Bond Breakage and Formation When a chemical reaction occurs, the atoms in the reactants rearrange their chemical bonds to make products. The new arrangement of bonds does not have the same total energy as the bonds in the reactants. Therefore, when chemical reactions occur, there will always be an accompanying energy change. In some reactions, the energy of the products is lower than the energy of the reactants. Thus, in the course of the reaction, the substances lose energy to the surrounding environment. Such reactions are exothermic and can be represented by an energy-level diagram in Figure 1 (left). In most cases, the energy is given off as heat (although a few reactions give off energy as light). In chemical reactions where the products have a higher energy than the reactants, the reactants must absorb energy from their environment to react. These reactions are endothermic and can be represented by an energy-level diagrams like Figure 1 (right). It is not uncommon that textbooks and instructors to consider heat as a independent "species" in a reaction.

called exothermic reactions, while others may require heat to enable the reaction to occur, which are called endothermic reactions. Typically, reaction rates A chemical reaction is a process that leads to the chemical transformation of one set of chemical substances to another. When chemical reactions occur, the atoms are rearranged and the reaction is accompanied by an energy change as new products are generated. Classically, chemical reactions encompass changes that only involve the positions of electrons in the forming and breaking of chemical bond In photochemical reactions, atoms and molecules absorb energy (photons) of the illumination light and convert it into an excited state. They can then release this energy by breaking chemical bonds, thereby producing radicals. Photochemical reactions include hydrogen–oxygen reactions, radical polymerization, chain reactions and rearrangement reactions. Many important processes involve photochemistry. The premier example is photosynthesis, in which most plants use solar energy to convert carbon dioxide and water into glucose, disposing of oxygen as a side-product. Humans rely on photochemistry for the formation of vitamin D, and vision is initiated by a photochemical reaction of rhodopsin. In fireflies, an enzyme in the abdomen catalyzes a reaction… A chemical reaction is a process that leads to the chemical transformation of one set of chemical substances to another. When chemical reactions occur, the atoms are rearranged and the reaction is accompanied by an energy change as new products are generated. Δ G = Δ H − T ⋅ Δ S {\displaystyle \Delta G=\Delta H-T\cdot \Delta S} . G: free energy, H: enthalpy, T: temperature, S: entropy, Δ: difference (change between original and product) Reactions can be exothermic, where ΔH is negative and energy is released. Typical examples of exothermic reactions are combustion, precipitation and crystallization, in which ordered solids are formed from disordered gaseous or liquid phases. In contrast, in endothermic reactions, heat is consumed from the environment. This can occur by increasing the entropy of the system, often through the formation of gaseous or dissolved reaction products, which have higher entropy. Since the entropy term in the free-energy change increases with temperature, many endothermic reactions preferably take place at high temperatures. On the contrary, many exothermic reactions such as crystallization occur preferably at lower temperatures. A change in temperature can sometimes reverse the sign of the enthalpy of a reaction, as for the carbon monoxide reduction of molybdenum dioxide: Reactant concentrations, which usually make the reaction happen at a faster rate if raised through increased collisions per unit of time. Some reactions, however, have rates that are independent of reactant concentrations, due to a limited number of catalytic sites. These are called zero order reactions. Surface area available for contact between the reactants, in particular solid ones in heterogeneous systems. Larger surface areas lead to higher reaction rates. Pressure – increasing the pressure decreases the volume between molecules and therefore increases the frequency of collisions between the molecules. Activation energy, which is defined as the amount of energy required to make the reaction start and carry on spontaneously. Higher activation energy implies that the reactants need more energy to start than a reaction with lower activation energy. Temperature, which hastens reactions if raised, since higher temperature increases the energy of the molecules, creating more collisions per unit of time. The presence or absence of a catalyst. Catalysts are substances that make weak bonds with reactants or intermediates and change the pathway (mechanism) of a reaction which in turn increases the speed of a reaction by lowering the activation energy needed for the reaction to take place. A catalyst is not destroyed or changed during a reaction, so it can be used again. For some reactions, the presence of electromagnetic radiation, most notably ultraviolet light, is needed to promote the breaking of bonds to start the reaction. This is particularly true for reactions involving radicals. Several theories allow calculating the reaction rates at the molecular level. This field is referred to as reaction dynamics. The rate v of a first-order reaction, which could be the disintegration of a substance A, is given by: In photochemical reactions, atoms and molecules absorb energy (photons) of the illumination light and convert it into an excited state. They can then release this energy by breaking chemical bonds, thereby producing radicals. Photochemical reactions include hydrogen–oxygen reactions, radical polymerization, chain reactions and rearrangement reactions. Many important processes involve photochemistry. The premier example is photosynthesis, in which most plants use solar energy to convert carbon dioxide and water into glucose, disposing of oxygen as a side-product. Humans rely on photochemistry for the formation of vitamin D, and vision is initiated by a photochemical reaction of rhodopsin. In fireflies, an enzyme in the abdomen catalyzes a reaction that results in bioluminescence. Many significant photochemical reactions, such as ozone formation, occur in the Earth atmosphere and constitute atmospheric chemistry. Nucleophilic addition of a carbanion or another nucleophile to the double bond of an alpha, beta-unsaturated carbonyl compound can proceed via the Michael reaction, which belongs to the larger class of conjugate additions. This is one of the most useful methods for the mild formation of C–C bonds. Some additions which can not be executed with nucleophiles and electrophiles can be succeeded with free radicals. As with the free-radical substitution, the radical addition proceeds as a chain reaction, and such reactions are the basis of the free-radical polymerization.