AE

Activity 5: Calorimetry Biodiesel & Other Fuels

The ready availability of high-quality energy sources is one of the most important issues facing the global community in the late twentieth century. There are advantages/disadvantages of various fossil fuels. Hydrocarbons (and mixtures of hydrocarbons) are among the most energy-rich fuels. Many of them are liquids, which makes them attractive for transportation fuels. In this experiment, you will investigate the energy content of several fuels by using them to heat water. The data that you and your classmates obtain will enable you to compare fuels to see which ones provide more energy for a Figure 1: Biodiesel Production given mass of fuel burned. In particular, you will be able to determine how the Process energy released by burning hydrocarbons compares to that released by burning oxygenated fuels such as alcohols and diesels. Ethanol, C2H5OH, is commonly used as a gasoline additive and as a gasoline substitute (E85 fuel is a mixture of 85% ethanol and 15% gasoline). It should be noted that two of the fuels we will test, lamp oil and biodiesel, are actually a mixture of hydrocarbons of various carbon chain length, but we will approximate their compositions as shown in the table below. You will be synthesizing biodiesel using canola oil, according to the process shown in figure 2 below. In this experiment, you will examine several characteristics of the biodiesel you prepare that are important to its use as a fuel, including viscosity, gelation temperature, and energy content.

P R E P A R I N G WHAT DO YOU THINK? LEARNING OBJECTIVES 1. Take a look at the chemical information on Wikipedia/Wolfram Alpha to complete this table. Ethanol Biodiesel
(Methyl Linoleate)

Molecular formula Molar mass Density Heat of Combustion (kJ/mol)

-1,380

-10921

2. Write and balance the reactions for each of these combustion reactions. Assume that the combustion of each fuel produces carbon dioxide and water. 3. If a car can hold 55.0 liters of fuel, compare how much carbon dioxide is produced from a fuel tank full of ethanol verses a fuel tank full of biodiesel. 4. Which fuel do you think would release the most energy upon burning, biodiesel or ethanol? Why? 5. When you burn fuels, where does the energy come from?
As always, include an objective for this activity and share that objective with a teammate or laboratory partner. If you have questions during the activity, be sure to ask your instructor.

E X P E R I M E N T I N G Biodiesel and Calorimetry

Part A: Preparation of Biodiesel 1. Measure 50 ml of your oil directly into a 250 ml beaker 2. Add a stir bar to your oil and place the beaker on a stirring hotplate. Adjust the stirring rate so that the solution is being well mixed without splashing. Turn the heat on low. 3. Heat your oil to 50.0 deg C. To measure the mixtures temperature, hold a thermometer in the mixture but well away from the spinning stir bar. 4. As soon as your oil reaches 50 deg C, turn off the heat. Do not let your mixtures temperature to exceed 55 deg C. If necessary, remove the beaker from the hot plate. 2

5. While your oil is heating, prepare your methanol/NaOH solution by using a 10 ml graduated cylinder to measure out 10 ml of methanol into a small beaker. Add approximately 11 drops of 9M NaOH to the methanol. 6. Slowly pour the methanol/NaOH mixture into your oil. Be sure that the mixture continues to stir sufficiently so that the methanol does not form a layer on top. Record the observations. 7. Continue to stir and heat the mixture for 20 minutes keeping the temperature between 45 and 55 deg C. Do not let the temperature exceed 60 deg C.
8. Pour your solution, which now contains biodiesel and glycerol, into a 250 mL separatory funnel. The top layer of your solution is biodiesel. Drain the bottom layer containing your glycerol waste into a beaker and discard according to your instructors direction.

Part B: Testing Biodiesel In this section, you will test your biodiesel by looking at viscosity and clarity. Viscosity 1. Obtain two 6-inch disposable glass pipets that have been marked with lines on the barrels 4 cm apart as shown in Figure 1. You'll also need a matching dropper bulb and a timer that can measure in seconds. 2. We will estimate viscosity by measuring the time required for the liquid level in the pipet to drop from the upper line to the lower line. Viscosity is proportional to this time. 3. Use the bulb to fill one of your pipets with your biodiesel so that the liquid is above the upper line. Hold the pipet vertically over the beaker of biodiesel. Quickly remove the bulb and place your index finger firmly over the top of the pipet. This will stop the biodiesel from dripping. 4. Have your partner ready to time. Remove your finger from the top of the pipet. Allow the liquid to drain freely back into the beaker. Measure the time required for the biodiesel level to drop from the upper line to the lower line. Record your time. 5. Repeat the measurement. Record your data and calculate the average. Discard the used pipet. Figure 2: Pipet w/marked lines 6. Use a test tube to get about 5 mL of the canola oil used in Part A as the starting material for your biodiesel. Use your second marked pipet to measure the viscosity of the canola oil. Allow the canola oil to drip back into its test tube. Do the measurement twice, recording your data and calculating the average time. Clarity 1. Fill a small test tube full with a sample of your biodiesel. Fill a second test tube full with a sample of canola oil. 2. Make a ice and saltwater bath by adding ice cubes, rock salt and water into a 250 mL beaker.

