Unit 4 Excerpt from The Web of Life by John H. Storer “Air, rock, water, and sunlight – these are the four sources from which come all living things and their environment. On the bare sands of the desert, the sun’s rays strike in tiny units of energy moving with atomic speed. Some of them we can feel as heat or see as light. These speeding units impart some of their energy to the dead sands, which temporarily store it in the form of heat, but when the sun sinks, this newly acquired energy is radiated back into the air and lost. The sand becomes as cold and dead as ever. But chlorophyll in the leaves of green plants exists as an agent for garnering these units of solar energy. It makes of the green leaf a laboratory in which nature creates food for living creatures and carries on unceasingly the magic of building life. Like the sand, a field of grass absorbs the sun’s rays; but when night comes the grass does not give back this newly gained energy. In its green laboratory, the chlorophyll blends the sun’s captured radiance together with elements taken from the air, the water, and the soil, and builds these dead materials into organized living form to make new blades of grass. This grass is cool and quiet, giving no hint of the sunlight stored within its framework. But dry it out and touch a match to it. The blades of grass – these tiny bits of organized gas and sunlight – blaze up with flame hot enough to kill a man. All of that fierce heat is merely a release of the same energy that the cool, moist plants have been quietly gathering from the sunlight and storing for later use. If the grass is not burned, the energy will remain stored within its substance. If it is eaten by an animal, its life force is transferred with it into the body of the animal to sustain the spark that we call life.” THE CONCEPT OF ENERGY: All physical and chemical changes are accompanied by changes in energy. Energy is defined as the ability to do work or to transfer heat. Forms of Energy: Energy can be classified as potential or kinetic. The total energy an object possesses Etot = K.E. + P.E. POTENTIAL ENERGY Potential energy is the energy that results from an object’s position. It is stored energy that can be converted to kinetic energy. EXAMPLES OF POTENTIAL ENERGY: Chemical potential energy: resulting from attractions among electrons and atomic nuclei in molecules. This is the energy associated with the forces within (Intramolecular) and between (Intermolecular) molecules. Chemicals store energy in bonds (Intramolecular forces). The stronger the bond = more energy stored Gravitational potential energy: such as that of a ball held well above the floor or that of water at the top of a waterfall. Gravitational potential energy (GPE) = mgh m = mass in kg; g = gravity, 9.801 m/s2; h = height in m KINETIC ENERGY An object has kinetic energy because it is moving. Kinetic energy can be converted into potential energy. EXAMPLES OF KINETIC ENERGY Thermal kinetic energy: atoms, molecules, or ions (atoms with a net charge) in motion at the submicroscopic level—All matter has thermal kinetic energy because, according to the kineticmolecular theory, the submicroscopic particles of matter are in constant motion. Mechanical kinetic energy of macroscopic objects: moving baseball or automobile Electrical kinetic energy: electrons moving through a conductor Radiant kinetic energy: electrons transitioning between energy levels with the atoms producing light Sound kinetic energy: corresponds to the compression and expansion of the spaces between molecules. Kinetic energy Where = mv2 2 m = mass in kg; v = velocity in m/s Let’s try some….. When gasoline is burned in a car engine, its chemical potential energy is converted into other forms of energy. Name three. What kind of energy conversion takes place in a toaster? What kind of energy conversion takes place in a hair dryer? UNITS OF ENERGY The SI unit for energy is Joule, J. This unit is named in honor of James P. Joule, a British scientist who devoted much of his life to investigating energy in all of its forms. He determined that work (or energy) could be measured in terms of the heat it could produce. kg m2 J= s2 Another energy unit specifically used when talking about heat energy is the calorie (cal). 