appear cloudy.)

5. Transfer exactly 10 mL of your 10% solution to the first petri dish using the same
graduated cylinder. Be sure to label the lid of this petri dish 10%

6. Add 10 mL of deionized water to the remaining 10 mL of the 10% solution. You have
now made a 5% solution. The technique of diluting a solution with a known quantity of
solvent, is called serial dilution. If you double the volume of a solution, you divide the
concentration by 2.

7. If your solution has separated be sure to recreate the emulsion by stirring.

8. Now take 10 mL of your 5% solution and add it to the second petri dish. Dont forget
to label the dish!

9. Now continue the serial dilution by adding 10 mL of deionized water to the remaining
5% solution, making it a 2.5% solution. And then add the volume to the next petri dish,
label, and repeat for the remaining 2 petri dishes.

10. In the end you will have petri dishes labeled 10%, 5%, 2.5%, 1.25%, and 0.625%

11. In the final petri dish, add 10 mL of deionized water. This will be your control
sample, and will be used to compare to all of the other samples.

12. Seal all of the petri dishes with parafilm to reduce evaporation of your solutions and
store the petri dishes in your lab drawer until the next lab period.


Part 2: Data Collection
Complete the data tables below.

Table 1: Germination

1. Count the number of seeds germinated in each dish, then calculate the percentage that
germinated.
Control 0.6% 1.25% 2.5% 5% 10%
# of Seeds
Germinated
(count)


Percentage

Germinated/
Total




Table 2: Root Elongation for germinated seeds

1. For the root elongation, only count seeds that germinated.
2. Measure the root, not shoot or seed body, to the nearest mm. Record the lengths in
your lab notebook. You will need these values.
3. If the root is bent, try rolling it along the ruler to estimate the length.
4. If the roots break, do your best to still do the measurement.
5. Use excel or a graphing calculator to obtain the average and the standard deviation for
each concentration.
Control 0.6% 1.25% 2.5% 5% 10%
Average root
length of
Seeds which
Germinated
(mm)


Before leaving lab write your percent germination and average root length values on
the chalk board.

Post lab Questions:

1) Graph the percent germination class data using a program like Excel or using
graph paper. Make a separate graph for each fuel. Express the percent of seeds
germinated as the percent biofuel in solution increases. Also include a plot of the
class averages.

EXAMPLES!

2) Compare the results for each of the biofuels examined in your lab section. Based
on the data, which fuel seems to be the most toxic to seeds? Do the fuels effect
both germination and root growth in the same fashion?



3) Express the percentage solution values in units of molarity (mol/L). Compare the
molarity of the 10% solutions for each of the biofuels used in your lab sections.
Does knowing the molarity of each of these solutions change your opinion of
which fuel is most toxic? Why? Suggest additional experiments to support your
conclusions.



4) Look up the LD
50
values for each of these fuels, how do the LD
50
values compare
to the trend you saw in class? The LD
50
value for biodiesel is hard to find,
because the LD
50
values are considered to be higher then the threshold for harm in
the species tested. In other words, the toxicity of biodiesel is insignificant.
(Remember that LD
50
values are a measure of animal, not plant toxicity!)

Bibliography
This lab was inspired by the work done by faculty and students at Gordon College,
who kindly shared their material on the GEMS database.
1) Soo Y. Kwon, Irvin J. Levy, Matthew R. Levy, Daniel V. Sargent, Dwight J.
Tshudy, and Marissa A. Weaver, "The dose makes the poison: Measuring
ecotoxicity using a lettuce seed assay" Department of Chemistry Gordon College.
GEMS database 2010.

Background reading for the LD
50
values can be found in the following sources.
2) Timbrell, J. Introduction to Toxicology, CRC Press: New York, 2002.
3) Girard, J. Principles of Environmental Chemistry 2
nd
ed., Jones and Bartlett Press:
Boston Mass. 2010, Chapter 16.