3. Place the test tubes in an ice-salt water bath and let them reach thermal equilibrium by sitting for a few minutes. 4. Note the difference in clarity between the liquids in your lab journal, as well as the temperature of the two liquid samples. Part C: Measuring Heats of Combustion of biodiesel and ethanol In order to calculate heat of combustion, you need to measure the amount of water that you use in your calorimeter, the mass of fuel burned, and the initial and final temperature of the water. Set up a table to record this necessary information. 1. Connect the probe to the computer interface. 2. Find and record the combined mass of the burner & biodiesel. 3. Wash out your cans and shake out as much water as possible. Add 150 g of cold tap water to the can. 4. Set up the apparatus as shown in Figure 2. Use a ring and stirring rod to suspend the can about 5 cm above the wick. Use a utility clamp to suspend the Temperature Probe in the water. The probe should not touch the bottom of the can. Important: The Temperature Probe must be in the water for at least 30 seconds to establish thermal equilibrium before you collect temperature data. 5. Light the wick of your burner, and allow the fuel to burn until the temperature of the water approaches 40 degrees C. Extinguish the flame once the water reaches a minimum of 40 degrees C.
Figure 3: Calorimetry Setup

6. Continue stirring the water until the temperature stops rising. Record the final temperature. 7. Determine and record the final mass of the cooled burner & remaining biodiesel. 8. Repeat the process using ethanol. Collate data from at least two other groups as well as your own (so you have three sets).

A N A L Y Z I N G READING QUESTIONS

Reading: Part A:
Turning waste materials into useful products offers both economic and ecological benefits. Waste oils from cooking can be burned directly for heat, but they don 't have the right characteristics to substitute for gasoline or diesel fuel in cars. Fortunately, a simple chemical reaction will convert oils to a more useful form called biodiesel. Either waste or new fats and oils derived from plants or animals can be utilized for biodiesel production. Used oil contains waste products that complicate the procedures by requiring the oil to be treated prior to biodiesel production, so you may use new oil or treated waste oil for this experiment at the discretion of your instructor. Oils and fats are composed of triglycerides like the one shown in the equation in the introduction to this lab. Triglycerides are even larger molecules than they appear in the equation because the three R-groups shown in the triglyceride each represent a long hydrocarbon chain with a length of 10-20 carbon atoms with hydrogens attached. As depicted in Figure //./ in the introduction, the triglyceride molecules react with methanol in the presence of a catalyst (NaOH) to form two products. The first is glycerol, which is useful for making cosmetics and other consumer products. However, due to biodiesel production there is currently a glut of glycerol and research is being directed into something useful to do with it all, including turning it into biodegradable plastics. The second is biodiesel, a methyl ester (discussed in section 10.3 of the textbook) of one of the long chain fatty acids that was removed from the triglyceride. Vegetable oils contain mixtures of several triglycerides, where the number of carbon atoms (designated as R in fig. 11.1) varies. As a result, any biodiesel fuel will also be a mixture of several molecules each with a different number of carbon atoms (R). Each type of vegetable oil will have a different mixture of triglycerides and give us a different mixture of biodiesel molecules. This means that biodiesel fuels prepared from different types of oils will have somewhat different properties.

Reading: Part B:
Viscosity is a measure of how easily a liquid flows or pours. For instance, water has a low viscosity and flows easily, while maple syrup has a much higher viscosity and pours slowly. Because a fuel must flow through the engine, its viscosity is important to the proper functioning of that engine. If the fuel's viscosity is too high, the engine will have to work harder, causing higher operating temperatures and greater wear. You will measure the viscosity of both your biodiesel product and the oil from which it was prepared by measuring how long it takes each liquid to drip from a small pipet. The longer it takes for the liquid to drain, the higher the viscosity of the liquid. Diesel engines are notoriously difficult to start in cold winter weather. The problem is that the diesel fuel thickens and turns to a gel at these temperatures. Gelled fuel will not flow or ignite properly. You will observe the biodiesel and oil to see if they begin to cloud and gel at typical winter temperatures, near 0C.

Questions: Part B:
1. How can you determine that youve actually made biodiesel? 2. What are the limitations of biodiesel based upon your results from part B?

Reading: Part C: Read Chem Talk Pages 535 539 (need reading of q=mcT here, as well as workedexample screencast) Questions: Part C:
1. Discuss heat loss factors (there were MANY) that contribute to the inefficiency of the experiment. 2. See table below to fill in each calculation. Show your work in your lab journal.

Ethanol Mass of water (g) Temperature change, T (C) Thermal energy (kJ) Mass of fuel (g) Heat of combustion (kJ/g) Heat of combustion (kJ/mol) % error

Biodiesel Biodiesel

3. Compare the heat of combustion for biodiesel and ethanol. 4. Go back and look at your answers to preparing question 3. How much energy would be produced from a tank of biodiesel? Of ethanol? 5. How much energy is produced per gram of carbon dioxide for biodiesel? For ethanol? [HINT: Youll need to divide your answer from question 4 with your answer from preparing question 3]

CT

C R I T I C A L L Y

T H I N K I N G

MEAN? KNOW? BELIEVE? CARE?

What does the activity mean?

Chemistry explains the macroscopic phenomenon (what you observe) with an explanation of what happens at the nanoscopic level (atoms and molecules) using symbolic structures as a way to communicate. Explain the meaning of this activity by completing the MNS table. MACRO What did you observe in this activity that led you to believe that the combustion of a fuel is an exothermic process? NANO When a fuel burns compare the bonds of the molecules on the product and reactant sides SYMBOLIC Use an energy diagram as a symbolic structure to describe what happens during the combustion of biodiesel

How do I know?
Oxygenated fuels will release less heat than similar hydrocarbons without oxygen. Of these two fuels (biodiesel and ethanol), which would you support as an alternative to octane? Support your claim with data.

Why do I believe?
Your everyday experiences make it easy to accept that when a fuel is burned it is an exothermic process. What examples of fires would you use to explain to someone that fires require fuel?

Why do I care?
You cannot always use fuels with the highest heat output per gram. Consider why not in terms of cost, convenience and safety.