1 calorie = 4.184 J One calorie represents a small quantity of heat, thus the kilocalorie (kcal) is preferred. A dietary calorie, represented Calorie (Cal), has the same value as kcal. 1000 cal = 1 kcal = 1 Cal Pg 77 in your text: #50, 51, and 90 Definition of Energy Units CONVERSION OF ENERGY AND ITS CONSERVATION: Law of Conservation of energy states that, “Energy cannot be created nor destroyed, just transferred.” The total amount or energy in the universe is CONSTANT. Is mass and energy related? E = mc2 E = Energy m = mass c = speed of light (2.998 x 108 m/s) This equation corresponds to when a body or system releases energy, the body or system decreases in mass. Likewise, when a body or system absorbs energy, the body or system increases in mass. Usually, these changes in mass go undetected, unless we discuss reactions that involve nuclei of atoms that occur in nuclear reactors or an atomic bomb. ENERGY AND CHEMICAL REACTIONS: Energy changes that accompany chemical changes are generally more noticeable than those that take place during physical changes. The substances that we begin with before the chemical reaction are referred to as the reactants. The substances that are produced as a result of a chemical change are referred to as the products. If a reaction takes place and the temperature of the surroundings drops, does this indicate the destruction of energy? NO, this indicates that energy was absorbed from the surroundings into the system (reaction) and can is classified as an endothermic reaction. What if the temperature of the surroundings increases? Was energy created? NO, This means the system (reaction) released energy to the surroundings. This is an exothermic reaction. HOW CAN THIS BE EXPLAINED????? When two atoms chemically bond together, their bond has a specific amount of energy due to its stability (strength). The energy required to break this bond varies depending on the type of bond and the atoms that are bonded together. During a chemical change, the reactants begin with a certain amount of potential energy. In order to break these bonds a specific amount of energy, called the activation energy, is needed. When the products are yielded they may have a higher or lower potential energy than the reactants due, once again, to the number of bonds formed and the relative strengths of the bonds. If the reactants have more energy than the products, then heat must be released from the reaction……. EXOTHERMIC. The products are more stable than the reactants. If the products require more energy than the reactants, then heat must be absorbed from the surroundings……… ENDOTHERMIC. The reactants are more stable than the products. The heat of reaction is the measure of the energy flow; quantity of heat released of absorbed during a reaction and is represented by q or H. (q = H at constant pressure) Bond Bond Energy kJ/mol F-F C=O O-H Br-Br C-Br H-Br Cl-Cl C-O H-H C-C C-Cl C-H C=C H-F H-Cl C-F I-I C-I CC C-N H-I 154 743 463 193 276 366 239 360 436 348 339 412 612 565 427 485 151 238 837 305 299 Potential Energy Diagrams POTENTIAL ENERGY DIAGRAMS Potential energy CH 4 + 2O 2 CO 2 + 2H 2 O + Heat CH 4 + 2O 2 Heat CO 2 + 2 H 2 O Potential energy N2 + O2 + HEAT 2 NO 2 NO Heat N2 + O2 Direction Every energy measurement has three parts. 1. A number (how many). 2. A unit (Joules or calories). 3. A sign to tell direction. negative - exothermic positive- endothermic The reaction: 2CO(g) + O2(g) 2CO2(g) is exothermic. What is the sign of H for this reaction? What is the sign of H for the reverse reaction? Is the heat content of the products greater or less than that of the reactants? For the reaction: CaCO3(s) CaO(s) + CO2(g) H = +176 KJ/mol Is this reaction exothermic or endothermic? b. What is the value of H for the reverse reaction? c. How does the heat content of the products compare to that of the reactants? HEAT ENERGY AND TEMPERATURE: We have all measured temperature before using a thermometer, but how does it work? When substances heat