1. CHAPTER 9 BALANCES ON REACTIVE PROCESSES By : Ms. Nor Helya Iman Bt Kamaludin Email: helya@unimap.edu.my 1 PTT 108: Mass and Energy Balances

2. Introduction The importance of energy balance on reactor: To tell the process engineer how much heating or cooling requires in order to operate at the desired conditions. Consequences of unstable heat on a reactor: Failure of the reactor temperature control system which can lead to  rapid overheating  possibly an explosion. 2 PTT 108: Mass and Energy Balances

3. Exothermic vs. Endothermic Reaction Exothermic ReactionEndothermic Reaction More energy is released when the product bonds form than it took to break the reactant bonds. More energy is required/ adsorbed to break the reactant bonds than it took to form the product bonds. Energy (heat or work) must be transferred away from the reactor to keep the temperature below a value that leads to safety and product quality problems. Energy (heat or work) must be added to the reactor to keep the reactor temperature (and hence the reaction rate) from decreasing; unprofitable. 3 PTT 108: Mass and Energy Balances

4. Heat of Reaction Definition: The heat of reaction (enthalphy of reaction), (T,P), is the enthalphy change for a process in which stoichiometric quantities of reactants at temperature, T and pressure, P react completely in a single reaction to form products at the same temperature and pressure. 4 PTT 108: Mass and Energy Balances

5. Heat of Reaction (cont’d) Consider a reaction: 5 PTT 108: Mass and Energy Balances

6. Heat of Reaction (cont’d) One O-O bond and two H-H bonds broken. System absorbs energy, U system and H system increase from reactants to transition state. 4 O-H bonds are formed. System releases energy, U system and H system decrease from transition state to products. 6 PTT 108: Mass and Energy Balances

7. Heat of Reaction (cont’d) Suppose stoichiometric quantities of the reactants (2 mol H 2 + 1 mol O 2 ) react completely, with the reactants starting at specified T and P and the products (2 mol H 2 O) ending at the same T and P. 7 PTT 108: Mass and Energy Balances

8. Heat of Reaction (cont’d) The change in enthalpy from reactants to products, is the heat of reaction. For stoichiometric quantities of H 2 and O 2 reacting completely at T=25ºC and P =1 atm, 8 PTT 108: Mass and Energy Balances

9. Heat of Reaction (cont’d) Negative more energy released by product bond formation than absorbed when reactant bonds break. The reaction is therefore exothermic. For example: 9 PTT 108: Mass and Energy Balances

10. Heat of Reaction (cont’d) If 5 mol H 2 /s consumed in which the reactants and products are at 25°C, then the energy balance is 10 PTT 108: Mass and Energy Balances

11. Standard Heat of Reaction is the heat of reaction when both the reactants and products are reacting completely at a specified reference temperature and pressure, usually at 25°C and 1 atm. (The “standard” part, which refers to the specified temperature and pressure, is denoted by the superscript°.) 11 PTT 108: Mass and Energy Balances

12. Heat of Reaction (cont’d) If A is a reactant or product, v A is its stoichiometric coefficient (negative for reactant, positive for product), and n A,r is mol of A are consumed or generated at 25°C and 1 atm, then the enthalpy change is where ξ is the extent of reaction. For an open system, dots would go above the ∆H, n A,r, and ξ. 12 PTT 108: Mass and Energy Balances

13. Heat of Reaction (cont’d) Properties of the heat of reaction (p. 443)  exothermic reaction if negative,  endothermic reaction if positive;  ΔĤ r (T, P) nearly independent of pressure at low and moderate pressures;  the value of heats of reaction depends on how the stoichiometric equation is written (e.g.,standard heat of the reaction 2A → 2B is twice that of A → B)  the value of heat of reaction depends on the states of aggregation (g, l, s) of the reactants and products. 13 PTT 108: Mass and Energy Balances

14. Class Discussion EXAMPLE 9.1-1 14 PTT 108: Mass and Energy Balances

15. Internal Energy of Reaction If a reaction take place in a closed reactor at constant volume, the heat released/absorbed is determined by the change in internal energy between reactants and products, not enthalpy. The internal energy of reaction, ΔÛ r (T) is the difference U products – U reactants if stoichiometric quantities of reactants react completely at temperature T. Suppose a reaction occurs by assuming ideal gas behavior and neglecting specific volume where υ i is the stoichiometric coefficient of species i, thus the internal energy of reaction is related to the heat of reaction (closed system) is given by 15 PTT 108: Mass and Energy Balances

16. Internal Energy of Reaction (cont’d) For example, for the reaction The internal energy of reaction is ∆Û r (T) = = 16 PTT 108: Mass and Energy Balances

