1. THERMOCHEMISTRY Study of heat change in chemical reactions

2. Systems, Surroundings & Internal Energy Surroundings Surroundings = rest of the universe (or as much as needed…)  the flask.  perhaps the flask and this classroom.  perhaps the flask and all of the building, etc. Universe Universe = System + Surroundings System System = the part of the universe under study  chemicals in a flask.  the coffee in your coffee cup.  my textbook.

3. The First Law of Thermodynamics Thermodynamics Deals with all kinds of energy effects in all kinds of processes Two types of energy: Heat (q) Work (w) The Law of Conservation of Energy Δ E system = - Δ E surroundings The First Law: Δ E = q + w The total change in energy is equal to the sum of the heat and work transferred between the system and the surroundings

4. The First Law of Thermodynamics Internal energy Internal energy = E within the system because of nanoscale position or motion Conservation of energy becomes: Δ E = q + w

5. Heat Thermal E transfer caused by a T difference. thermal equilibriumHeat flows from hotter to cooler objects until they reach thermal equilibrium (have equal T ).

6. Work In an internal combustion engine, a significant fraction of the energy of combustion is converted to useful work – The expansion of the combustion gases produces a volume and a pressure change – The system does work on its surroundings Propels the car forward Overcomes friction Charges battery

7. Pressure- Volume Work

8. Note the same sign convention for q and w ΔE = q + w Heat transfer out q < 0 Work transfer in w > 0 Heat transfer in q > 0 Work transfer out w < 0 SURROUNDINGS SYSTEM

9. 1. A liquid cools from 45°C to 30°C, transferring 911 J to the surroundings. No work is done on or by the liquid. What is Δ E liquid ? SAMPLE PROBLEMS 2. A system does 50.2 J of work on its surroundings and there is a simultaneous 90.1 J heat transfer from the surroundings to the system. What is Δ E system ?

10. State functions Always have the same value whenever the system is in the same state. Two equal mass samples of water produced by: 1.Heating one from 20°C to 50°C. 2.Cooling the other from 100°C to 50°C. have identical final H (and V, P, E…). State functions H HE PV Tetc. State Functions and Path Independence path independent State function changes are path independent. Δ H = H final – H initial is constant.

11. ENTHALPY of Chemical Reactions At constant V, Δ V = 0 At constant p,

12. Enthalpy, Δ H H = E + PV Δ H = Δ E + P Δ V ; Δ H = q p – The PV product is important only where gases are involved; it is negligible when only liquids or solids are involved Δ H = Δ E + Δ n g RT –Δ n g is the change in the number of moles of gas as the reaction proceeds

13. Measurement of Heat Flow: Calorimetry A calorimeter is a device used to measure the heat flow of a reaction – The walls of the calorimeter are insulated to block heat flow between the reaction and the surroundings – The heat flow for the system is equal in magnitude and opposite in sign from the heat flow of the calorimeter q reaction = - q calorimeter q reaction = - C cal Δ t

14. The Calorimetry Equation q = C x Δ t –Δ t = t final – t initial – C (uppercase) is the heat capacity of the system: it is the quantity of heat needed to raise the temperature of the system by 1 °C q = m x c x Δ t – c (lowercase) is the specific heat: the quantity of heat needed to raise the temperature of one gram of a substance by 1 °C c depends on the identity and phase of the substance

16. Coffee-cup calorimeter Nested styrofoam cups prevent heat transfer with the surroundings. Constant P. Δ T measured. q = q p = Δ H Assume the cups do not absorb heat. (C cal = 0 and q cal = 0) Measuring Enthalpy Changes

17. or − q reaction = q bomb + q water with q bomb = m cal c cal Δ T = C cal Δ T Bomb Calorimeter Measure Δ T of the water. Constant V: q V = Δ E Conservation of E: q reaction + q bomb + q water = 0 Measuring Enthalpy Changes A constant for a calorimeter

18. Sample Problem Copper is used in building the integrated circuits, chips and printed circuit boards for computers. When 228 J of heat are absorbed by 125 g of copper at 22.38 o C, the temperature increases to 27.12 o C. What is the specific heat of copper?

19. A student wishes to determine the heat capacity of a coffee-cup calorimeter. After she mixes 100.0 g of water at 58.5°C with 100.0 g of water, already in the calorimeter, at 22.8°C, the final temperature of the water is 39.7°C. Calculate the heat capacity of the calorimeter in J/°C. Use 4.184 J/g - °C as the specific heat of water.

