CHAPTER 17: THERMOCHEMISTRY. Heat vs. Temperature. Heat vs. Temperature. q = mc T. Heat Capacity vs. Specific Heat

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1 CHAPTER 17: THERMOCHEMISTRY Page Heat vs. Temperature ATOM Heat energy= Kinetic energy SUBSTANCE Heat energy = TOTAL Kinetic energy of all atoms in a substance Temperature = AVERAGE Kinetic energy of the atoms in a substance Each atom contains Kinetic energy Like each test has a score All the energy can be added together = amount of heat energy Total points The energy can be averaged= temperature Average of all scores Test Total Average Points Heat vs. Temperature Heat Units: Joule (J) 1KJ = 1000J Units: calories 1Kcal = 1000cal 4.18J = 1cal Temperature Units: Celsius ( C)( or Kelvin (K) Kelvin = C C Heat Capacity vs. Specific Heat q = mc T Heat Capacity (C) J/ C Specific Heat (c) J/g C Table page 508 Water= 4.18J/g C Water= 1.00cal/g C q = heat (J) m = mass (g) c = specific heat (J/g C) T T = change in temperature ( C)( 1

2 Example The temperature of a 95.4g piece of copper increases from 25.0 C C to 48.0 C when the copper absorbs 849J of heat. What is the specific heat of copper. q= m= c= T= 849J/95.4g x 23.0 C C = 0.387J/g C Solving for q Find the amount of heat needed to raise the temperature of 15.0g of water from 25.0 to 35.0 C q = m= c= T= 15.0g x 4.18J/g C C x 10.0 C q= 627J Solving for T How much temperature change would occur if 627J of heat were added to 15.0g of aluminum? Q = m= c= T= 627J/15.0g x 0.90J/g C 46.4 C Thermochemical Equations Include the heat change Include the phase of substances Amount of heat given is for the number of moles of each substance indicated by the coefficients in the equation Why Phase of Substance Must Be Included Decomposition of 1 mole of Water H 2 O (l) H 2(g) + ½O 2(g) H 2 O (g) H 2(g) + ½O 2(g) H=285.8KJ H=241.8KJ difference= 44.0KJ Difference in H H is due to the difference in physical state H 2 O (l) H 2 O (g) H=44.0KJ Exothermic vs. Endothermic Exo = out Endo = within Thermic = pertaining to heat C (s) + O 2(g) CO 2(g) KJ Exothermic or Endothermic 2CuO (s) KJ 2Cu (s) + O 2(g) Exothermic or Endothermic 2

3 Another Way to Write C (s) + O 2(g) CO 2(g) H= KJ Negative (-)( H H = heat is given off by the reaction 2CuO (s) 2Cu (s) + O 2(g) H H = KJ Positive (+) H H = heat is put into the reaction Standard enthalpy of formation ( Hf 0 ) is the heat change that results when one mole of a compound is formed from its elements at a pressure of 1 atm. The standard enthalpy of formation of any element in its most stable form is zero. H 0 (O 2 ) = 0 f H 0 (O 3 ) = 142 kj/mol f H 0 (C, graphite) = 0 f H 0 (C, diamond) = 1.90 kj/mol f 6.6 Enthalpy Change ( H)( Find the heat change for the burning of 25.0g of carbon 1-balanced chemical equation C (s) + O 2(g) CO 2(g) KJ 2-given over g C/1 3-check to see if given is in moles if not convert to moles 25.0g 4-Use mole to energy ratio 6.6 The standard enthalpy of reaction ( Hrxn 0 ) is the enthalpy of a reaction carried out at 1 atm. aa + bb cc + dd H 0 rxn = [ c H 0 f (C) + d H 0 f (D)] - [ a H 0 f (A) + b H 0 f (B)] H 0 rxn = Σ H 0 (products) f - Σ H 0 f (reactants) Hess s Law: When reactants are converted to products, the change in enthalpy is the same whether the reaction takes place in one step or in a series of steps. (Enthalpy is a state function. It doesn t matter how you get there, only where you start and end.) 6.6 Benzene (C 6 H 6 ) burns in air to produce carbon dioxide and liquid water. How much heat is released per mole of benzene combusted? The standard enthalpy of formation of benzene is kj/mol. 2C 6 H 6 (l) + 15O 2 (g) 12CO 2 (g) + 6H 2 O (l) H 0 rxn = Σ H 0 f(products) - Σ H 0 f(reactants) H 0 rxn = [ 12 H 0 f (CO 6 H 0 2 ) + f (H 2 O) ] - [ 2 H 0 f (C 6 H 6 )] H 0 rxn = [ ] [ ] = kj kj 2 mol = kj/mol C 6 H

