Intersection 6: Thermochemistry

1. A Intersection 6: Thermochemistry 10/10/05 6.4 p228-232; 6.7 p240-242; 6.10-6.11 p 248-256 11.3-11.4 p494-507

2. A A Review of Thermochemistry (from Studio) • Thermochemical Equations C(graphite) + O2(g)→ CO2(g)  ΔH = -393.509 kJ/mol • Endothermic and exothermic • Heats of reactions are additive (Hess’s Law) • Calorimetry • How heats of reaction are measured • Heat capacity q = mCDT

3. A Problem 1 Suppose you burn 0.300 g C(graphite) in an excess of O2(g) to give CO2(g). The temperature of the calorimeter which contains 775 g of water increases from 25.00oC to 27.38oC. What is the quantity of thermal energy evolved per mole of graphite?

4. A Question 1 100 mL of water at 25°C and 100 mL of alcohol at 25°C are both heated at the same rate under identical conditions. After 3 minutes the temperature of the alcohol is 50°C. Two minutes later the temperature of the water is 50°C. Which liquid received more heat as it warmed to 50°C? • The water. • The alcohol. • Both received the same amount of heat. • It is impossible to tell from the information given.

5. A Do all substances have the same heat capacity? Explain why at the beginning of the summer, the air is really warm, but the water at the beach is not. It takes 145 J to raise the temperature of 1 mole of air by 5oC. Is the heat capacity of air higher, lower, or the same as water?

6. A

8. M Thermochemistry (in IS) • Heat and bonds • Breaking bonds takes energy • Making bonds releases energy • Trends in bond enthalpy • Calculate Heats of Reactions • Heats of reaction can be calculated using bond enthalpy • Heat of reactions can be calculated using heats of formation • Change of state and heat energy

9. M Bonds Why do bonds form? Does it take energy or give off energy to break a bond? Picture from: www.nios.ac.in/ sc10/ch5sc10.htm

10. M The energy given off to make H-H bonds is shown below. H(g) + H(g) → H2(g)     Δ H = -435 kJ/mol    The opposite process, breaking H-H bonds requires the input of the same amount of energy that was given off in making the bond   H2(g) → H(g) + H(g)      Δ H = +435 kJ/mol    Which process is endothermic? Exothermic?  

11. M Bond Enthalpy (kJ/mol) (average energy needed to break bonds)

12. M Energy terms Heat energy: enthalpy, DH, q Enthalpy (H) is the quantity of thermal energy transferred into a system at constant pressure.   Δ E = Δ H + wexpansion "ΔH accounts for all the energy transferred except the quantity that does the work of pushing back the atmosphere, which is usually relatively small.  Whenever heat transfer is measured at constant pressure, it is ΔH that is determined." (Moore, p232)  

13. A Holy Contradiction! It takes energy to break bonds….and yet we get energy from fats (and carbohydrates and alcohol) by breaking them down ???

14. A How do we get energy from food? Food is broken down by adding O2 and converting all of the carbon and hydrogen in the food molecules to CO2 and H2O.

15. A Energy from Ethanol 3 2 3 CH3CH2OH  +  O2 →   CO2 + H2O 5 1 1 1 3 4 6 4733 kJ (-) 6014 kJ

16. A A Picture of Breaking Down Ethanol

17. A Total D H 4733 kJ into reactants 6014 kJ out of products Δ Hreaction = Σ Hreactants - Σ Hproducts = -1281 kJ Watch your signs!!!!!!!!!!….!!!!!

18. M Δ Hreaction = Σ Hreactants - Σ Hproducts = -3023 kJ Breaking Down Glucose 6 6 6 C6H12O6 + ___O2 ____CO2 + ___H2O 7 5 7 5 6 1212 12217 kJ 15240 kJ

19. C6O5H10 + 6 O2 6 CO2 + 5 H2O 4 C6O11N3H7 + 9 O2 24 CO2 + 14 H2O + 6 N2 Inflaming Nitrocellulose HNO3/H2SO4 Cellulose Oxidation Nitrocelluose Oxidation

20. Δ Hreaction = -2870 kJ/mol Δ Hreaction = -12,520 kJ/mol DHreaction Comparison

21. M Conversion to food Calories • 1 Calorie = 1 kilocalorie = 1000 calories • 1 calorie = 4.184 J • Convert the enthalpies for glucose and ethanol to Cal and Cal/g: For glucose = 722.5 Cal/mol = 4.0 Cal/g

22. M Comparing Energy Sources C18H36O2 + 26 O2 18 CO2 + 18 H2O DH = -10622 kJ Stearic acid *http://www.unlimited-health.com/nutrition/

23. M Evolution due to fat storage….. "Animals, though they store small amounts of glycogen in the muscles and liver, and rely on glucose in the bloodstream for immediate energy needs, bank most of their energy reserves in fat.  Economy in weight is important for an organism that must work not only to move, but simply to stand up against the force of gravity.  The body of a typical woman is about 25% fat by weight (a man's body is closer to 15%).  This means that if her fat supply were converted to its energy equivalent in carbohydrates, a 120-pound woman would weigh 150 pounds.  In a world where swiftness and agility increase an animal's chances for survival, fat is clearly the preferable means of energy storage. (Harold McGee, On Food and Cooking.Scribners, New York:  1984, p. 597.)

