Introduction to Thermochemistry That’s Me! Okay…not really …Or is it?
Transcription
Introduction to Thermochemistry That’s Me! Okay…not really …Or is it?
Introduction to Thermochemistry That’s Me! Okay…not really …Or is it? Why study thermochemistry? • We depend on energy for nearly every aspect of our lives • Think about how you use energy every day… Electricity Cooking Automobiles Heating/Cooling Batteries • Cars, cell phones, iPods, watches Human Body • Temperature regulation • Conversion of food into usable cellular energy Seriously, why are we studying this? • Energy crisis in the world! • Over-use/dependence on fossil fuels (petroleum, gasoline, diesel, methane, propane) • Research/Development of alternative energy resources • • • • • Nuclear Fuel Cells (H2, Methanol, Solid oxide) Hydro Wind Solar NEWS FLASH: This is going to be OUR problem! Major Sources of Energy over the last 150 years An interesting quote… “So called “global warming” is just a secret ploy by wacko tree-huggers to make America energy independent, clean our air and water, improve the fuel efficiency of our vehicles, kick-start 21st century industries, and make our cities safer and more livable. Don’t let them get away with it!” - Chip Giller Founder of Grist.com, where environmentally minded people gather online. Organizing the Universe Any process can be defined by the following… • Universe = everything, the big enchilada, the whole kit and caboodle, all that and a bag of chips, the whole all that we jazz, tout, • System = the partshabang, of the universe are studying todos, alles, everything-ay, Chuck Norris, • i.e. a sarra, particular chemical reaction, etc. • etc. Surroundings = everything else in the universe that is NOT being studied • i.e. the environment, the lab, the students, your mom, etc. Universe System Surroundings Internal Energy • Total Energy = Kinetic Energy + Potential Energy due to motion stored energy • Endothermic process: energy enters the system (from the surroundings) System Energy Surroundings • Exothermic process: energy leaves the system (to the surroundings) System Energy Surroundings Kinetic Energy in Atoms & Molecules is proportional to • Temperature average KE of particles in a sample • Components of Kinetic Energy: Translation Rotation • KEtot = all components added together Vibration Potential Energy (PE) • Chemical Change: intramolecular potential energy • Breaking and forming chemical bonds (PEnucleus-electron) Example: 2H2 + O2 2H2O H H H O H O H O O H H H • Physical Change: intermolecular potential energy • Disrupting or forming intermolecular attractions (PEIMF) Example: H2O(ℓ) H2O(g) H H O H H H H H O O H O O H H O H H The Law of Conservation of Energy is also known as The First Law of Thermodynamics • Energy cannot be created or destroyed ΔEuniverse = 0 (reminder: Δ = “change in”) ΔEuniverse = ΔEsystem + ΔEsurroundings = 0 ΔEsystem = - ΔEsurroundings Energy can be transferred as: heat (q) work (w) ΔEsys = q + w The First Law of Thermodynamics Endothermic process: Universe System Energy Surroundings Exothermic process: Universe System Energy Surroundings In either case, the energy of the universe remains constant Conservation of Energy in a Chemical Reaction In this example, the energy Endothermic of the reactants Reaction and products increases, while the energy of the surroundings decreases. Reactant + Energy Product In every case, however, the total energy does not change. Surroundings Energy Surroundings System System Myers, Oldham, Tocci, Chemistry, 2004, page 41 Before reaction After reaction Conservation of Energy in a Chemical Reaction In this example, the energy Exothermic of the reactants Reaction and products decreases, while the energy of the surroundings increases. Reactant Product + Energy In every case, however, the total energy does not change. Energy Surroundings