Synthesis of Biodiesel


Chem Connections:
The diesel engine was first designed by Rudolf Diesel in 1895. The original diesel
engines had two key design features. First they used heaver fuels, in other words, fuels
with longer carbon chains. Typical gasoline engines use saturated hydrocarbons with 7-
11 carbon atoms per chain (high octane fuel). Diesel engines use fuels with longer chains,
often containing between 12-18 carbon atoms. Rudolf Diesel envisioned running his
diesel engine with vegetable oil, which contains three chains that are 16-18 carbons long
(See Figure 1: octane, soybean oil, and petroleum diesel, biodiesel). His design became a
reality in 1900, when the first diesel engines where produced and used peanut oil as a fuel
source.
The second distinguishing feature of a diesel engine is that the fuel ignites without
using a spark system. Compression of air before injection of the fuel creates heat, which
ignites the fuel in a diesel engine. This is a great application of the ideal gas law!
This simple design allows engines to operate with higher efficiency than traditional
gasoline engines which rely on spark plugs to ignite the air/fuel mixture.
These two design features, multiple fuel sources and higher efficiencies, have
stimulated the resurgent interest in diesel engines. Biodiesel can be used in engines
designed to run on petroleum diesel, making biodiesel an attractive renewable fuel.
Biodiesel can be produced from many vegetable oil sources, and can even be made from
oil which has already been used for cooking. This means that the 1-3 billion gallons of
frying oil used in the US every year could be used to power vehicles instead of ending up
in land fills or sewers!
















Figure 1: Primary Components in Common Fuels. The fuels currently used in
combustion engines are all complex mixtures. The primary component of each fuel is
shown above.


O
O
CH
2
CH CHCH
2
CH CHCH
2
CH
3
7
4
H
3
C
Methyl linoleate (in biodiesel)
H
2
C
HC
H
2
C
O
O
O
O
O
O
CH
2
CH CHCH
2
CH CHCH
2
CH
3
7
4
CH
2
CH CHCH
2
CH CHCH
2
CH
3
7 4
CH
2
CH CHCH
2
CH CHCH
2
CH
3
7 4
Glyceryl trilinoleate (in soybean oil)
Dimethyldecadiene (in diesel)
H
3
C
C
H
3
C
H
C
C
H
2
H
C
C
H
H
2
C H
C
H
3
C
H
2
C
CH
3
H
3
C
C
H
3
C
CH
3
C
H
2
CH
CH
3
CH
3
Isooctane (in gasoline)
This experiment will give you the opportunity to make some biodiesel starting from
vegetable oil. If you trust your chemistry skills you could even put your product from this
lab into any diesel car. During the next experiment you will get to see how this fuel
burns.

New Chemistry
In order to make biodiesel from naturally occurring oils the long chain
hydrocarbons must be chemically separated. This can be accomplished through a process
called hydrolysis. In your body this is the first step in the digestion of fats and oils in our
diet.

H
2
C
HC
H
2
C
O
O
O
O
O
O
CH
2
CH CHCH
2
CH CHCH
2
CH
3
CH
2
CH CHCH
2
CH CHCH
2
CH
3
CH
2
CH CHCH
2
CH CHCH
2
CH
3
7 4
7 4
7 4
+ 3 H
2
O
HO
O
CH
2
CH CHCH
2
CH CHCH
2
CH
3
7 4
+
3
HO
C
H
2
CH
OH
C
H
2
OH
Fatty Acid (linoleic acid)
Glycerol

Figure 2: This process of breaking down oil into fatty acids and glycerol (also known
as glycerin) proceeds very slowly without the addition of catalysts.

