Adventures with energy and fuels

David A. Katz Chemist, educator, and consultant Tucson, Arizona, U.S.A. Email: [email protected] Web site: http://www.chymist.com Courses taught Non‐major courses: CHM 121IN, and Society CHM 125IN, Consumer Chemistry Both taught as hands‐on learning courses Meet in lab, 2 hours – 40 minutes, 2X per week

CHM 130, Fundamental Chemistry (First half of the GOB course)

CHM 151‐152IN, General Chemistry There is a lot more that needs to be in a general chemistry course than what is in the textbook.

Students must be able to locate information, read and understand it, and have the knowledge to make intelligent, rational decisions regarding the accuracy of that information to become informed, active citizens in today’s world. Petroleum Formation of Petroleum Drilling for Petroleum

For land deposits, an oil rig needs to drill through the An oil rig system cap rock into the oil deposit Colonel Edwin Drake and the first commercial oil well Titusville, PA 1858 Drilling for oil in Pennsylvania

Left: Empire Well, Funkville, PA, 1863

Below: Triumph Hill, 1871 The rebuilt Drake well and pump at the Drake Museum, Titusville, PA Vaseline Oil derricks Oil well drill bits Petroleum Museum, Midland, TX

Once the petroleum is found, the rig is removed and a pump is placed on the well head. The Athabasca Tar (Oil) Sands Fort McMurray, Alberta, Canada Tar (oil) Sands

The tar sands are composed of 83% silica sand 10% crude bitumen 4% water 3% clay Oil Shale Colorado, Wyoming and Utah Estimates of global deposits range from 2.8 trillion to 3.3 trillion barrels of recoverable oil Refining Petroleum

Anacortes Refinery, north end of March Point southeast of Anacortes, Washington Crude oil contains hundreds of different hydrocarbons mixed together. To obtain useful products, the process of fractional distillation is used. The following diagram shows a schematic of a fractional distillation column.

Longer hydrocarbon chain lengths have progressively higher boiling points, so they can all be separated by distillation. Crude oil is heated and the different chains are separated by boiling temperatures. Synthesis of Biodiesel from Vegetable Oil The preparation of the biodiesel is a transesterification reaction where the triglycerides are converted into simpler methyl esters of the fatty acids (the biodiesel) O 

HC2  O C R HC2  OH OO   NaOH H C O C R + 3 CH32 OH (catalyst) 3 H C O C R HC OH O 

HC2  O C R HC2  OH Triglyceride methanol fatty acid methyl ester glycerin

Test for pH, freezing point, and combustion A History of Electricity/ • Thales of Miletus (640‐546 B.C.) is credited with the discovery that amber when rubbed with cloth or fur acquired the property of attracting light objects. • The word electricity comes from "elektron" the Greek word for amber. Thales of Miletus Otto von Guericke • Otto von Guericke (1602‐1686) invented the first electrostatic generator in 1675. It was made of a sulphur ball which rotated in a wooden cradle. The ball itself was rubbed by hand and the charged sulphur ball had to be transported to the place where the electric experiment was carried out. • Ewald Jürgen von Kleist (1700‐1748), invented the Leyden Jar in 1745 to store electric energy. The Leyden Jar contained water or mercury and was placed onto a metal surface with ground connection. • In 1746, the Leyden jar was independently invented by physicist Pieter van Musschenbroek (1692‐ 1761) and/or his lawyer friend Andreas Cunnaeus in Leyden/the Netherlands • Leyden jars could be joined together to store large electrical charges Count Alessandro Giuseppe Antonio Anastasio Volta (1745 – 1827) developed the first electric cell, called a Voltaic Pile, in 1800. A voltaic pile consist of alternating layers of two dissimilar metals, separated by pieces of cardboard soaked in a sodium chloride solution or sulfuric acid.

Volta determined that the best combination of metals was zinc and silver

Volta’s electric pile (right)

A Voltaic pile at the Smithsonian Institution, (far right) Build a voltaic pile • John Frederic Daniell (1790‐1845), professor of chemistry at King's College, . • Daniell's research into development of constant current cells took place at the same time (late ) that commercial telegraph systems began to appear. Daniell's copper battery (1836) became the standard for British and American telegraph systems. • In 1839, Daniell experimented on the fusion of metals with a 70‐ cell battery. He produced an electric arc so rich in ultraviolet rays that it resulted in an instant, artificial sunburn. These experiments caused serious injury to Daniell's eyes as well as the eyes of spectators. • Ultimately, Daniell showed that the ion of the metal, rather than its oxide, carries an electric charge when a metal‐salt solution is electrolyzed.

Left: An early Daniell Cell

Right:Daniell cells used by Sir William Robert Grove, 1839. Voltaic Cells

• The salt bridge is used to prevent electrons flowing directly from the zinc to the copper • The salt bridge consists of a U‐ shaped tube that contains a salt solution, sealed with porous plugs, or an agar gel solution of the salt • The salt bridge keeps the charges balanced and forces the electron to move through the wire • Cations move toward the cathode. • Anions move toward the anode. Cell Potentials

Oxidation: E°red = -0.76 V Reduction: E°red = +0.34 V Electrochemical Cells and Batteries

Measure potentials for different metals Construct cells BATTERIES Primary, Secondary, and Fuel Cells Batteries Most commercial batteries produce 1.5 V. To get a higher voltage, batteries are joined together. Dry Cell Battery

Primary battery — uses redox reactions that cannot be restored by recharge.

Anode (-)

Zn  Zn2+ + 2e-

Cathode (+)

+ - 2 NH4 + 2e 2 NH3 + H2 Alkaline Battery

Nearly same reactions as in common dry cell, but under basic conditions.