4 Chemistry in Action: Fuel Values of Foods and Other Substances C 6 H 12 O 6 (s) + 6O 2 (g) 6CO 2 (g) + 6H 2 O (l) H = kj/mol 1 cal = J 1 Cal = 1000 cal = 4184 J CALORIMETRY Technique to measure amount of heat absorbed or released Calorimeter instrument used for calorimetry Heat & Phase Changes Heat of Fusion & Solidification H fus = - H solid H 2 O (s) H 2 O (l) H 2 O (l) H 2 O (s) H = H H = 6.01KJ/mol H = -6.01KJ/mol Heat of Fusion Problem How many grams of ice at 0 C 0 C will melt if 2.25KJ of heat are added? 1-given over 1 2-use heat of fusion to convert Heat of Vaporization & Condensation H Vap = - H cond H 2 O (l) H 2 O (g) H H = 40.7KJ/mol H 2 O (g) H 2 O (l) H H = -40.7KJ/mol Heat of Vaporization Problem How much heat (in KJ) is absorbed when 24.8g H 2 O (l) at 100 C C and 101.3kPa is converted to steam at 100 C 4

5 What You Need To Know About Water Molar Mass = 18.02g Boiling Point = C Freezing Point= 0.0 C Specific Heat= Heat of fusion= Heat of vaporization 4.18J/g C C or 1cal/g C 6.01 KJ/mol 40.7KJ/mol The enthalpy of solution ( H soln ) is the heat generated or absorbed when a certain amount of solute dissolves in a certain amount of solvent. H soln = H soln - H components Which substance(s) could be used for melting ice? Which substance(s) could be used for a cold pack? Calculating the Enthalpy Change in Solution Formation How much heat (in KJ) is released when 2.500mol NaOH (s) is dissolved in water? List the knowns and the unknown Knowns H soln = KJ/mol (off table) Amount of NaOH (s) dissolved = 2.500mol 6.7 First Law of Thermodynamics Energy can be converted from one form to another but energy cannot be created or destroyed. Second Law of Thermodynamics The entropy of the universe increases in a spontaneous process and remains unchanged in an equilibrium process. Spontaneous process: S univ = S sys + S surr > 0 of Reaction The heat given off by the corrosion reaction of an iron- magnesium alloy with salt water can produce a hot meal. The rate of reaction is increased by adding salt water, so heat is produced rapidly. You will learn some ways in which the rate of a reaction can be increased. Equilibrium process: S univ = S sys + S surr =

6 In chemistry, the rate of chemical change, or the reaction rate, is usually expressed as the amount of reactant changing per unit time. A rate is a measure of the speed of any change that occurs within an interval of time. of chemical reactions are often measured as a change in the number of moles during an interval of time. According to collision theory,, atoms, ions, and molecules can react to form products when they collide with one another, provided that the colliding particles have enough kinetic energy. Effective Collision Ineffective Collision 6

7 The minimum energy that colliding particles must have in order to react is called the activation energy. Energy Diagrams Exothermic Endothermic (a) Activation energy (Ea) for the forward reaction (b) Activation energy (Ea) for the reverse reaction (c) Delta H 50 kj/mol 150 kj/mol -100 kj/mol 300 kj/mol 100 kj/mol +200 kj/mol An activated complex is an unstable arrangement of atoms that forms momentarily at the peak of the activation-energy barrier. The activated complex is sometimes called the transition state. The rate of a chemical reaction depends upon temperature, concentration, particle size, and the use of a catalyst. Animation 22 Explore several factors that control the speed of a reaction. Temperature Storing foods in a refrigerator keeps them fresh longer. Low temperatures slow microbial action. 7

8 Concentration a. In air, a lighted splint glows and soon goes out. b. When placed in pure oxygen (higher oxygen concentration), the splint bursts into flame. Particle Size The minute size of the reactant particles (grain dust), and the mixture of the grain dust with oxygen in the air caused the reaction to be explosive, destroying the grain elevator. Catalysts Simulation 23 Explore the effects of concentration, temperature, and a catalyst on reaction rate. An inhibitor is a substance that interferes with the action of a catalyst. Antioxidants and antimicrobials used in drying fruits and preserving fruit juices slow the action of microbes and limit contact with air. Section Quiz. 8

9 Section Quiz. 1. The units below that would be appropriate to measure the rate of a chemical reaction is mmol/s. mol/l. kj/mol. h/mol. Section Quiz. 2. In a chemical reaction, the energy of reactants is always greater than the energy of the products. more than the activation energy. less than the activation energy. less than the energy of the products. Section Quiz. 3. An increase in which one of the following will NOT increase the reaction rate? temperature concentration of reactants total mass of reactants surface area of reactants Section Quiz. 4. A catalyst works because it lowers the activation energy. increases the temperature. is permanently changed in a reaction. supplies energy to a reaction Reversible Reactions 18.2 Reversible Reactions At chemical equilibrium, no net change occurs in the actual amounts of the components of the system. A reversible reaction is one in which the conversion of reactants to products and the conversion of products to reactants occur simultaneously. 9