up, typically they expand, which explains the concept behind a thermometer. A glass (or plastic) tube is attached to a bulb. The bulb is filled with alcohol or liquid mercury. Upon heating the liquid expands and is forced from the bulb into the tube. Upon cooling, the liquid contracts and flows back into the tube. The tube is then calibrated to precisely record changes in temperature. TEMPERATURE SCALES The three temperature scales are Fahrenheit, F Celsius, C Kelvin, K. The Celsius temperature scale is the one most commonly used for scientific work. Comparison of the Three Temperature Scales F C Water Boils 212.00 100.00 Body Temperature 98.6 37.0 Water Freezes 32.0 0.00 Absolute Zero -459.67 -273.15 K 373.15 310.2 273.15 0.00 FAHRENHEIT: The Fahrenheit scale was created (1714, Gabriel Fahrenheit) based on temperatures he could recreate in the lab. The lowest temperature he could achieve was with a mixture of freezing ice, snow salt, and water. This became 0F. The reference point for 100F is told to be based on the body temperature of a cow, around 98.6F, simply because Fahrenheit liked cows!! Except he chose a sick cow when he created the scale. CELSIUS The Celsius scale was created in 1742 by Anders Celsius. He designated the freezing and boiling points of water to be the 0C and 100C, respectively, and then divided the difference into 100 graduations. This is why the Celsius scale is sometimes referred to as “Centigrade.” KELVIN The Kelvin temperature scale (1848) was derived from the observation of gases. Theoretically, the lowest possible temperature an object can obtain is that of absolute zero. This temperature has never been reached. Scientists have come to within 1 billionth of a degree above absolute zero. This value is the basis for Lord Kelvin’s scale. At absolute zero, all motion will cease. TEMPERATURE CONVERSIONS The size of one degree is the same for both the Celsius and Kelvin scales, however not for Fahrenheit. To convert among these three scales: F = 1.8 (C) + 32 C = F – 32 K = C + 273.15 C = K – 273.15 1.8 Convert the following temperatures from one unit to another. 1. 2. 3. 4. 5. 263 K to oF 38 K to oF 13 oF to oC 1390 oC to K 3000. oC to oF F – 32+ 32 F = C 1.8 =(K – 273.15) KF= =C + 1.8273.15 (C) + 32 1.8 F F==-391 14 F F F = C K =5432 -111663 CFK How to Derive Equations 0º C = 32 ºF Compare Freezing Points 0ºC 32ºF 100 ºC = 212 ºF Compare Boiling Points 0ºC 100ºC 212ºF 32ºF 100ºC = 212ºF 0ºC = 32ºF 100ºC = 180ºF 0ºC 100ºC Find the distance between the two points on both scales 212ºF 32ºF 100ºC = 212ºF 0ºC = 32ºF 100ºC = 180ºF 1ºC = (180/100)ºF 1ºC = 1.8ºF 0ºC 100ºC A 1º change in Celsius corresponds to 212ºF 1.8ºF 32ºF A 1º change in Celsius corresponds to 1.8ºF Whatever data set has a zero point, assign that scale as the x coordinate m= m= y x 1.8 y = mx + b Lets set-up ordered pairs to determine the equation of the line. (0,32) (100, 212) m= 212 - 32 100 - 0 ºF = 1.8(ºC) + b Find the y-intercept (b) by substitution!!! ºF = 1.8(ºC) + b 212 = 1.8(100) + b 32 = 1.8(0) + b 212 - 180 = b 32 = b 32 = b ºF = 1.8(ºC) + 32 Water boils at 140 °X and freezes at 14 °X. Derive the relationship between °X and °C. °X °C oiling point BBoiling point 140 100 Freezing point 14 0 Difference 126 100 1ºC = (126/100)ºX 1ºC = 1.26ºX Lets set-up ordered pairs to determine the equation of the line. A 1º change in Celsius corresponds to 1.26ºX (0,14) (100, 140) m= y x m= ºX = 1.26(ºC) + b 140 - 14 100 - 0 m = 1.26 y = mx + b Find the y-intercept (b) by substitution!!! 140 = 1.26(100) + b 14 = 1.26(0) + b 140 - 126= b 14 = b 14 = b ºX = 1.26(ºC) + 14 HEAT AND ITS MEASUREMENT: We can now convert among the three temperature scales, but what exactly is temperature? Temperature: the average kinetic energy of a substance’s particles. Are temperature and heat the same thing? NO!!! Heat: form of energy that is often associated with the changing temperature of an object. An objects temperature increases because energy is transferred to it. The energy transfer, in the form of heat, happens when two objects are brought into contact, as nature attempts to equalize their temperatures, that is, to