ENTHALPY Ms Dunishiya de Silva Reaction Energies The

ENTHALPY Ms. Dunishiya de Silva

Reaction Energies The energy change associated with a chemical reaction is called the enthalpy of reaction and abbreviated H.

Enthalpy of Reactions There actually a number of different types of enthalpies because enthalpy depends on conditions. THEY ARE ALL JUST SPECIFIC TYPES OF A GENERAL CONCEPT CALLED “ENTHALPY”. H = Hfinal - Hinitial

Energy General Reaction Scheme Ea Reactants ΔH Reaction Coordinate Products

Energy Exothermic Reaction – “hot pack” Ea Reactants ΔH Reaction Coordinate Products

Energy Endothermic Reaction – “cold pack” Ea Products Reactants ΔH Reaction Coordinate

Where does the Energy go? In the case of a chemical reaction, you need to keep the different types of energy separate in your mind: Bond energy – energy INSIDE the molecules Thermal energy (heat) – kinetic energy of the molecules Energy of the “both” – kinetic energy of solvent or other molecules in the system

Energy changes H represents the change in INTERNAL MOLECULAR ENERGY. H = Hfinal - Hinitial

Energy Exothermic Reaction – “hot pack” Ea Reactants ΔH Reaction Coordinate Products

Exothermic energy changes H = Hfinal – Hinitial < 0 Hinitial>Hfinal This energy is internal to the molecule. The excess gets absorbed by the rest of the system as heat causing the molecules to move faster (more kinetic energy) and the temperature to increase.

Energy Endothermic Reaction – “cold pack” Ea Products Reactants ΔH Reaction Coordinate

Endothermic energy changes H = Hfinal – Hinitial > 0 Hinitial<Hfinal This energy is internal to the molecule and must come from somewhere. The additional energy required by the system gets absorbed from the rest of the system as heat causing the molecules to move slower (less kinetic energy) and the temperature to decrease.

Energy The hard part is getting over the hump. Ea Products Reactants ΔH Reaction Coordinate

Ea = Activation Energy The tale of a reaction is not limited strictly to the identity and energetics of the products and reactants, there is a path (reaction coordinate) that must get followed. The “hump” represents a hurdle that must be overcome to go from reactants to products.

If you are at the top, it is easy to fall down into the valley (on either side), but how do you get to the top? Energy How do you get over the hump? Ea Products Reactants ΔH Reaction Coordinate

How do you get over the hump? The energy comes from the “both”, the rest of the system. Energy The molecules acquire or lose energy the same way: by colliding with each other! Ea Products Reactants ΔH Reaction Coordinate

Enthalpy is a “State Function” What’s a “state function”? A “state function” is a value that is a function only of the initial and final states of the system, not the path you take to get there!

Enthalpy as a State Function Enthalpy is like that. It doesn’t care how you got where you are going, it simply looks at the difference from where you started.

Path doesn’t matter! Actual path H Reactants Products

Ways to determine H 1. 2. 3. 4. 5. Find H 0 in a table Find Hf 0 in a table Calculate from Bond Energies Calculate from Hf 0 Calculate from other H that you already know (Hess’s Law)

CH 4 (g) + 4 Cl 2 (g) CCl 4 (l) + 4 HCl (g) This is not, itself, a formation reaction. BUT remember H is a STATE FUNCTION What does that mean? H doesn’t depend on the path, just the start and the end.

CH 4 (g) + 4 Cl 2 (g) CCl 4 (l) + 4 HCl (g) 4 HCl(g) 4 Cl 2 CH 4 CCl 4(l) All the elements known to mankind!

CH 4 (g) + 4 Cl 2 (g) CCl 4 (l) + 4 HCl (g) How does that help? You can take the long road. Don’t do the reaction as written, take a convenient path that you know the value of each step.

CH 4 (g) + 4 Cl 2 (g) CCl 4 (l) + 4 HCl (g) Can you think of a path where you know the value of each step? Make the products from elements (formation reactions). Make the reactants from elements (formation reactions). The difference between the Hf 0 of the products and the reactants must be the H 0 rxn

CH 4 (g) + 4 Cl 2 (g) CCl 4 (l) + 4 HCl (g) 4 HCl(g) 4 Cl 2 CH 4 CCl 4(l) All the elements known to mankind!

CH 4 (g) + 4 Cl 2 (g) CCl 4 (l) + 4 HCl (g) CH 4 + 4 Cl 2 H CCl 4(l) + 4 HCl(g) All the elements known to mankind!

CH 4 (g) + 4 Cl 2 (g) CCl 4 (l) + 4 HCl (g) H 0 rxn = Σ Hf, prod - Σ Hf, react H 0 rxn = [ Hf(CCl 4) + 4* Hf(HCl)] – [ Hf(CH 4) + 4* Hf(Cl 2)] H 0 rxn = [-139. 3 k. J/mol + 4*(-92. 3 k. J/mol)]– [74. 8 k. J/mol + 4* 0 k. Jmol] H 0 rxn = -433. 7 k. J anything = final anything – initial anything

CH 4 (g) + 4 Cl 2 (g) CCl 4 (l) + 4 HCl (g) H 0 rxn = Σ Hf, prod - Σ Hf, react H 0 rxn = [ Hf(CCl 4) + 4* Hf(HCl)] – [ Hf(CH 4) + 4* Hf(Cl 2)] H 0 rxn = [-139. 3 k. J/mol + 4*(-92. 3 k. J/mol)]– [74. 8 k. J/mol + 4* 0 k. Jmol] H 0 rxn = -433. 7 k. J/mol CH 4 -433. 7 k. J/4 mol Cl 2