10 18.2 Reversible Reactions 18.2 Reversible Reactions SO 2 and O 2 react to give SO 3 SO 3 decomposes to SO 2 and O 2 When the rates of the forward and reverse reactions are equal, the reaction has reached a state of balance called chemical equilibrium. The relative concentrations of the reactants and products at equilibrium constitute the equilibrium position of a reaction. At equilibrium, all three types of molecules are present Reversible Reactions Factors Affecting Equilibrium: Le Châtelier âtelier s Principle Stresses that upset the equilibrium of a chemical system include changes in the concentration of reactants or products, changes in temperature,, and changes in pressure. Le Châtelier s principle: : If a stress is applied to a system in dynamic equilibrium, the system changes in a way that relieves the stress. Factors Affecting Equilibrium: Le Châtelier âtelier s Principle Concentration Rapid breathing during and after vigorous exercise helps reestablish the body s s correct CO 2 :H 2 CO 3 equilibrium, keeping the acid concentration in the blood within a safe range. Factors Affecting Equilibrium: Le Châtelier âtelier s Principle 18.2 Temperature Dinitrogen tetroxide is a colorless gas; nitrogen dioxide is a brown gas. The flask on the left is in a dish of hot water; the flask on the right is in ice. 10

11 Factors Affecting Equilibrium: Le Châtelier âtelier s Principle Pressure Pressure affects a mixture of nitrogen, hydrogen, and ammonia at equilibrium Conceptual Problem Conceptual Problem Conceptual Problem 18.2 Section Quiz Section Quiz. 1. In a reaction at equilibrium, reactants and products decrease in concentration. form at equal rates. have equal concentrations. have stopped reacting. 11

12 18.2 Section Quiz. 2. In the reaction 2NO 2 (g) 2NO(g) ) + O 2 (g), increasing the pressure on the reaction would cause the amount of NO to increase. the amount of NO 2 to increase. nothing to happen. the amount of O 2 to increase Section Quiz. 3. Changing which of the following would NOT affect the equilibrium position of a chemical reaction? concentration of a reactant only concentration of a product only temperature only volume only 18.4 Entropy and Free Energy Inside a pile of oily rags or a stack of hay that has not been thoroughly dried, decomposition causes heat to build up. When heat cannot escape, the temperature can become high enough to cause a fire. You will learn about the conditions that will produce a spontaneous chemical reaction. Free Energy and Spontaneous Reactions A spontaneous reaction occurs naturally and favors the formation of products at the specified conditions. Free Energy and Spontaneous Reactions A nonspontaneous reaction is a reaction that does not favor the formation of products at the specified conditions. Photosynthesis is a nonspontaneous reaction that requires an input of energy Free Energy and Spontaneous Free Energy and Spontaneous Reactions Spontaneous reactions produce substantial amounts of products at equilibrium and release free energy. Free energy is energy that is available to do work. 12

13 18.4 Entropy Entropy is a measure of the disorder of a system. Physical and chemical systems attain the lowest possible energy. The law of disorder states that the natural tendency is for systems to move in the direction of maximum disorder or randomness Entropy An increase in entropy favors the spontaneous chemical reaction; a decrease favors the nonspontaneous reaction Entropy For a given substance, the entropy of the gas is greater than the entropy of the liquid or the solid. Similarly, the entropy of the liquid is greater than that of the solid. Entropy Entropy increases when a substance is divided into parts Entropy Entropy tends to increase in chemical reactions in which the total number of product molecules is greater than the total number of reactant molecules Entropy Entropy tends to increase when temperature increases. As the temperature increases, the molecules move faster and faster, which increases the disorder. 13

14 Enthalpy, Entropy, and Free Energy The size and direction of enthalpy changes and entropy changes together determine whether a reaction is spontaneous; that is, whether it favors products and releases free energy. Enthalpy, Entropy, and Free Energy Gibbs Free-Energy Gibbs Free-Energy Gibbs Free-Energy Is the Gibbs free-energy energy change positive or negative in a spontaneous process? The Gibbs free-energy energy change is the maximum amount of energy that can be coupled to another process to do useful work. The numerical value of G is negative in spontaneous processes because the system loses free energy Section Quiz Section Quiz. 1. Free energy from a reaction is the amount of energy that is absorbed by an entropy decrease. equal to the enthalpy change. wasted as heat. available to do work. 14

15 18.4 Section Quiz. 2. Free energy is always available from reactions that are endothermic. nonspontaneous. at equilibrium. spontaneous Section Quiz. 3. Choose the correct words for the spaces: Spontaneous reactions produce and substantial amounts of at equilibrium. free energy, products no free energy, reactants free energy, reactants no free energy, products 18.4 Section Quiz. 4. Which of the following involves a decrease in entropy? Natural gas burns. A liquid freezes. Dry ice sublimes. Water evaporates Section Quiz. 5. A reaction is spontaneous if enthalpy decreases and entropy increases. enthalpy increases and entropy increases. enthalpy decreases and entropy decreases. enthalpy increases and entropy decreases Section Quiz. 6. Choose the correct words for the spaces: Gibbs free-energy energy change is the amount of energy that can be another process to do useful work. maximum, coupled to maximum, duplicated by spontaneous, coupled to minimum, duplicated by END OF SHOW 15

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