Myers, Oldham, Tocci, Chemistry, 2004, page 41 System Before reaction Surroundings System After reaction Heat (q) • Heat: the transfer of energy between objects due to a temperature difference • Flows from higher-temperature object to lower-temperature object System (T1) System (T1) Heat Heat Surroundings (T2) Surroundings (T2) If T1 > T2 q system = q surroundings = + exothermic If T1 < T2 q system = + q surroundings = endothermic Pressure/Volume Work (PV work) work = force distance force = pressure area = P m2 distance = m work = P m2 m = P V Assuming external pressure (Pext) is constant, the volume can change (ΔV) wsystem = -PextΔV (in L atm) Where ΔV = Vf – Vi (in L) Sign Conventions In chemistry, always take the system’s perspective (physics takes the surr’s view) • Heat (q) q>0 q<0 heat is added to the sys by surr (q is +) heat is leaving sys to surr (q is -) • Work (w) w>0 w<0 work done on sys by surr (work added to sys by surr, so w is +) work done by sys on surr (work is leaving surr, so w is -) Sign Conventions: Heat and Work Surroundings -w +w Work Work Heat System Heat + q (endo) - q (exo) Practice with Work and Heat An ideal gas expands from 5.0 L to 12.0 L against a constant external pressure of 2.0 atm. How much work is done? w = -PextΔV Pext = 2.0 atm Pext = 2.0 atm w = -(Pext)(Vfinal – Vinitial) w = -(2.0 atm)(12.0 L – 5.0 L) w = -14 L atm 1 L atm = 101.325 J w = -14 L atm (101.325 J/1 L atm) w = -1400 J If ΔE = 0 for this process, what is q? ΔE = q + w = q + (-1.42 103 J) = 0 q = 1400 J V1 = 5.0 L V2 = 12.0 L Practice with Work and Heat Calculate the change in energy for a system that loses 15 kJ of heat and expands from a volume of 10. L to 200. L under a constant Remember: external pressure of 2.0 atm. ΔE = q + w 101.325 J = 1 L atm w = -Pext ΔV 1000 J = 1 kJ w = -(2.0 atm)(200L -10L) = -380 L atm w = -380 L atm (101.325 J/1 L atm) (1 kJ/1000 J) = -38.5035 kJ ΔE = -15 kJ + -38.5035 kJ = -53.5035 kJ -54 kJ Calorimetry (Calorie Measuring) • Calorimetry: the science of measuring heat • C = heat capacity • the heat required to raise temp by 1°C (or 1 K) • Units → Joules/oC (J/oC or J/K) Because the temperature increase depends on the amount of “stuff”… • Specific heat capacity (Cp) • heat capacity per gram = J/goC or J/gK • Molar heat capacity (Cm) • heat capacity per mole = J/moloC or J/mol K Various Heat Capacities Substance Specific heat capacity (J/K g) Molar mass (g/mol) Molar heat capacity (J/K mol) Gold 0.129 197.0 25.4 Silver 0.235 107.9 25.4 Copper 0.385 63.55 24.5 Iron 0.449 55.85 25.1 Aluminum 0.897 26.98 24.2 H2O(l) 4.184 18.02 75.3 H2O(s) 2.03 18.02 36.6 H2O(g) 1.998 18.02 36.0 Using heat capacities… q = m C ΔT q (J) = mass (g) C (J/goC) ΔT (oC) q = joules (J) q (J) = moles (mol) C (J/K mol) ΔT (K) q = joules (J) Mnemonic device: q = m “CAT” Heating Curve of water Gas Temperature (oC) 140 120 l↔g 100 80 Boiling Point 60 40 20 0 -20 Liquid s↔l Melting Point -40 -60 -80 Solid -100 Energy Added Heating Curves • Temperature Change within phase • change in KE (molecular motion) • depends on heat capacity of phase C H2O (l) = 4.184 J/goC (requires the most heat) C H2O (s) = 2.03 J/goC C H2O (g) = 1.998 J/goC (requires the least heat) • Phase Changes (s ↔ l ↔ g) • change in PE (molecular arrangement) • temperature remains constant • overcoming intermolecular forces Calculating Energy Changes Temperature (oC) 140 120 q= ? q= ? 