Spontaneous Change

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In chemistry, spontaneous change is change which occurs by itself, without outside assistance.


Enthalpy

Heat of Formation The amount of heat that's released or absorbed when 1 mole of the compound is formed from its elements. Note that when we talk about heat of formation, we use the same symbol we use for enthalpy change but we put subscript "f" on it.


C, Ni, Cl2, O2, H2 and N2--or all other elemental atoms or molecules-have a heat of formation of zero.


Heats of reaction The total enthalpy of a system cannot be measured directly; the enthalpy change of a system is measured instead. Enthalpy change is defined by the following equation:

where ΔH is the enthalpy change Hfinal is the final enthalpy of the system, measured in joules. In a chemical reaction, Hfinal is the enthalpy of the products.

H initial is the initial enthalpy of the system, measured in joules. In a chemical reaction, Hinitial is the enthalpy of the reactants. For an exothermic reaction at constant pressure, the system's change in enthalpy is equal to the energy released in the reaction, including the energy retained in the system and lost through expansion against its surroundings. In a similar manner, for an endothermic reaction, the system's change in enthalpy is equal to the energy absorbed in the reaction, including the energy lost by the system and gained from compression from its surroundings. A relatively easy way to determine whether or not a reaction is exothermic or endothermic is to determine the sign of ΔH. If ΔH is positive, the reaction is endothermic, that is heat is absorbed by the system due to the products of the reaction having a greater enthalpy than the reactants. On the other hand if ΔH is negative, the reaction is exothermic, that is the overall decrease in enthalpy is achieved by the generation of heat. Although enthalpy is commonly used in engineering and science, it is impossible to measure directly, as enthalpy has no datum (reference point). Therefore enthalpy can only accurately be used in a closed system. However, few real world applications exist in closed isolation, and it is for this reason that two or more closed systems cannot be compared using enthalpy as a basis, although sometimes this is done erroneously.


Entropy

Entropy is a measure of randomness, or disorder. If the changes of entropy is negative, this means that the products are more "orderly" than the reactants. If the changes of entropy is positive, this means that the products are less "orderly" than the reactants

The second law of thermodynamics states that entropy in the combination of a system and its surroundings (or in an isolated system by itself) increases during all spontaneous chemical and physical processes. Spontaneity in chemistry means “by itself, or without any outside influence”, and has nothing to do with speed. The Clausius equation of δqrev/T = ΔS introduces the measurement of entropy change, ΔS. Entropy change describes the direction and quantitates the magnitude of simple changes such as heat transfer between systems – always from hotter to cooler spontaneously.[12] Thus, when a mole of substance at 0 K is warmed by its surroundings to 298 K, the sum of the incremental values of qrev/T constitute each element's or compound's standard molar entropy, a fundamental physical property and an indicator of the amount of energy stored by a substance at 298 K.[13][14] Entropy change also measures the mixing of substances as a summation of their relative quantities in the final mixture.[15]

Entropy is equally essential in predicting the extent of complex chemical reactions, i.e. whether a process will go as written or proceed in the opposite direction. For such applications, ΔS must be incorporated in an expression that includes both the system and its surroundings, ΔSuniverse = ΔSsurroundings + ΔS system. This expression becomes, via some steps, the Gibbs free energy equation for reactants and products in the system: ΔG [the Gibbs free energy change of the system] = ΔH [the enthalpy change] −T ΔS [the entropy change].[13]

The second law

Main article: Second law of thermodynamics

An important law of physics, the second law of thermodynamics, states that the total entropy of any isolated thermodynamic system tends to increase over time, approaching a maximum value; and so, by implication, the entropy of the universe (i.e. the system and its surroundings), assumed as an isolated system, tends to increase. Two important consequences are that heat cannot of itself pass from a colder to a hotter body: i.e., it is impossible to transfer heat from a cold to a hot reservoir without at the same time converting a certain amount of work to heat. It is also impossible for any device that can operate on a cycle to receive heat from a single reservoir and produce a net amount of work; it can only get useful work out of the heat if heat is at the same time transferred from a hot to a cold reservoir. This means that there is no possibility of a "perpetual motion" which is isolated. Also, from this it follows that a reduction in the increase of entropy in a specified process, such as a chemical reaction, means that it is energetically more efficient.


In general, according to the second law, the entropy of a system that is not isolated may decrease. An air conditioner, for example, cools the air in a room, thus reducing the entropy of the air. The heat, however, involved in operating the air conditioner always makes a bigger contribution to the entropy of the environment than the decrease of the entropy of the air. Thus the total entropy of the room and the environment increases, in agreement with the second law.

Spontaneity and Gibbs Free Energy

The combination of entropy and enthalpy.

If Gibb's free energy is negative, then the reaction occurs spontaneously in the forward direction.

If Gibb's free energy is positive, the the reaction occurs spontanously at the temperature in the reverse direction.

If Gibb's is zero, then the reaction is in equilibrium.

Note: If the reaction is endothermic but creates greater disorder, and the disorder the reaction creates exceeds the energy it requires, then the reaction may occur spontaneously as long as its exothermic and the negative enthalpy change exceeds the energy it requires