2

Structure and Reactivity

1. Chemical Thermodynamics, which deals with the changes in energy that take place when
processes such as chemical reactions occur. Thermodynamics controls the extent to which a reaction goes to completion.

2. Chemical Kinetics, which concerns the velocity or rate at which the concentrations of
reactants and products change. In other words, kinetics describes the speed at which a reaction goes to completion.

3. Thermodynamic Control, a transformation that yields the most stable products is said to
be under Thermodynamic Control.

4. Kinetic Control, a reaction in which the product obtained is the one formed fastest is defined
as being under Kinetic Control.

5. Reversible Reactions, all chemical reactions are reversible, and reactants and products
interconvert to various degrees. Equilibria are described by equilibrium constants, K.

6. Equilibrium constant, to find an equilibrium constant, divide the arithmetic product of the
concentrations of the components on the right side of the reaction by that of the components on the left, all given in units of moles per liter.

7. Gibbs Standard free energy, the equilibrium constant can be related directly to the
thermodynamic function called the Gibbs Standard free energy change.

8. When K = 1, starting materials and products are present in equal concentrations. 9. Change in Enthalpy and Entropy, the Gibbs standard free energy change is related to two
other thermodynamic quantities: the change in Enthalpy, and the change in Entropy.

10. The Enthalpy Change of a reaction is the heat absorbed or released at constant pressure
during course of the reaction.

Chapter 2, Structure and Reactivity | Vollhardt Organic Chemistry Structure Function 6th

11. Exothermic and Endothermic reactions, if the bonds formed are stronger than those broken,
the value of is negative and the reaction is defined as exothermic (releasing heat). In contrast, a positive is characteristic of an endothermic (heat-absorbing) process.

12. In many organic reactions the change in entropy is small, and in those cases we will equate
approximately Gibbs standard free energy change to Enthalpy Change. Exceptions: 1. Transformations in which the number of molecules on each side of the chemical equation differ 2. Energy dispersal is greatly affected by profound structural changes, such as, for example, ring closures and ring openings.

13. The thermodynamic features of chemical reactions do not by themselves tell us anything about
their rates.

14. Transition State, the energy of the transition state may be viewed as a barrier to be overcome
in order for the reaction to take place.

15. Activation Energy, The energy input required to raise the energy of the starting compounds to
that of the transition state is called the activation energy.

16. Boltzmann distribution curve, depicts the distribution of kinetic energy. The shape of the
Boltzmann curve depends on the temperature. At higher temperatures, as the average kinetic energy increases, the curve flattens and shifts toward higher energies.

17. The kinetic energy of molecules increases when they are heated, which means that a larger
fraction of them have sufficient energy to overcome the activation barrier

18. The Arrhenius Equation noticed the dependence of reaction rate k on temperature T and
describes how rates of reactions with different activation energies vary with temperature.

The A term can be imagined as the maximum rate constant that the reaction would have if every molecule had sufficient collisional energy to overcome the activation barrier. This will occur at very high temperature, when to A. will be close to zero, thus rendering k nearly equal

19. Bonds consist of electrons. Chemical change is defined as a process in which bonds are
broken and/or formed. Therefore, when chemistry takes place, electrons move.

Chapter 2, Structure and Reactivity | Vollhardt Organic Chemistry Structure Function 6th

20. Following the basic principles of electrostatics, electrons, being negatively charged,
are attracted to sites of electron deficiency, or positive charge.

21. Either highly electronegative or electron-deficient (and, therefore, electron-attracting) atoms,

positively charged ions, or the partially positive atom in a polar covalent bond can be the destination for electron movement.

22. Electron-movement patterns

1. Dissociation of a polar covalent Bond into ions 2. Formation of a polar covalent bond from ions 3. Simultaneous formation and dissociation of two covalent bonds 4. Addition of (a) and electron-pair donor or (b) and electron-pair acceptor to a multiple bond.

Chapter 2, Structure and Reactivity | Vollhardt Organic Chemistry Structure Function 6th