Notice that the reaction in figure 2 is balanced. By adding water the bonds between
the fatty acid chains and the glycerol have been broken. This process proceeds very
slowly without the addition of a catalyst. However, the hydrolysis reaction can be
catalyzed by the addition of either an acid or a base (this is one of the reasons your
stomach is an acidic environment). The product of the hydrolysis reaction is a carboxylic
acid, attached to the long-chain hydrocarbon. Although this looks a lot like the biodiesel
shown in figure 1, the carboxylic acid can be corrosive inside an engine. For this reason,
chemists have devised another way to chemically modify the chains found in natural oils.
This new way is shown in Figure 3 below. Notice that instead of water, methanol
is used along with NaOH, which is a strong base that will act to catalyze the reaction. No
water is used and the desired product of the reaction belongs to a class of chemicals
called esters. Esters are like carboxylic acids, but instead of having the form RCOOH,
esters are terminated with a carbon chain RCOOR. Notice that esters were present in the
original soybean oil. Since we changed one ester into another ester, this reaction is called
a transesterification. What physical properties would change when the soybean oil is
changed to three separate esters?

H
2
C
HC
H
2
C
O
O
O
O
O
O
CH
2
CH CHCH
2
CH CHCH
2
CH
3
CH
2
CH CHCH
2
CH CHCH
2
CH
3
CH
2
CH CHCH
2
CH CHCH
2
CH
3
H
3
C OH
NaOH
HO
C
H
2
CH
OH
C
H
2
OH
H
3
CO
O
CH
2
CH CHCH
2
CH CHCH
2
CH
3
+
7 4
7 4
7 4
7 4
+
3
biodiesel (methyl linoleate)
Glycerol
3

Figure 3: The process we will use to produce biodiesel from soybean oil.

In addition to the desired biodiesel, this reaction also creates the byproduct glycerol.
Before the biodiesel can be used for combustion, the glycerol will have to be separated
from the biodiesel. This is relatively easy because the two chemicals are immiscible (they
do not mix) and they have significantly different densities. Biodiesel has a density of
0.884 g/mL and glycerol has a density of 1.261 g/mL. This means that the biodiesel will
float on top of the glycerol.

Prelab Questions

1) Complete the table below for all of the reactants and products used in this
experiment.

Chemical mp (
o
C)
bp (
o
C)
or smoke
point
density
(g/mL)
at 25C
Molecular
Weight
(g/mol)
Hazards
soybean oil -21 241 0.894 879.4
methanol
sodium hydroxide
methyl linoleate
(biodiesel)
-35 373 0.884 294.5
glycerol
water


2) If you have 10.0 kg of oil that you want to turn into biodiesel, how many liters of
methanol will you need? Use the balanced equation in Figure 3 and the molecular
weight for soybean oil to complete the calculation.








Experimental Procedures
Today you will be making biodiesel and you will be collecting data from the seed
germination experiment. the class will start by running the biodiesel reaction, while the
other gets starting collecting germination data. Then you will switch.

The Problem
Produce biodiesel from soybean oil, and compare the properties of biodiesel to other
fuels.

The Approach
Work in groups of 2 or three to synthesize the biodiesel.

Equipment needed:
250 mL Erlenmeyer flask
50 mL Beaker
100 mL Beaker
Graduated Cylinder
Magnetic stir bar
Heating and Stirring Plate
Thermometer (-20 100
o
C)
Parafilm to cover the 50 mL beaker while being stored

Chemicals Needed:
0.4 M solution of NaOH in methanol
Soybean or other vegetable oil

Day 1
1. Note: Remember that water and vegetable oil reacts to form the unwanted fatty
acid product, so please use all clean and dry glassware for this experiment.

2. Use a graduated cylinder to measure 40 mL of soybean oil (vegetable oil).
Transfer the oil in a 250 mL Erlenmeyer flask and warm the oil to between 40 and
50
o
C while rapidly stirring with a magnetic stir bar. (Note: For both your safety
and the effectiveness of the reaction do not allow the temperature to exceed 50
o
C.

3. Turn off the heat.

4. Add 10 mL of the 0.4 M sodium hydroxide in methanol solution to the warm oil.

5. Stirring the reaction for 45 minutes.

6. Stop the stirring and pour the mixture into a 50 mL beaker. Allow the mixture to
cool and then cover the beaker with parafilm. Label the beaker with your name
and date.