establish a thermal equilibrium. A lit match burns at a temperature of 200C. A building on fire burns at a temperature of 200C. Which one is hotter? Neither, they are the same temperature. Which one produces more heat? The burning building. A hot cup of coffee is 85C. A Jacuzzi is 85C. A hot cup of coffee contains enough heat energy to probably melt one ice cube before coming to room temperature. A Jacuzzi would melt an entire freezer full of ice before coming to room temperature. Heat is affected by both temperature and mass. THE KINETIC THEORY OF HEAT AND TEMPERATURE: Temperature can be used to determine the direction of flow of energy. Energy spontaneously flows from a warmer object to a cooler one. (HEAT DOES NOT RISE). Kinetic theory explains the flow of energy in terms of particle collisions. Because the warm object is at a higher temperature than the cool object, the average kinetic energy of its particles is greater than that of the cool object. Because the objects are in contact, the particles of the warm object collide with those of the cool object. Gradually the particles in the warm object will transfer kinetic energy to the particles in the cool object through collisions. As a result, the particles in the cool object gain kinetic energy. Eventually the average kinetic energy of the particles in both objects will be equal and the two objects will have the same temperature. For example: You can feel that a bowl of hot soup warms the air around it. Left undisturbed, the soup and bowl will eventually cool to room temperature. MEASURING CHANGES IN HEAT : In the early 1780’s Antoine Lavoisier measured the heat given off by a guinea pig. He kept the animal enclosed in a container so that its body heat would melt ice. From the amount of ice melted, he calculated the body heat produced by the animal. This was an example of an ice calorimeter. A calorimeter is a device used to measure the energy given off or absorbed during chemical or physical changes. There are two main types of calorimeters, a constant pressure calorimeter (coffeecup) and a constant volume calorimeter (bomb calorimeter). In a coffee cup calorimeter, the reaction takes place in the water. A coffee cup calorimeter is great for measuring heat flow in a solution, but it can't be used for reactions which involve gases, since they would escape from the cup. The coffee cup calorimeter can't be used for high temperature reactions, either, since these would melt the cup. A bomb calorimeter works in the same manner as a coffee cup calorimeter, with one big difference. A bomb calorimeter is used to measure heat flows for gases and high temperature reactions. In a bomb calorimeter, the reaction takes place in a sealed metal container, which is placed in the water in an insulated container. Heat flow from the reaction crosses the walls of the sealed container to the water. The temperature difference of the water is measured, just as it was for a coffee cup calorimeter. Analysis of the heat flow is a bit more complex than it was for the coffee cup calorimeter because the heat flow into the metal parts of the calorimeter must be taken into account: Bomb Calorimeter CALORIMETRY We will use the coffee-cup calorimeter in the lab. A bomb calorimeter is the preferred calorimeter to measure the heat released in combustion reactions. Both types of calorimeters contain water, which is used to measure the heat absorbed or discharged. Some substances require little heat to cause a change in their temperature. Other substances require a great deal of heat to cause a change in their temperature. For example: One gram of liquid water requires 4.184 joules of heat to cause a temperature change of 1C. It only takes 0.902 joules to raise the temperature of one gram of aluminum 1C. The heat needed to raise the temperature of one gram of a substance by 1C is called the specific heat (Cp) of a substance. Every substance has its own specific heat (intensive physical property). The heat required to raise the temperature of one gram of water 1C is 4.184 J or 1 cal. The Specific Heat of water (Cp) is 4.184 J/gC or 1 cal/gC. Specific heats