17. Class Discussion EXAMPLE 9.1-2 17 PTT 108: Mass and Energy Balances

18. Hess’s Law General statement of Hess’s Law: If the stoichiometric equation for reaction 1 can be obtained by algebraic operations (multiplication by constants, addition, and substraction) on stoichiometric equations for reaction 2, 3,…, then the heat of reaction ΔĤ r1 can be obtained by performing the same operations on the heat of reactions ΔĤ r2, ΔĤ r3,… In the other words: Hess’s law states that if you can obtain a stoichiometric equation as a linear combination of the stoichiometric equations for other reactions, you can determine its heat of reaction by performing the same operations on the heats of the other reactions. 18 PTT 108: Mass and Energy Balances

19. For example, suppose we experimentally determine the following two standard heats of reaction: We want to determine the heat of the reaction A → B + 2D but can’t carry out that reaction experimentally. We observe, however, that we can obtain that stoichiometric reaction as [1] + 2x[2]: 19 PTT 108: Mass and Energy Balances

20. Class Discussion EXAMPLE 9.2-1 20 PTT 108: Mass and Energy Balances

21. Formation Reactions and Heats of Formation Formation reaction: A reaction in which a compound is formed from its elemental constituents as they occur in nature [e.g., O 2 (g), and not O]. Standard heat of formation : The enthalpy change associated with the formation of 1 mole of the compound at a reference pressure and temperature (25˚C, 1 atm). Standard heats of formation of many species are given in Table B.1. For example, liquid benzene: The standard heat of formation of an elemental species [C(s), H 2 (g), O 2 (g),...] is zero. 21

22. Formation Reactions and Heats of Formation (cont’d) We can use Hess’s law to show that for any reaction a hypothetical process path can be drawn from reactants to elements to products: 22 PTT 108: Mass and Energy Balances

23. Formation Reactions and Heats of Formation (cont’d) It may shown using Hess’s Law that: if v i is the stoichiometric coefficient of the ith species participating in a reaction (+ for products, - for reactants) and is the standard heat of formation of this species and since enthalpy is a state function, 23 PTT 108: Mass and Energy Balances

24. Class Discussion EXAMPLE 9.3-1 24 PTT 108: Mass and Energy Balances

25. Heat of Combustion Standard Heat of Combustion : Heat of the combustion of any substance with oxygen to yield specified products [e.g., CO 2 (g), H 2 O (l), SO 2 (g) and N 2 (g)], with both reactants and products at 25°C and 1 atm. The standard heats of combustion can be found in Table B-1. For example, for acetone: 25 PTT 108: Mass and Energy Balances

26. Heat of Combustion (cont’d) If a reaction only involves combustible reactants and products, then we can calculate the standard heat of the reaction from tabulated standard heats of combustion. The formula is: where v i is the stoichiometric coefficient of the ith reactant or product species and is the standard heat of combustion of that species. The formula looks like the one involving heats of formation, except that summations are reversed (reactants - products). 26 PTT 108: Mass and Energy Balances

27. Heat of Combustion (cont’d) This formula is derived from Hess’s law in the same way that the heat of formation formula was derived: 27 PTT 108: Mass and Energy Balances

28. Class Discussion EXAMPLE 9.4-1 28 PTT 108: Mass and Energy Balances

29. Energy Balances on Reactive Processes To perform energy balance calculation on a reactive system, you must include the following aspects: 1.Draw and label flowchart 2.Use material balances and phase equilibrium relationship to determine the amount of stream component and flow rates 3.Choose reference states for specific enthalpy/internal energy 4.Prepare and fill the inlet-outlet enthalpy table 5.Calculate 6.Calculate 29 PTT 108: Mass and Energy Balances

30. Energy Balances on Reactive Processes Two methods are commonly used to choose reference states for enthalpy calculations: 1.Heat of Reaction Method - Generally preferable when there is a single reaction for which is known. 2.Heat of Formation Method - Generally preferable for multiple reactions and single reactions for which is not readily available. 30 PTT 108: Mass and Energy Balances

31. Energy Balances for Heat of Reaction Method Energy balance equation for heat of reaction method: 31 PTT 108: Mass and Energy Balances

32. The process path that leads to this expression for (recalling that the reference states are the reactants and products at 25˚C and 1 atm) is Writing and substituting for each of the three enthalpy changes on the right leads to the given expression for 32 PTT 108: Mass and Energy Balances Energy Balances for Heat of Reaction Method (cont’d)

33. Energy Balances for Heat of Formation Method Energy balance equation for heat of formation method: 33 PTT 108: Mass and Energy Balances

34. Energy Balances for Heat of Formation Method (cont’d) The process path for (recalling that the reference states are the elemental species at 25°C and 1 atm) is Writing and substituting for each of the two enthalpy changes on the right leads to the given expression for 34 PTT 108: Mass and Energy Balances

35. Class Discussion EXAMPLE 9.5-1 EXAMPLE 9.5-2 EXAMPLE 9.5-3 EXAMPLE 9.5-4 35 PTT 108: Mass and Energy Balances

36. THANK YOU…. 36 PTT 108: Mass and Energy Balances