1. Covalent Bond Strength Most simply, the strength of a bond is measured by determining how much energy is required to break the bond. This is the bond enthalpy. The bond enthalpy for a Cl—Cl bond, D(Cl—Cl), is measured to be 242 kJ/mol.

2. Average Bond Enthalpies This table lists the average bond enthalpies for many different types of bonds. Average bond enthalpies are positive, because bond breaking is an endothermic process.

3. Average Bond Enthalpies NOTE: These are average bond enthalpies, not absolute bond enthalpies; the C—H bonds in methane, CH 4, will be a bit different than the C—H bond in chloroform, CHCl 3.

4. Enthalpies of Reaction Yet another way to estimate  H for a reaction is to compare the bond enthalpies of bonds broken to the bond enthalpies of the new bonds formed. In other words,  H rxn =  (bond enthalpies of bonds broken)   (bond enthalpies of bonds formed)

5. Enthalpies of Reaction CH 4 (g) + Cl 2 (g)  CH 3 Cl (g) + HCl (g) In this example, one C—H bond and one Cl—Cl bond are broken; one C—Cl and one H—Cl bond are formed.

6. Enthalpies of Reaction So,  H rxn = [D(C—H) + D(Cl—Cl)  [D(C—Cl) + D(H—Cl) = [(413 kJ) + (242 kJ)]  [(328 kJ) + (431 kJ)] = (655 kJ)  (759 kJ) =  104 kJ

7. Bond Enthalpy and Bond Length We can also measure an average bond length for different bond types. As the number of bonds between two atoms increases, the bond length decreases.

8. Work When a process occurs in an open container, commonly the only work done is a change in volume of a gas pushing on the surroundings (or being pushed on by the surroundings).

9. Work We can measure the work done by the gas if the reaction is done in a vessel that has been fitted with a piston. w = −P  V

10. Enthalpy If a process takes place at constant pressure (as the majority of processes we study do) and the only work done is this pressure-volume work, we can account for heat flow during the process by measuring the enthalpy of the system. Enthalpy is the internal energy plus the product of pressure and volume: H = E + PV

11. Enthalpy When the system changes at constant pressure, the change in enthalpy,  H, is  H =  (E + PV) This can be written  H =  E + P  V

12. Enthalpy Since  E = q + w and w = −P  V, we can substitute these into the enthalpy expression:  H =  E + P  V  H = (q+w) − w  H = q So, at constant pressure the change in enthalpy is the heat gained or lost.