25. A Who wants to count up bonds every time? Δ Hof standard enthalpy of formation is the energy given off or needed to form a substance from its elements in their standard states [ie, O2(g), H2(g), N2(g), Br2(l), Na(s)..etc].   The o stands for standard conditions of 1 atm and 298K.    The formation reaction of gaseous water would be written: H2(g)  +  1/2 O2(g)  →  H2O(g)   Δ Hrxn (1 atm, 298K) = Δ Hof  H2O(g) = -241.83 kJ/mol Δ Hof found in Appendix J of Moore or back of coursepack

26. A Table 6-2, p.250

27. A Standard Enthalpy of Formation H2(g)  +  1/2 O2(g)  →  H2O(g)     Δ Hof H2O(g) = -241.83 kJ/mol Do you get a different answer from bond enthalpies?

28. M DHof : Signs and Multiplicity C(graphite) + O2(g)→ CO2(g)   ΔH = -393.509 kJ/mol CO2(g) → C(graphite) + O2(g)   ΔH = +393.509 kJ/mol 2C(graphite) +2 O2(g)→ 2CO2(g)   ΔH = -787.018 kJ/mol 4CO2(g) → 4C(graphite) + 4O2(g)   ΔH = +1574.04 kJ/mol

29. M 3C(s,graphite)+ 4H2(g)→ CH3CH2CH3(g) DH = - 103.82 kJ/mol Calculate the DHrxn using heats of formation CH3CH2CH3 (g) +   5 O2 (g)   →   3 CO2 (g) + 4 H2O (g) O2 (g)DH = 0 kJ/mol C(s,graphite)+ O2 (g) → CO2(g)DH = - 393.5 kJ/mol H2(g) + ½ O2(g) → H2O(g)DH = - 241.82 kJ/mol CH3CH2CH3(g) → 3C(s,graphite) + 4H2(g)DH = + 103.82 kJ/mol 3C(s,graphite)+ 3O2 (g) → 3CO2(g) 3(DH = - 393.5 kJ/mol) 4H2(g) + 2 O2(g) → 4H2O(g) 4(DH = - 241.82 kJ/mol) -2043.96 kJ/mol

30. M Calculate the DHrxn using heats of formation CH3CH2CH3 (g) +   5 O2 (g)   →   3 CO2 (g) + 4 H2O (g) Δ Hrxn = Σ nHofproducts - Σ nHofreactants Form the products (keep sign) Unform the reactants (change sign)  Σ nΔ Hof products = -393.5 kJ/mol (3 mol CO2)  +  -241.83 kJ/mol (4 mol H2O) = - 2147.82 kJ  Σ nΔ Hof reactants = -103.82 kJ/mol (1 mol propane)  +  0 kJ/mol (5 mol O2) = -103.82 kJ Δ Hrxn = Σ nHof products - Σ nHof reactants          = -2147.82 kJ - (-103.82 kJ)         = -2044 kJ

31. 4 Fe + 3 O2 2 Fe2O3 Iron Oxidation DHf for Fe2O3 = -824.2 kJ/mol What is DHf for Fe and O2?? Δ Hrxn = Σ nHofproducts - Σ nHofreactants Δ Hrxn = Σ nHof products - Σ nHof reactants          = 2(-824.2 kJ/mol) - 0         = -1648 kJ/mol

32. M Problem 2 2 C8H6(l) + 25 O2(g)16 CO2(g) + 18 H2O(g) H = -10,992 kJ Write a thermochemical equation for: • The production of 4.00 mol CO2(g) • The combustion of 100. mol C8H6 • How much heat energy is produced when 50 g of C8H6 is burned?

33. A Problem 3 The standard molar enthalpy of formation of AgCl(s) is –127.1 kJ/mol. Write a balanced thermochemical equation for which the enthalpy of reaction is –127.2 kJ

34. A Problem 4 The Romans used CaO as mortar in stone structures. The CaO was mixed with water to give Ca(OH)2, which slowly reacted with CO2 in the air to give limestone. Ca(OH)2(s) + CO2(g)  CaCO3(s) + H2O(g) Calculate the enthalpy change for this reaction

35. A Question 2 Heat is given off when hydrogen burns in air according to the equation 2H2 + O2  2H2O Which of the following is responsible for the heat? • Breaking hydrogen bonds gives off energy. • Breaking oxygen bonds gives off energy. • Forming hydrogen-oxygen bonds gives off energy. • Both (a) and (b) are responsible. • (a), (b), and (c) are responsible.

37. A Debate: _________is the safest and best artificial sweetener Friday, October 13th in studio • Splenda (sucralose) • Aspartame • Saccharin • Acesulfame K

38. A