100 80 q = mass x Cgas x DT 60 40 20 0 q = mass x Cliquid x DT -20 -40 -60 -80 q = mass x Csolid x DT -100 Energy Added Same Formulas Different C Values Phase Transitions • During phase transitions, added heat is used to overcome intermolecular forces rather than to increase temperature ΔHfusion = energy needed to convert solid to liquid • For water, ΔHfusion = 6.02 kJ/mol • For liquid to solid, ΔH = - 6.02 kJ/mol ΔHvaporization = energy needed to convert liquid to gas • For water, ΔHvap = 40.7 kJ/mol • For gas to liquid, ΔH = - 40.7 kJ/mol Depending on the process occurring, all q’s are calculated individually and then added together Note: steps 2 and 4 → kJ Unit Conversions! steps 1, 3, 5 → J 4. q = mol x DHvap Temperature (oC) 140 120 2. q = mol x DHfus 100 80 5. q = mass x Cgas x DT 60 40 20 0 3. q = mass x Cliquid x DT -20 -40 -60 -80 1. q = mass x Csolid x DT -100 Energy Added Heating Curve of Water From Ice to Steam in Five Easy Steps 4 5 q1: Heat the ice to 0°C q = m Cice ΔTice 3 2 q2: Melt the ice into a liquid at 0°C q = mol ΔHfus q3: Heat the water from 0°C to 100°C q = m Cwater ΔTwater 1 Heat q4: Boil the liquid into a gas at 100°C Heat q = mol ΔHvap q5: Heat the gas above 100°C q = m Csteam ΔTsteam Heating Curve Practice How much energy (J) is required to heat 12.5 g of ice at –10 oC to water at 0.0 oC? 4 5 3 2 1 q1: Heat the ice from -10 to 0°C q = 12.5 g (2.03 J/g oC)(0.0 - -10.0 oC) = 253.75 J q2: Melt the ice at 0°C to liquid at 0 oC q = 12.5 g ice 1 mol 6.02 kJ = 4.177 kJ 18.016 g 1 mol qtot = q1 + q2 = 253.75 J + 4,177 J = 4,430 J Heating Curve Practice How much energy (J) is required to heat 25.0 g of ice at –25.0 oC to water at 95.0 oC? 4 3 2 1 5 Notice that your q values are positive because heat is added… q1: Heat the ice from -25 to 0°C q = 25.0 g (2.03 J/g oC)(0.0 - -25.0 oC) = 1268.75 J q2: Melt the ice at 0°C to liquid at 0 oC q = 25.0 g ice 1 mol 6.02 kJ = 8.352 kJ 18.016 g 1 mol q3: Heat the water from 0°C to 95 °C q = 25.0 g (4.184 J/g oC)(95.0 – 0.0oC) = 9937 J qtot = q1 + q2 + q3 = 1268.75 J + 8,352 J + 9937 J = 19,560 J Heating Curve Practice How much energy (J) is removed to cool 50.0 g of steam at 115.0 oC to ice at -5.0 oC? 4 3 2 1 5 Notice that your q values are negative because heat is removed… q5: Cool the steam from 115.0 to 100°C q = 50.0 g (1.998 J/g oC)(100.0 - 115.0 oC) = -1498.5 J q4: Condense the steam into liquid at 100°C q = 50.0 g H2O - 40.7 kJ 1 mol = -112.96 kJ 18.016 g 1 mol q3: Cool the water from 100°C to 0 °C q = 50.0 g (4.184 J/g oC)(0.0 – 100.0oC) = -20920 J q2: Freeze the water into ice at 0 °C q = 50.0 g H2O 1 mol - 6.02 kJ = -16.71 kJ 18.016 g 1 mol q1: Cool the ice from 0°C to – 5.0 °C q = 50.0 g (2.03 J/g oC)(- 5.0 – 0.0oC) = -507.5 J qtot = q1 + q2 + q3+ q4 + q5 = -1498.5 J + -112,960 J + -20920 J + -16,710 J + -507.5 J = -153,000 J Heating Curve Challenge Problems 1. A sample of ice at is placed into 75 g of water initally at 85oC. If the final temperature of the mixture is 15oC, what was the mass of the ice? 52.8 g ice Temperature (oC) -25oC 140 120 100 80 60 40 20 0 -20 -40 -60 -80 -100 DH = mol x DHvap DH = mol x DHfus Heat = mass x Dt x Cp, gas Heat = mass x Dt x Cp, liquid Heat = mass x Dt x Cp, solid Time 2. A 38 g sample of ice at -5oC is placed into 250 g of water at 65oC. Find the final temperature of the mixture assuming that the ice sample completely melts. 45.6 oC 3. A 35 g sample of steam at 116oC are bubbled into 300 g water at 10oC. Find the final temperature of the system, assuming that the steam condenses into liquid water. 76.6 oC What will happen over time? Zumdahl, Zumdahl, DeCoste, World of Chemistry 2002, page 291 Let’s take a closer look… Zumdahl, Zumdahl, DeCoste, World of Chemistry 2002, page 291 Eventually, the temperatures will equalize Zumdahl, Zumdahl, DeCoste, World of Chemistry 2002, page 291 Calorimetry • Allows us to measure the flow of heat • Think back to the ΔHfus expt.. q system = - q surroundings • In other words, whatever energy is lost by one is gained by the other (direct E transfer) • Major Assumption: No E is lost to other parts of the surroundings Typical Apparatus A Coffee Cup Calorimeter Used for calorimetry under constant pressure Thermometer Styrofoam cover Styrofoam cups i.e. normal lab conditions Stirrer Zumdahl, Zumdahl, DeCoste, World