7. You will store the mixture in the lab drawer until next week, which will give
ample time for the layers to separate.

Note: Use the remainder of your lab time to count the seeds in the germination
experiment started during the last lab period. Directions and tables for this data
collection can be found in the previous experiment!



Day 2
1. By comparing the densities for each of the products, identify the biodiesel layer.
(Remember liquids that are less dense float on liquids that are denser.) Determine
the amount of biodiesel in mL. Record this value in your lab notebook.

2. Transfer the biodiesel to a 100 mL beaker.

3. Dry your biodiesel by heating the biodiesel at 80
o
C while stirring for 20 min.
Heating your sample will generate methanol vapors and other fumes, so this
MUST be done in the fume hood.

4. Measure the volume of your final isolated biodiesel. Record this value in your
notebook.





Postlab Questions

1) Determine the limiting reagent in your synthesis of biodiesel.

2) What is the theoretical yield for this reaction?

3) Calculate your actual yield based on the amount of biodiesel you isolated after
heating to remove residual methanol. Calculate the actual yield of biodiesel based
on the amount of biodiesel before separation and heating.

Use this table to answer the following questions.


4) If you had four containers without labels one biodiesel, one veggie oil, one
petroleum diesel, one gasoline what experiments would you have to run to
differentiate them?







5) How would you expect the viscosity of fuel to affect its performance on a cold
day (think about -20
o
C in the winter in Minnesota)? Which of the fuels listed in
the table above would work best on a cold day?




Fuel mp (
o
C)
bp (
o
C)
or smoke point
density (g/mL)
at 25C
viscosity (mPa s)
at 25C
Soybean Oil -21 241 0.894 69
Biodiesel -35 373 0.884 6.4
Gasoline (isooctane) -60 121 0.735 1.2
Petroleum diesel -40 315 0.848 3.5
Bibliography
Numerous versions of this lab are available in the chemical education literature and
can be found online. Our development was informed by the versions listed below.
1. John E. Thompson, "Biodiesel Synthesis" Lane College 2006 GEMS database,
follow-up personal communication, 2010.
2. Amy Cannon, "Green Chemistry in the Curriculum: Biodiesel Module" Beyond
Benign and Fisher science education, downloaded 2010.
3. Ehren C. Bucholtz, Biodiesel Synthesis and Evaluation: An Organic Chemistry
Experiment J. Chem. Ed. 2007, 84, 296-298.



Biodiesel Heat of Combustion and
Energy Efficiency

Chem Connections:
The heat of combustion is the amount of heat energy released when a substance is
completely burned. From a chemical perspective, burning is the complete oxidation of a
chemical. For example, a hydrocarbon is completely burned when all of the carbon atoms
have be transferred to CO
2
and the hydrogen atoms have turned into H
2
O. Consider a
relatively simple case, the burning of methane (the primary component of natural gas).

C
H
H H
H
+ 2 O
2
CO
2
+ 2 H
2
O
H
f
(kJ/mol) =
-75 0 -394 -242

The amount of energy produced by this reaction can be calculated by summing the bond
energies of each of the products (H
f
is the heat of formation in kJ/mol), and by
subtracting the sum of the H
f
for the reactants. (When you are looking these values up
you should always use the values assuming your products are in the gas phase.) The heat
of combustion for this reaction is: -394 + 2(-242) (-75) = -803 kJ/mol. Remember that
the negative sign indicates that this energy is given off, so this is an exothermic reaction
that will produce 803 kJ/mol. That energy can then be used to do work.
Last week we discussed a few of the possible advantages of biodiesel, this week we want
to consider the concept of efficiency from a chemical point of view. It was mentioned
that diesel engines are more efficient than gasoline engines. Rather, diesel engines
convert heat energy to mechanical energy more efficiently than gasoline engines. This
week we want to determine how efficiently various chemical fuels produce heat energy.
This can be done by determining the heat of combustion for a given fuel.
In addition to calculating the amount of heat produced by a reaction, we can also
measure the amount of heat using a technique called calorimetry. Calorimetry is a general
term for a number of techniques used to measure heat. In todays lab we are going to use
a very simple setup to measure the amount of heat produced when we burn our biodiesel.
It is very hard to measure the heat produced by burning fuel directly, so we will use the
heat produced to heat water. It takes 4.18 J of energy to raise 1 g of water 1
o
C. For
example, consider heating 200 g of water from 25
o
C to 35
o
C. This is a change of 10
o
C.
So to find the energy that this change took, we multiply (10
o
C)(200 g)(4.18 J/g
o
C)=
8,360 J or 8.4 KJ. If it took 0.3 g of fuel to heat the water, then we can determine the heat
of combustion by dividing (8.4 KJ)/(0.3g)= 27.8 KJ/g. So, by measuring both the
temperature increase in the water and how much fuel is used, we can determine the heat
of combustion.