can be used in calculations involving the change in temperature of a specific mass of a substance. Further, the amount of energy transferred can be calculated from the relationship. q = mCT q = heat gained or lost by substance m = mass in grams C = specific heat T = change in temperature (T2 – T1) or (Tfinal – Tinitial) According to the Law of Conservation of Energy, in a calorimeter containing water, any heat gained by the substance is lost by the water. Likewise, any heat lost by the substance is gained by the water. This transfer of energy takes place between these two quantities of matter that are at different temperatures until the two reach the same (equilibrium) temperature. The heat released or absorbed by water is calculated using the following equations: q = mCT q = m 4.184 J g C T or q = m 1 cal T g C Note: Any heat lost by the substance (-q) equals the heat gained by the water (+q) and vice versa. Notice that throughout our discussion of calorimetry, we have assumed that the calorimeter itself does not absorb any heat. We have also assumed that no heat escapes from the calorimeter. Neither of these assumptions is completely true. However, we will continue to make these assumptions in order to simplify our calculations. The error from actual losses of heat should be considered in any laboratory exercise using calorimeters. EXAMPLE: Phosphorus trichloride, PCl3, is a compound used in the manufacture of pesticides and gasoline additives. How much heat is required to raise the temperature of 96.7 g of PCl3 from 31.7°C to 69.2°C. The specific heat of PCl3 is 0.874 J/g°C. 69.2 C q = mCT -69.2 31.7CC q ??? m 96.7 g 96.7 g o.874 J qC = 0.874 J/g J/g°C C g C T1 31.7°C 31.7 C T2 q = T 96.7 g Co.874 J 69.2°C 69.2 T2 – T1 g C - 31.7 37.5CC T q = 3169.3425 J 37.5 C q = 3170 J Examples The specific heat of graphite is 0.71 J/g°C. Calculate the energy needed to raise the temperature of 75 kg of graphite from 294 K to 348 K. 348 K q = mCT q = q = 75 kg 75 kg 1000 o.71 Jg o.71 T J g1 kg C g C 1000 g o.71 J 1 kg g C T 54 C q = 2.9 x 106 J q = 2.9 x 103 kJ - 294 K 54 K EXAMPLE: An Oreo® is burned in a bomb calorimeter containing 5.0 L of water originally at 25.0 °C. After igniting the Oreo®, the water temperature increases to 30.6°C. How many Calories of energy did the Oreo® contain? Volume of water = 5.0 L T1 = 25.o °C T2 = 30.6 °C How What does happened the heat togained the Why? bytemperature the water compare of the to the heat water? lost by the Oreo? Law of Conservation of Energy!!! Volume of water = 5.0 L If we calculate the T1 = 25.o °C heat gained by the How can we find water, this the T2 = 30.6 °C mass of the water? necessarily equals the heat lost by the Density = mass / volume cookie CH2O= 1 cal/g °C mass = Density * volume mass = 1.0gg 1.0 mL mL 5.0L L 5.0 mass = 1000 mL 1L 5.0 x 103 g Putting it all together…. qH2O = 5.0 x 103 g 1 cal 5.6 °C qH2O = 28 Calories g °C 1 Cal 1000 cal EXAMPLE: A reaction changes the temperature of a calorimeter with 500. mL of water from 10.°C to 50.°C. What is the ΔH for the reaction? = 500. g 4.184 J g °C = 40. °C ??? m 500. g C 4.184 J/g°C 84000 J = - 84000 J = q - 8.4 x 104 J T1 10.°C T22 50.°C T 40. °C Calorimetry Example A 12.5 g metal block was heated to 100.00°C and dropped into a coffee-cup calorimeter containing 48.0 g of water at 24.37°C. After the block was dropped into the water, the temperature of the water rose to 26.43°C. What is the specific heat capacity of the metal? m= C= T1 = T2 = ΔT = T2 – T1 METAL 12.5 g 100.00°C 26.43°C -73.57 °C WATER 48.0 g 4.184 J/g°C 24.37°C 26.43°C 2.06°C Law of Conservation of Energy!!! qH2O = 48.0 g qH2O = 4.184 J g °C 2.06°C 413.7139 J - 413.7139 J The unknown is Cmetal - 413.7139 J 12.5 g .4499 J/g °C .450 J/g °C -73.57 °C The unknown is Cmetal Cmetal = Cmetal = 48.0 g 4.184 J g °C Cmetal = 2.06°C - 12.5 g .450 .4499J/g J/g°C °C -73.57 °C Examples A 46.2 g sample of copper is heated to 95.4°C and then placed in a calorimeter containing 75.0 g of water at 19.6°C. The final temperature of both the water and the copper is 21.8°C. What is the specific heat of copper? COPPER m= 46.2 g C= 95.4°C T1 = 21.8°C T2 = ΔT = T2 – T1 Cmetal = 75.0 g -73.6°C 4.184 J Cmetal g °C = WATER 75.0 g 4.184 J/g °C 19.6° 21.8°C 2.2°C 2.2°C .20 J/g -°C 46.2 g -73.6 °C ENERGY AND CHANGES OF STATE: When energy is added to a solid substance, its temperature increases. Before the melting point is reached, the added energy increases the kinetic energy of the particles. Thus, because the particles in a solid are held together in a fixed position, the addition of heat causes the particles to vibrate faster about a fixed position. At the melting point, the addition of more energy causes the substance to melt. The temperature, however, remains the same until all of the substance has melted. Melting is when the added energy changes the positions of the particles and now they can leave their original positions and move to other locations in the substance. (This is why liquids take on the shape of the container.) The potential energy changes as the physical state changes. The energy required to melt one gram of a specific substance is called the enthalpy of fusion, Hfus, of that substance. A similar phenomenon takes place at the boiling point (condensation point). The addition of energy to the liquid causes the particles to move about at a faster rate. These liquid particles are free enough to slip past one another and appear to vibrate about a moving point. At the boiling point, the addition of more energy causes the particles to spread apart even more, and undergo a phase change into a gas. The energy required to vaporize one gram of a substance at its boiling point is called the enthalpy of vaporization, Hvap of the substance. As a gas, these particles move independent of each other in rapid, random motion. When matter is heated further near temperatures of 5000C, the collisions between the particles are so violent that electrons are knocked away from the atoms. The action produces a state of matter composed of electrons and positive ions, which is called plasma. CALCULATIONS: The enthalpy of vaporization of water is 2.25 kJ/g. The enthalpy of fusion of water is 0.333 kJ/g. Change in kinetic energy q = mCT Increase in potential energy H = m (Hvap) at the boiling point Decrease in potential energy H = m (-Hvap) at the condensation point Increase in potential energy H = m (Hfus) at the melting point Decrease in potential energy H = m (-Hfus) at the crystallization point REMEMBER THAT q = H at constant pressure Heating Curve for Water 120 Water and Steam 100 80 Steam 60 Water 40 20 0 Ice Water and Ice -20 0 40 120 220 760 800 Heating Curve for Water 120 HeatWater of and Vaporization Steam 100 80 Steam 60 Water 40 20 0 Ice Water and Ice -20 0 40 120 220 760 800 Heating Curve for Water 120 Water and Steam 100 80 Steam 60 Water 40 20 Heat ofWater and Ice Ice Fusion 0 -20 0 40 120 220 760 800 Heating Curve for Water 120 Both Water Water and and Steam Steam 100 80 Steam 60 Water 40 20 0 Ice Water and Ice -20 0 40 120 220 760 800 Heating Curve for Water 120 Water and Steam 100 80 Steam 60 Water 40 20 Ice andWater Ice Waterand Ice 0 -20 0 40 120 220 760 800 Examples How much heat does it take to heat 12 g of ice at -6C to 25C water? When constructing the graph, note the •Beginning and Ending temperatures •T he temperature(s) of any phase change(s) within that range. For every segment of the graph, you must calculate the heat involved. q1 q2 q3 How much heat does it take to heat 12 g of ice at -6°C to 25°C water? q1 = mCiceT q2 = mHfusion q3 = mCwater T q1 = mCice T q231 = q1 = 149.76 J q1 12 g q2 q1 = 149.76 J 0.333 4.184 2.08 kJ JJ 1000 25 6 °C °CJ q2 = 3996 J g g°C 1 kJ q3 = 1255.2 J = J5400 = 5400.96 J q3q qq2tot = 3996 J =tot 1255.2 q3 J How much heat does it take to heat 35 g of ice at 0 C to steam at 150. C? q3 q1 = mHfusion q2 = mCwater T q3 = mHvap q2 q4 = mCsteam T q1 q4 How much heat does it take to heat 35 g of ice at 0 °C to steam at 150.°C? q1 = mHfusion q1 = 35 g 0.333 kJ 1000 J g 1 kJ q1 = 11655 J q2 = mCwater T 35 g q2 = q2= 14644 J q3 = mHvap q3= 79100 J q4 = mCsteam T q4= 3573.5 J 4.184 J g °C 100. °C 35 g q3 = qTot= 108972.5 J 35 g q4 = qTot= 109000 J 2.26 kJ g 2.042 J g °C 1000 J 1 kJ 50. °C