Energy Changes, Reaction Rates and Equilibrium Thermodynamics: study of energy, work and heat

1. Energy Changes, Reaction Rates and Equilibrium Thermodynamics: study of energy, work and heat Kinetic energy: energy of motion Potential energy: energy of position, stored energy Chemical reactions involve changes in energy. Types of energy include: Heat, sound, electricity, light, motion, etc. Example: 2H + O2 2H2O + energy

2. Energy Law of conservation of energy: the total energy in a system does not change. (Energy cannot be created or destroyed during chemical reactions.) • Chemical bonds store potential energy. • A compound with lower potential energy is more stable than a compound with higher potential energy. • Reactions that form products having lower potential energy than the reactants are favored.

3. The Units of Energy calorie (cal): the amount of energy needed to raise the temperature of 1 g of water by 1 oC. Joule (J): is another unit of energy; 1 cal = 4.184 J • Both joules and calories can be reported in the • larger units kilojoules (kJ) and kilocalories (kcal). 1,000 J = 1 kJ 1,000 cal = 1 kcal

4. Energy Changes in Reactions When molecules come together and react, bonds are broken in the reactants and new bonds are formed in the products. • Bond breaking always requires an input of energy. • Bond formation always releases energy. To cleavethis bond, 58 kcal/mol must be added. Cl Cl To form this bond, 58 kcal/mol is released.

5. Energy Changes in Reactions Enthalpy change (H): the energy absorbed or released in a reaction; it is also called the heat of reaction • When energy is absorbed, the reaction is endothermic; H is positive (+). • When energy is released, the reaction is exothermic; H is negative (−). To cleave this bond, H = +58 kcal/mol. Cl Cl To form this bond, H = −58 kcal/mol.

6. Energy Diagrams The difference in energy between reactants and the products is H. • If H is negative, the reaction is exothermic:

7. If H is positive, the reaction is endothermic: 7

8. Exothermic Reaction: Reaction that releases heat to surroundings Endothermic Reaction: Reaction that absorbs heat from surroundings Exothermic Rxn H is negative (−) Endothermic Rxn H is positive (+)

9. Summary of Energy Changes in Reactions

10. Practice: Identify each reaction as exothermic or endothermic, and indicate the if the H is positive or negative. A. N2 + 3H2 2NH3 + 22 kcal B. CaCO3 + 133 kcal CaO + CO2 C. 2SO2 + O2 2SO3 + heat Exo, -H Endo, +H Exo, -H

11. Energy of activation (Ea): the minimum amount of energy necessary for a reaction to occur

12. Note the Activation Energy (Ea) in Exothermic and Endothermic Rxns Exothermic Rxn Endothermic Rxn

13. Activation Energy (Ea) • The Ea is the minimum amount of energy that the • reactants must possess for a reaction to occur. • Ea is called the energy barrier and the height of the barrier determines the reaction rate. • When the Ea is high, few molecules have enough • energy to cross the energy barrier, and the reaction • is slow. • When the Ea is low, many molecules have enough • energy to cross the energy barrier, and the reaction • is fast.

14. Factors that Influence Reaction Rates • Temperature of Reactants • Increasing the temperature increases the kinetic energy of the particles, allowing more collision to occur • Concentration of Reactants • The greater the concentration of reactants, the more collisions leading to a reaction will occur

15. Presence of Catalysts • Catalyst: Substance that increases rate of a reaction without being used up in the reaction • Catalysts provide alternate way for reaction to occur, with a lower activation energy than the normal way

16. Effect of Catalyst on Activation Energy With Catalyst (Lower Ea) Without Catalyst (High Ea)

17. The uncatalyzed reaction (higher Ea) is slower. • The catalyzed reaction (lower Ea) is faster. • H is the same for both reactions.

18. Chemical Equilibrium • Chemical reactions can go both directions (forward and reverse) • H2 + I2 2HI • Equilibrium: Condition when rate of forward reaction equals rate of reverse reaction • Equilibrium Concentrations: Unchanging concentrations of products and reactants in a reaction that is at equilibrium

19. The Equilibrium Constant Equilibrium constant, K: relationship between concentration of products and concentration of the reactants; concentration of products divided by concentration of reactants a A + b B c C + d D equilibrium constant [products] [reactants] [C]c[D]d = K = = [A]a [B]b

20. Note: The coefficient becomes the exponent! N2 + O2 2 NO [NO]2 equilibrium constant = K = [N2] [O2]

21. What does the Equilibrium Constant Tell Us? • When K is much greater than 1 (K > 1): [products] The numerator is larger. [reactants] Equilibrium favors the products and lies to the left. • When K is much less than 1 (K < 1): [products] The denominator is larger. [reactants] Equilibrium favors the reactants and lies to the right.

22. When K is around 1 (0.01 < K < 100): [products] Both are similarin magnitude. [reactants] Both reactants and products are present. 2 H2(g) + O2(g) 2 H2O(g) K = 2.9 x 1082 The product is favored because K > 1. The equilibrium lies to the right.

23. Equilibrium 23

24. Calculating the Equilibrium Constant Example: Calculate K for the reaction between the general reactants A2 and B2. The equilibrium concentrations are as follows: [A2] = 0.25 M [B2] = 0.25 M [AB] = 0.50 M A2 + B2 2 AB [AB]2 K = [A2][B2]

25. [AB]2 [0.50]2 K = = [A2][B2] [0.25][0.25] 0.25 = = 4.0 0.0625

26. Le Châtelier’s Principle If a chemical system at equilibrium is disturbed or stressed, the system will react in a direction that counteracts the disturbance or relieves the stress. Some of the possible disturbances: • concentration changes • temperature changes • pressure changes

27. Le Châtelier’s Principle: Concentration Changes 2 CO(g) + O2(g) 2 CO2(g) What happens if [CO(g)] is increased? • The concentration of O2(g) will decrease. • The concentration of CO2(g) will increase.

28. 2 CO(g) + O2(g) 2 CO2(g) What happens if [CO2(g)] is increased? • The concentration of CO(g) will increase. • The concentration of O2(g) will increase.

29. What happens if a product is removed? • The concentration of ethanol will decrease. • The concentration of the other product (C2H4) will increase.

30. Le Châtelier’s Principle: Temperature Changes • When the temperature is increased, the reaction that absorbs heat is favored. • An endothermic reaction absorbs heat, so increasing the temperature favors the forward reaction.

31. An exothermic reaction releases heat, so increasing the temperature favors the reverse reaction. • Conversely, when the temperature is decreased, the reaction that adds heat is favored.

32. Le Châtelier’s Principle: Pressure Changes • When pressure increases, equilibrium shifts in the direction that decreases the number of moles in order to decrease pressure.

33. When pressure decreases, equilibrium shifts in the direction that increases the number of moles in order to increase pressure.