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# Spontaneous and Nonspontaneous Reactions

## Defines spontaneous and nonspontaneous reactions in terms of entropy and enthalpy.

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Spontaneous and Nonspontaneous Reactions

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Watch that nitro!

Nitroglycerin is tricky stuff. An active ingredient in dynamite (where it is stabilized), “raw” nitroglycerin is very unstable. Physical shock will cause the material to explode. The reaction is shown below:

$4\text{C}_3\text{H}_5(ONO_2)_3\rightarrow 12\text{CO}_2+10\text{H}_2\text{O}+6\text{N}_2+\text{O}_2$

The explosion of nitroglycerin releases large volumes of gases and is very exothermic.

### Spontaneous Reactions

Reactions are favorable when they result in a decrease in enthalpy and an increase in entropy of the system. When both of these conditions are met, the reaction occurs naturally. A spontaneous reaction is a reaction that favors the formation of products at the conditions under which the reaction is occurring. A roaring bonfire is an example of a spontaneous reaction, since it is exothermic (there is a decrease in the energy of the system as energy is released to the surroundings as heat). The products of a fire are composed partly of gases such as carbon dioxide and water vapor. The entropy of the system increases during a combustion reaction. The combination of energy decrease and entropy increase dictates that combustion reactions are spontaneous reactions.

Source: http://commons.wikimedia.org/wiki/File:Scottish_bonfire.jpg

Bonfire. [Figure2]

A nonspontaneous reaction is a reaction that does not favor the formation of products at the given set of conditions. In order for a reaction to be nonspontaneous, it must be endothermic, accompanied by a decrease in entropy, or both. Our atmosphere is composed primarily of a mixture of nitrogen and oxygen gases. One could write an equation showing these gases undergoing a chemical reaction to form nitrogen monoxide.

$\text{N}_2(g)+\text{O}_2(g)\rightarrow 2\text{NO}(g)$

Fortunately, this reaction is nonspontaneous at normal temperatures and pressures. It is a highly endothermic reaction with a slightly positive entropy change $(\Delta \text{S})$ . Nitrogen monoxide is capable of being produced at very high temperatures and has been observed to form as a result of lightning strikes.

One must be careful not to confuse the term spontaneous with the notion that a reaction occurs rapidly. A spontaneous reaction is one in which product formation is favored, even if the reaction is extremely slow. A piece of paper will not suddenly burst into flames, although its combustion is a spontaneous reaction. What is missing is the required activation energy to get the reaction started. If the paper were to be heated to a high enough temperature, it would begin to burn, at which point the reaction would proceed spontaneously until completion.

In a reversible reaction, one reaction direction may be favored over the other. Carbonic acid is present in carbonated beverages. It decomposes spontaneously to carbon dioxide and water according to the following reaction.

$\text{H}_2\text{CO}_3(aq)\rightleftarrows \text{CO}_2(g)+\text{H}_2\text{O}(l)$

If you were to start with pure carbonic acid in water and allow the system to come to equilibrium, more than 99% of the carbonic acid would be converted into carbon dioxide and water. The forward reaction is spontaneous because the products of the forward reaction are favored at equilibrium. In the reverse reaction, carbon dioxide and water are the reactants and carbonic acid is the product. When carbon dioxide is bubbled into water, less than 1% is converted to carbonic acid when the reaction reaches equilibrium. The reverse reaction, as written above, is not spontaneous.

#### Summary

• Spontaneous and nonspontaneous reactions are defined.
• Examples of both types of reactions are given.

#### Practice

Questions

1. Why is system I a spontaneous reaction?
2. Why is system II not spontaneous?
3. Why is system III spontaneous?

#### Review

Questions

1. Why is a combustion reaction spontaneous?
2. Is NO formation spontaneous at room temperature?
3. How do we know that the equilibrium between carbonic acid and CO 2 goes strongly to the right?

1. [1]^ Credit: Image copyright TFoxFoto, 2014; Source: http://www.shutterstock.com; License: CC BY-NC 3.0