Why is active mass of a pure solid or liquid always taken as unity?

Active mass is defined as the molar concentration ie. number of Gram-moles per litre.

My book then wrote

Active mass of pure solid/liquid is always 1 .

The book reasoned that

Molar concentration is directly proportional to density. Since density of solid or liquid always remains constant, the active mass is taken as 1 .

Really? Doesn't the density of the solid reactant decrease when the forward reaction is about to reach the equilibrium??

In a word, I am greatly confused. What is the reason for taking the active mass 1 ? Please help.

• The density of a solid or liquid reactant doesn't change over the course of a reaction. The mass and volume do, but the ratio of the two is constant. If there is a temperature change then there are small changes in density, but that would also alter the equilibrium constant and the concentrations of reactants and all the rest. The equilibrium constant is based on activities, which you can think of as the ratio of the concentration (molar density) at standard state to the concentration in the reaction. Since solid/liquid density is constant at a given temperature, activity is too. – Jason Patterson Oct 31 '14 at 13:30
• No, it's not a convention. Activities (active mass or any other activities) are ratios. If the ratio is between reaction conditions and standard state, and the reaction conditions happen to match standard state, then the activity is 1. That happens to solutions when they are 1 molar (standard state for a solution is 1M at 25°C) and gases at 1 atm (again, standard state is 1 atm at 25°C.) For solids and liquids, it's based on their densities. Since their densities don't change appreciably, solids and liquids are effectively always at standard state, so their ratio is very nearly 1 always. – Jason Patterson Oct 31 '14 at 17:23
• @JasonPatterson comments are not meant for answering use the answer box below – RE60K Oct 31 '14 at 18:14
• @Aditya Indeed, I started with a comment that was an insufficient answer and it has spiraled out of control. – Jason Patterson Oct 31 '14 at 19:09
• @Jason Would you mind copying your comments into an answer? At least I would upvote it ;) – Martin - マーチン Apr 7 '15 at 8:25

Does the activity of a solid or liquid change over the course of a reaction?

The density of a solid or liquid reactant doesn't change over the course of a reaction. The mass and volume do as it is consumed, but the ratio of the two is constant. If the reaction causes a temperature change then there are small changes in density, but that would also alter the equilibrium constant and the concentrations of the species involved.

The equilibrium constant is based on activities, which you can think of as the ratio of the concentration (molar density) at standard state to the concentration in the reaction. Since solid/liquid density is constant at a given temperature, activity is too. It takes quite a large change of temperature or pressure to make a substantial change in the density of a substance, assuming no phase changes occur.

What about gases, why don't they show the same phenomenon and have fixed activities? (Asked in comments.)

For solids or liquids, as mass decreases the volume also decreases by a proportional amount. For example, $\mathrm{100mL}$ $\ce{H2O}$ $\mathrm{= 100g}$ and half as much, $\mathrm{50mL}$ $\ce{H2O}$ $\mathrm{= 50g}$. Both have molar densities of $\mathrm{55.5 mol/L}$.) Gases keep the volume of their container, so if you remove some via a reaction, the mass of the gas decreases, but its volume remains the same, and its concentration decreases as a result.

Why is active mass given a value of 1 then? Is this simply a convention? Shouldn't its value depend on the compound? (Asked in comments.)

No, it's not a convention. Activities, active mass or any other activities, are really ratios. The ratio here is a comparison between the activity under experimental conditions and the activity at standard state under standard conditions. For gases that is 1 bar of pressure at 25°C, for solutions that is 1 molar at 25°C and 1 bar, and for solids and liquids that is the molar density of the substance in its most stable phase and allotrope at 25°C and 1 bar. The activities of real substances require some additional work and there are particular compounds that do not behave quite as nicely as expected, but the basic idea of activity being the ratio between experimental state and standard state is sound.

With that in mind, consider the activity of solids and liquids. Their standard state is their density at standard conditions. Their experimental state is their density at experimental conditions. It takes significant pressure and temperature changes to cause substantial changes in the density of a solid or liquid, so their experimental state is approximately equal to their standard state, and the ratio of these two states is therefore quite close to 1.

Density is an intensive property that is:

An intensive property is a bulk property, meaning that it is a physical property of a system that does not depend on the system size or the amount of material in the system. Examples of intensive properties include temperature, refractive index, density, and hardness of an object.