Prelab Questions



1) It was mentioned that diesel engines take advantage of the ideal gas law (PV=nRT) to
create the conditions for combustion. Calculate the temperature inside a piston which
compresses air at room temperature and pressure (298 K, 1 atm) with a volume ratio
of V
1
/V
2
= 15/1. The final pressure in the piston is 30 atm. How hot is the air after
compression?



2) For the fuels listed below, calculate the theoretical heats of combustion using the
H
comb
= H
f, products
- H
f, reactants
. Assume that 1 mole of the fuel burns completely to
give CO
2
and H
2
O. Finally, convert this value to energy density (kJ/g) which is the
unit we will be measuring in todays lab.


Fuel Formula
Heat of
Compustion
(kJ/mol)
Energy
Density
(kJ/g) Fuel
H
f

(kJ/mol)
Isooctane C8H18 Gasoline -44.3
Hydrogen H2 biodiesel -839.2
Ethanol C2H5OH
Soybean
oil -4171.6
Mythyl
Linoleate
(biodiesel) C19H34O2
Soybean oil C57H100O6





3) Calculate the final temperature for 225 g of water, which starts at 20
o
C, after 0.75
grams of biodiesel have to be burned to heat the water. Assume all of the energy goes
to heating the water.
Experimental Procedure


The Problem
Determine the heat of combustion for biodiesel using ethanol as a standard to calibrate
your calorimetry apparatus.

The Approach
Work in groups of 2.

Equipment needed:
Oil Lamp with a wick
Ring Stand
Metal container for water with wire to suspend from the ring stand
Thermometer (-20 100
o
C)

Access to an analytical balance

Chemicals Needed:
Biodiesel (from last week)
Ethanol

PREPARING BIODIESEL FOR COMBUSTION
1) Complete the separation and purification of your biodiesel from last lab period.
Directions can be found in lab manual Synthesis of Biodiesel under the
DAY 2 heading.


MEASURING HEAT TRASNFER
2) Once the biodiesel has been isolated and purified, fill an oil lamp with ~15 mL of
your biodiesel. Then put the wick holder into the biodiesel, making sure that the
wick is exposed to fuel along the entire length. (If the wick is not completely
whetted by the fuel, it will not burn correctly.)
3) Make a precise measurement of the total weight of your lamp + biodiesel.
Record this starting weight.
4) Add exactly 225 ml of water into a soda can calorimeter. Be careful to use the
exact same amount of water in each measurement.
5) Suspend the metal can from the ring stand and measure the temperature of the
water. Record this temperature.
6) If the temperature is less than the temperature in the room, allow the water to
warm to room temperature before starting your experiment.
7) Once the temperature of the water has equilibrated with the room, light the oil
lamp and make sure it is placed as close to the metal can as possible, so that the
tip of the flame is slightly below the bottom of the can.
8) Monitor the change in temperature with your thermometer, while also gently
stirring the water to insure even heat distribution.
9) Once the temperature of the water has raised about 10
o
C, extinguish the flame.
10) Check the temperature again, if it continued to increase after the flame was
extinguished, record the highest temperature.
11) Weigh the oil lamp again, recording the final weight.
12) Calculate the amount of oil used to raise 225 mL to heat the water.
13) Now repeat this procedure at least two more times so that you are able to average
your data. Each time start with fresh water at room temperature. Also make sure
you record the starting and ending weight of the fuel + lamp.


