Pure solids or liquids or gases at 1 atmosphere the activity is taken as unity why
Answers
Answer:
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.
Answer:
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, 100mL100mL H2OHX2O =100g=100g and half as much, 50mL50mL H2OHX2O =50g=50g. Both have molar densities of 55.5mol/L55.5mol/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.