20. Octane (0.600 g) was burned in a bomb calorimeter containing 751 g of water. T increased from 22.15°C to 29.12°C. Calculate the heat evolved per mole of octane burned. C cal = 895 J°C -1. 2 C 8 H 18 (l) + 25 O 2 (g) 16 CO 2 (g) + 18 H 2 O (l) q sys + q surr = 0 q reaction + q bomb + q water = 0 q bomb = C cal Δ T = 895 J°C -1 (29.12 – 22.15)°C = +6238 J q water = m c Δ T = 751 g (4.184 J g -1 °C -1 )(29.12 – 22.15)°C = +2.190 x 10 4 J So − q reaction = +6238 + 2.190 x 10 4 J = 2.81 x 10 4 J = 28.1 kJ q reaction = − 28.1 kJ Measuring Enthalpy Changes

21. Octane (0.600 g) was burned in a bomb calorimeter… Calculate the heat evolved per mole of octane burned Molar mass of C 8 H 18 = 114.23 g/mol. n C8H18 = (0.600 g) / (114.23 g/mol) = 0.00525 mol C 8 H 18 Heat evolved /mol octane = − 28.1 kJ 0.00525 mol = − 5.35 x 10 3 kJ/mol = − 5.35 MJ/mol Measuring Enthalpy Changes

22. Thermochemical Equations a chemical equation with the Δ H for the reaction included Example NH 4 NO 3 (s)  NH 4 + (aq) + NO 3 - (aq) Δ H = +28.1kJ This means: +28.1 kJ +28.1 kJ +28.1 kJ Or or 1 mol NH 4 NO 3(s) 1 mol NH 4 + (aq) 1 mol NO 3 - (aq)

23. Conventions for Thermochemical Equations 1. The sign of Δ H indicates whether the reaction is endothermic or exothermic 2. The coefficients of the thermochemical equation represent the number of moles of reactant and product 3. The phases of all reactant and product species must be stated 4. The value of ΔH applies when products and reactants are at the same temperature, usually 25 °C

24. Rules of Thermochemistry Δ H is directly proportional to the amount of reactant or product – If a reaction is divided by 2, so is Δ H – If a reaction is multiplied by 6, so is Δ H Δ H changes sign when the reaction is reversed Δ H has the same value regardless of the number of steps

25. Sample Problem In photosynthesis, the following reaction takes place: 6CO 2(g) + 6H 2 O (l)  6O 2(g) + C 6 H 12 O 6(s)  H = + 2801 KJ a. Calculate  H when one mole of carbon dioxide reacts? b. How many kilojoules of energy are liberated when 15.00 g of glucose is burned in oxygen?

26. METHODS OF DETERMINING  H reaction 1.DIRECT METHOD - using  H o f of every reactants and products of chemical reaction 2. INDIRECT METHOD - using HESS LAW (for reaction involving several steps)

27. DIRECT METHOD Δ H° =  {(n products )( Δ H f ° products)} –  {(n reactants )( Δ H f ° reactants)} Where: Δ H f ° = standard molar enthalpy of formation taken from Thermodynamic data

28. Standard state Standard state = most stable form of the pure element at P = 1 bar.  e.g. C standard state = graphite (not diamond) Δ H f ° for any element in its standard state is zero. (take 1 mol of the element and make… 1 mol of element) Δ H f ° (Br 2 ( l ) ) = 0at 298 K Δ H f ° (Br 2 (g) ) ≠ 0at 298 K Standard Molar Enthalpy of Formation

29. 1 but the formation reaction is: H 2 (g) + ½ O 2 (g) H 2 O (l) Δ H f ° = − 285.83 kJ H 2 combustion: 2 H 2 (g) + O 2 (g) 2 H 2 O (l) Δ H° = − 571.66 kJ f = formation Formation reaction Make 1 mol of compound from its elements in their standard states.

31. Δ H° =  {(n products )( Δ H f ° products)} –  {(n reactants )( Δ H f ° reactants)} 3 Δ H° = [1 Δ H f °(HCN) + 3 Δ H f °(H 2 )] − [1 Δ H f °(NH 3 ) + 1 Δ H f °(CH 4 )] DIRECT METHOD = [+134 + 3(0)] − [ − 46.11 + ( − 74.85)] = 255 kJ Example Calculate Δ H° for: CH 4 (g) + NH 3 (g)  HCN(g) + 3 H 2 (g) Δ H f ° :-46.11 -74.85 +134 0

33. INDIRECT METHOD - Hess’s Law “If the equation for a reaction is the sum of the equations for two or more other reactions, then Δ H° for the 1 st reaction must be the sum of the Δ H° values of the other reactions.” Another version: “ Δ H° for a reaction is the same whether it takes place in a single step or several steps.” H is a state function

34. SAMPLE PROBLEMS