14) Now repeat the same procedure with ethanol.
15) Repeat the measurement at least 3 times so that you will be able to average your
data.

Data and Calculation

Fuel
grams
burned
moles
burned Tinitial Tfinal T
EtOH
EtOH
EtOH
EtOH
EtOH
Biodiesel
Biodiesel
Biodiesel
Biodiesel
Biodiesel

The ethanol experiment will give us a sense of how much heat the calorimeter itself
will absorbs from the burning flame. We can then use this data to calibrate our
calorimetry based on ethanols heat of combustion.

The best way to determine the heat of combustion for a reaction is to use a bomb
calorimeter, where all of the heat from the combustion reaction is trapped inside a
closed system. In this system the amount of heat absorbed by the calorimeter is given
by the equation:
q
cal
= C
cal
X T

C
cal
is the heat capacity for the entire bomb calorimeter. And is expressed in the units
kJ/C. This value must be determined experimentally for the calorimeter and is based
on the amount of heat that both the water and the surroundings absorb. This will be
true for our calorimeter as well.

In order to calculate C
cal
for our soda can calorimeters we will use the known value
for the combustion of ethanol. (H
comb, EtOH
= -1278 kJ/mol EtOH) Since q
cal
is the
amount of heat aborbed during the reaction it will have a positive value for
exothermic reactions, and will be equal to q
combustion.

q
cal
= -q
combustion
= C
cal
X T
-q
combustion
= H
comb
X

(moles EtOH)
(H
comb
X

(moles EtOH))/T = C
cal


Calculate C
cal
for your calorimeter using the combustion data you gathered for from
the burning of Ethanol.

Reaction Ccal
EtOH 1
EtOH 2
EtOH 3
Average


Then use the q
cal
expression to calculate the H
comb
for the biodiesel that you made
last week.
Reaction H
comb

Biodiesel 1
Biodiesel 2
Biodiesel 3
Average



Postlab Questions

1) Compare the values you measured for biodiesel, to the predicted values you
calculated in the prelab. Do they match? If not explain, why they dont and
suggest ways that the experiment could be improved.

2) The heat of combustion for biodiesel is a measure of chemical energy. Explain the
relationship between chemical energy and fuel efficiency. Does a higher heat of
combustion for a fuel mean it is more efficient? Explain what contributes to fuel
efficiency.


Bibliography
This lab was inspired by following experiments.
1) Stephen M. Akers, Jeremy L. Conkle, Stephanie N. Thomas, and Keith B. Rider.
"Determination of the Heat of Combustion of Biodiesel Using Bomb
Calorimetry" J. Chem. Ed. 83, 2006, 260-262.
2) American Chemical Society, Chemistry in Context Laboratory Manual. 6
th
ed.
McGraw-Hill Science, 2008. In particular a personal communication with
Jennifer Tripp, an editor for the newest version of these labs.

Report for the biofuels unit
In addition to answering all of the post lab questions, please prepare short paper
for these three labs which examines various biofuel alternatives. Your short paper (1-2
pages) should compare and contrast two or more of the fuels sources that you have
studied during the last 3 weeks. You should consider the sources, synthesis, health
effects, and efficiency of the fuel sources in the paper. Finally, include a recommendation
for or against the use of one or more of the fuels you choose to discuss. Evaluation of this
report will be based on your ability to discuss the biofuels using data you collected from
lab or found in other scientific references.


Recommended Reading:
1) Howard Wolinsky, The Economics of Biofuels, European Molecular Biology
Organization Reports, 10, 551-553, doi:10.1038/embor.209.121
2) Melinda Wenner, The next Generation of Biofuels, Scientific American, March
2009, 46-51. (http://www.scientificamerican.com/article.cfm?id=the-next-
generation-of-biofuels)