of Chemistry 2002, page 302 Constant-Pressure Calorimetry Example: 5.8 g of NaCl dissolves in 50.0 mL H2O NaCl(s) Na+(aq) + Cl-(aq) Ti = 22.2 °C Tf = 20.5 °C What is qrxn? Coffee cup calorimeter In this case, of the surroundings… We can’t directly measure q sys qrxn = qsystem = -qsurroundings qsurr = m C ΔT qsurr = (55.8 g)(4.184 J/°C g)(20.5 °C – 22.2°C) qsurr = -397 J qsystem = -qsurr = 397 J qrxn? Bomb Calorimeter • Constant V calorimetry (as opposed to P) • “Bomb” has own heat capacity (kJ/0C) • Multiply heat capacity by the ΔT to find the total heat transferred • Factor heat into # of g or mol burned (kJ/g or kJ/mol) Bomb Calorimeter Example A 1.800 g sample of sugar, C12H22O11, was burned in a bomb calorimeter whose total heat capacity is 15.34 kJ/oC. Once burned, the temperature of the calorimeter plus contents increased from 21.36oC to 28.78oC. What is the heat of combustion per gram of sugar? per mole of sugar? q = Cbomb x ΔT More sugar = more energy! q = 15.34 kJ/oC (28.78 oC – 21.36 oC) q = 113.8 kJ 113.8 kJ released per 1.800 g sugar 113.8 kJ / 1.800 g = 63.23 kJ/g 63.23 kJ 342.3 g g mol = 21640 kJ/mol Food and Energy Caloric Values Food joules/grams calories/gram Protein 17,000 4,000 4 Fat 38,000 9,000 9 Carbohydrates 17,000 4,000 4 1 calorie = 4.184 joules “Calories”/gram 1000 calories = 1 “Calorie” "science" "food" or… 1 Kcal = 1 “Calorie” Smoot, Smith, Price, Chemistry A Modern Course, 1990, page 51 Does water have negative calories…? How many Calories (nutritional) will you burn by drinking 1.0 L of water, initially at 36.5 oF (standard refrigeration temperature)? Assume that the body must expend energy to heat the water to body temperature at 98.6 oF. 37 oC 1 L = 1000 mL 2.5 oC 5 C F 32 1 mL = 1 g 9 1 calorie = 4.184 joules q mCDT 1000 calories = 1 “Calorie” q = 1.0 x 103 g (4.184 J/g oC)(37 oC - 2.5 oC) = 144,348 J 144348 J 1 cal 1 “Cal” 4.184 J 1000 cal = 35 Cal Heat Transfer Experiments Cu What is the final temperature, Tf, of the mixture? 20.0 g 150. mL 250.0 °C 20.0 °C C = 0.385 J/°C g - qCu = qwater q = m x C x ΔT for both cases, although specific values differ Plug in known information for each side Density of water = 1 g/mL(150 mL H2O) = 150 g H2O -mCuCCuΔT = mwaterCwater ΔT -20 g (0.385 J/goC)(Tf – 250 oC) = 150 g (4.184 J/goC)(Tf – 20oC) Solve for Tf ... Tf = 22.8 °C 240. g of water (initially at 20.0oC) are mixed with an unknown mass of iron initially at 500.0oC (CFe = 0.4495 J/goC). When thermal equilibrium is reached, the mixture has a temperature of 42.0oC. Find the mass of the iron. Fe T = 500oC mass = ? grams T = 20oC mass = 240 g - LOSE heat = GAIN heat -q1 = q2 - [ (mass) (CFe ) (DT)] = (mass) (CH2O) (DT) - [ (X g) (0.4495 J/goC) (42oC - 500oC)] = (240 g) (4.184 J/goC) (42oC - 20oC)] - [ (X) (0.4495) (-458)] = (240 g) (4.184) (22) 205.9 X = 22091 X = 107 g Fe A 97.0 g sample of gold at 785oC is dropped into 323 g of water, which has an initial temperature of 15.0oC. If gold has a specific heat of 0.129 J/goC, what is the final temperature of the mixture? Assume that the gold experiences no change in state of matter. Au T = 785oC mass = 97.0 g T = 15.0 oC mass = 323 g - LOSE heat = GAIN heat - [(C Au) (mass) (DT)] = (C H2O) (mass) (DT) - [(0.129 J/goC) (97 g) (Tf - 785oC)] = (4.184 J/goC) (323 g) (Tf - 15oC)] - [(12.5) (Tf - 785oC)] = (1.35) (Tf - 15oC)] -12.5 Tf + 9.82 x 103 = 1.35 x 103 Tf - 2.02 x 104 3 x 104 = 1.36 x 103 Tf Tf = 22.1oC If 59.0 g of water at 13.0 oC are mixed with 87.0 g of water at 72.0 oC, find the final temperature of the system. T = 72.0 oC mass = 87.0 g T = 13.0 oC mass = 59.0 g - LOSE heat = GAIN heat - [ (mass) (C H2O) (DT)] = (mass) (C H2O) (DT) - [ (59 g) (4.184 J/goC) (Tf - 13oC)] = (87 g) (4.184 J/goC) (Tf - 72oC)] - [(246.8) (Tf - 13oC)] = (364.0) (Tf - 72oC)] -246.8 Tf + 3208 = 364 Tf - 26208 29416 = 610.8 Tf Tf = 48.2oC