‐ Anode (‐): Zn + 2 OH  ZnO + H2O + 2e‐ ‐ Cathode (+): 2 MnO2 + H2O + 2e‐  Mn2O3 + 2 OH Lead Storage Battery

• Secondary battery • Uses redox reactions that can be reversed. • Can be restored by recharging Ni‐Cad Battery Anode (-) - Cd + 2 OH  Cd(OH)2 + 2e- Cathode (+) - NiO(OH) + H2O + e-  Ni(OH)2 + OH Construct a Dry Cell Battery

Dry cell battery kit from IASCO Build a Wind Turbine Source: Pembina Institute, Ontario, Canada

Students wind coils Uses rare Earth magnets Lights an LED Fuel Cells: H2 as a Fuel •Fuel cell ‐reactants are supplied continuously from an external source. •Cars can use electricity

generated by H2/O2 fuel cells.

•H2 carried in tanks or generated from hydrocarbons. Hydrogen—Air Fuel Cell H2 as a Fuel

Comparison of the volumes of substances required to store 4 kg of hydrogen relative to car size. Storing H2 as a Fuel

One way to store H2 is to adsorb the gas onto a metal or metal alloy. Construction of a Microscale Fuel Cell

Uses 1 mL syringes Electrode is drafting pencil lead

Electrolyte is Epsom salt, MgSO4∙7H2O Titanium Dioxide Raspberry Solar Cell

Grind nanocrystalline

TiO2 with dilute Coat surface acetic acid conducting glass

Bake coating on hot plate Dip into berry juice Rinse

Coat 2nd piece of glass with carbon Clamp together

Dope with KI3 solution Measure voltage Nuclear Reactors Nuclear Reactors In nuclear reactors the heat generated by the reaction is used to produce steam that turns a turbine connected to a generator. Number of reactors in operation and under construction for the countries with the largest nuclear power generation Sources of electricity generation, worldwide and for select countries Nuclear Reactors

• The reaction is kept in check by the use of control rods. • These block the paths of some neutrons, keeping the system from reaching a dangerous supercritical mass. • The control rods must be withdrawn from between the fuel rods to initiate the nuclear reaction. • The normal position of the control rods is in between the fuel rods. Pressurized Water Reactors In a typical pressurized light‐water reactor 1. The core inside the reactor vessel creates heat 2. Pressurized water in the primary coolant loop carries the heat to the steam generator, 3. Inside the steam generator, heat from the steam, and the steam line directs the steam to the main turbine, turning the turbine generator to produce electricity. 4. Unused steam is exhausted in to the condenser, condensed into water, pumped out of the condenser, reheated and pumped back to the steam generators. 5. The reactor's fuel assemblies are cooled by water circulated using electrically powered pumps. If power is lost emergency cooling water is supplied by other pumps, powered by onsite diesel generators.. 6. Pressurized‐water reactors contain between 150‐200 fuel assemblies. The Pressurized Water Reactor Boiling Water Reactors In a typical commercial boiling‐water reactor: 1.The core inside the reactor vessel creates heat, producing a steam‐water mixture 2.The steam‐water mixture enters two stages of moisture separation where water droplets are removed before the steam is allowed to enter the steam line 3.The steam line directs the steam to the main turbine, turning the turbine generator, which produces electricity. 4.Unused steam is exhausted into the condenser, condensed into water, pumped out of the condenser, reheated and pumped back to the reactor vessel. 5. The reactor's core fuel assemblies are cooled by water circulated using electrically powered pumps. 6.Pumps and other operating systems in the plant receive their power from the electrical grid. If offsite power is lost emergency cooling water is supplied by other pumps, which can be powered by onsite diesel generators. 7.Boiling‐water reactors contain between 370‐800 fuel assemblies. The Boiling Water Reactor Nuclear Reactors: Nuclear Fuel

• The most common fuel for a nuclear reactor is usually uranium dioxide pressed into pellets

• The UO2 is produced from enriched UF6 gas. • The pellets are encased in long metal tubes, usually made of zirconium alloy (zircalloy) or stainless steel, to form fuel rods. • The fuel rods are sealed and assembled in clusters to form fuel assemblies for use in the core of the nuclear reactor. Nuclear Reactors: Nuclear Fuel Left: Looking into the core of a pressurized water reactor.

Below: A close‐up view of the reactor core.

The spent fuel pool

Photos courtesy of Palisades Power Plant The spent fuel pool Nuclear Reactors: Nuclear Waste

Pictures courtesy of Palisades Power Plant Nuclear Reactors: Nuclear Waste Nuclear Reactors: Nuclear Waste Yucca Mountain, Nevada Test Site, Nevada Nuclear Reactors: Nuclear Waste Yucca Mountain, Nevada Test Site, Nevada Nuclear Reactors: Nuclear Waste Yucca Mountain, Nevada Test Site, Nevada Nuclear Fusion • Fusion would be a superior method of generating power. • Once fusion reactors are perfected, the products of the reaction will not be radioactive. (There are radioactive products of hydrogen fusion.) • In order to achieve fusion, the material must be in the plasma state at several million Kelvin's. Nuclear Chemistry Experiments Measure nuclear radiation Inverse square law Half‐life measurement Web site: http://www.chymist.com On left‐hand menu, click on Laboratory Experiments and/or Chem Courses and Information pdf’s of PowerPoints at Chem 121: Energy Chem 151: Nuclear Chemistry Chem 152: Oxidation‐Reduction and Electrochemistry Contact information: [email protected]