2. Calorimetry is the technological process of measuring energy changes of an isolated system called a calorimeter Calorimetry is the technological process of measuring energy changes of an isolated system called a calorimeter

3. Thermochemistry The study of energy changes by a chemical system during a chemical reaction The study of energy changes by a chemical system during a chemical reaction

4. Isolated System Calorimetry deals with an isolated system, where matter NOR energy can move in or out Calorimetry deals with an isolated system, where matter NOR energy can move in or out

5. Laws of Thermodynamics 1 st Law = energy cannot be created or destroyed but transferred 1 st Law = energy cannot be created or destroyed but transferred 2 nd Law = heat flows from hot to cold, and heat loss is equal to heat gained 2 nd Law = heat flows from hot to cold, and heat loss is equal to heat gained

6. -mc Δ t = nH m Heat lost = heat gained Heat lost = heat gained “system” “calorimeter” “system” “calorimeter” nH m = -mc Δ t nH m = -mc Δ t Ep = -Ek Ep = -Ek

7. Within the calorimeter there is a known volume of liquid (usually water) in which the chemical reaction to be studied occurs Within the calorimeter there is a known volume of liquid (usually water) in which the chemical reaction to be studied occurs

8. Energy (as heat) is transferred between the chemical system and the water Energy (as heat) is transferred between the chemical system and the water

9. Calorimetry requires careful measurements of masses and temperature changes Calorimetry requires careful measurements of masses and temperature changes the chemical energy lost by the chemical system is calculated by the thermal energy gained by the surroundings the chemical energy lost by the chemical system is calculated by the thermal energy gained by the surroundings

10. remember: thermal energy is the total kinetic energy remember: thermal energy is the total kinetic energy q = mc Δ t q = mc Δ t

11. remember potential energy of a reaction is the enthalpy remember potential energy of a reaction is the enthalpy Δ H = nH m

12. Assumptions in Calorimetry

13. styrofoam is considered a perfect insulator… styrofoam is considered a perfect insulator… energy lost to the calorimeter is ignored energy lost to the calorimeter is ignored

14. only the water releases or absorbs heat… only the water releases or absorbs heat… so we only need to use the specific heat capacity of water (4.19 kJ/kgC) so we only need to use the specific heat capacity of water (4.19 kJ/kgC)

15. volume of water is equal to (and interchangeable with) the mass of water… volume of water is equal to (and interchangeable with) the mass of water… mL = g mL = g L = kg L = kg

16. these assumptions allow the idea that energy gained by the calorimeter water equals the energy lost by the reaction and vice versa these assumptions allow the idea that energy gained by the calorimeter water equals the energy lost by the reaction and vice versa

17. nH m = mc Δ t calorimeter

18. Example 2 When excess zinc is added to 50.0mL of 0.25mol/L aqueous copper(II)sulfate, the calorimeter warms by 12.5°C. What is the molar enthalpy of reduction of aqueous copper(II) ions? When excess zinc is added to 50.0mL of 0.25mol/L aqueous copper(II)sulfate, the calorimeter warms by 12.5°C. What is the molar enthalpy of reduction of aqueous copper(II) ions?

19. Answer: - 209500J/mol

20. Example 2 When 50.0mL of 1.0mol/L NaOH, initial temperature 17.4°C is mixed with 50.0mL of 1.0mol/L HCl, initial temperature 24.2°C. What is the molar enthalpy change for the neutralization of the base?

21. Answer: 28492J/mol

22. Bomb Calorimetry

23. professionals use a bomb calorimeter to measure the energies released and absorbed by reactions. professionals use a bomb calorimeter to measure the energies released and absorbed by reactions.

24. bomb calorimetry minimizes heat loss with superior insulation and very exact temperature measurements giving more accurate enthalpies of reaction bomb calorimetry minimizes heat loss with superior insulation and very exact temperature measurements giving more accurate enthalpies of reaction

26. Heat Change of the Calorimeter Includes water, bomb, thermometer stirrir, container… Includes water, bomb, thermometer stirrir, container…

27. the masses and heat capacities of all the components of the bomb calorimeter are constants… the masses and heat capacities of all the components of the bomb calorimeter are constants…

28. therefore we can use the formula therefore we can use the formula nHm = -C Δ T

29. Example 1 Consider a 1.00g sample of benzoic acid burning in a bomb calorimeter. The initial temperature is 25.00°C and the heat capacity of the calorimeter is 5.43kJ/°C. The combustion causes the temperature of the calorimeter to rise to 29.86°C. Using this data, what is the molar enthalpy of the combustion of benzoic acid? Consider a 1.00g sample of benzoic acid burning in a bomb calorimeter. The initial temperature is 25.00°C and the heat capacity of the calorimeter is 5.43kJ/°C. The combustion causes the temperature of the calorimeter to rise to 29.86°C. Using this data, what is the molar enthalpy of the combustion of benzoic acid?

30. Answer: -3223kJ/mol

31. Example 2 A reaction in a bomb calorimeter absorbs 22.4kJ of heat energy. What is the initial temperature of the calorimeter if its final temperature was 24.22°C and its heat capacity is 28.7kJ/°C. A reaction in a bomb calorimeter absorbs 22.4kJ of heat energy. What is the initial temperature of the calorimeter if its final temperature was 24.22°C and its heat capacity is 28.7kJ/°C.

32. Answer: +25C