Gas Laws

When seventeenth-century scientists began studying the physical properties of gases, they noticed simple relationships between some of the measurable properties of gases. Take pressure (P) and volume (V), for example. Scientists noted that for a given amount of a gas (usually expressed in units of moles [n]), if the temperature (T) of the gas is kept constant, pressure and volume are related: as one increases, the other decreases. As one decreases, the other increases. We say that pressure and volume are inversely related.

There is more to it, however: pressure and volume of a given amount of gas at a constant temperature are numerically related. If you take the pressure value and multiply it by the volume value, the product is a constant for a given amount of gas at a constant temperature:

P × V = constant at constant n and T

If either volume or pressure changes while the amount and temperature stay the same, then the other property must change so that the product of the two properties still equals that same constant. That is, if the original conditions are labelled P₁ and V₁ and the new conditions are labelled P₂ and V₂, we have

P₁V₁ = constant = P₂V₂

where the properties are assumed to be multiplied together. Leaving out the middle part, we have simply

P₁V₁ = P₂V₂ at constant n and T

This equation is an example of a gas law. A gas law is a simple mathematical formula that allows you to model, or predict, the behaviour of a gas. This particular gas law is called Boyle’s law, after the English scientist Robert Boyle, who first announced it in 1662. Figure 1.1 Boyle’s Law shows two representations of what Boyle’s law describes.

Boyle’s law is an example of a second type of mathematical problem we see in chemistry—one based on a mathematical formula. Tactics for working with mathematical formulas are different from tactics for working with conversion factors. First, most of the questions you will have to answer using formulas are word-type questions, so the first step is to identify what quantities are known and assign them to variables. Second, in most formulas, some mathematical rearrangements (i.e., algebra) must be performed to solve for an unknown variable. The rule is that to find the value of the unknown variable, you must mathematically isolate the unknown variable by itself and in the numerator of one side of the equation. Finally, units must be consistent. For example, in Boyle’s law there are two pressure variables, and they must have the same unit. There are also two volume variables; they also must have the same unit. In most cases, it won’t matter what the unit is, but the unit must be the same on both sides of the equation.

As mentioned, you can use any units for pressure or volume, but both pressures must be expressed in the same units, and both volumes must be expressed in the same units.

There are other measurable characteristics of a gas. One of them is temperature (T). One could vary the temperature of a gas sample and note what effect it has on the other properties of the gas. Early scientists did just this, discovering that if the amount of a gas and its pressure are kept constant, then changing the temperature changes the volume (V). As temperature increases, volume increases; as temperature decreases, volume decreases. We say that these two characteristics are directly related.

A mathematical relationship between V and T should be possible except for one question: What temperature scale should we use? We know that science uses several possible temperature scales. Experiments show that the volume of a gas is related to its absolute temperature in Kelvin, not its temperature in degrees Celsius. If the temperature of a gas is expressed in kelvins, then experiments show that the ratio of volume to temperature is a constant:

We can modify this equation as we modified Boyle’s law: the initial conditions V₁ and T₁ have a certain value, and the value must be the same when the conditions of the gas are changed to some new conditions V₂ and T₂, as long as pressure and the amount of the gas remain constant. Thus, we have another gas law:

This gas law is commonly referred to as Charles’s law, after the French scientist Jacques Charles, who performed experiments on gases in the 1780s. The tactics for using this mathematical formula are similar to those for Boyle’s law. To determine an unknown quantity, use algebra to isolate the unknown variable by itself and in the numerator; the units of similar variables must be the same. But we add one more tactic: all temperatures must be expressed in the absolute temperature scale (Kelvin). As a reminder, we review the conversion between the absolute temperature scale and the Celsius temperature scale:

K = °C + 273

where K represents the temperature in kelvins, and °C represents the temperature in degrees Celsius.

Figure 1.2 “Charles’s Law” shows two representations of how Charles’s law works.

It is more mathematically complicated if a final temperature must be calculated because the T variable is in the denominator of Charles’s law. There are several mathematical ways to work this, but perhaps the simplest way is to take the reciprocal of Charles’s law. That is, rather than write it as

write the equation as

It is still an equality and a correct form of Charles’s law, but now the temperature variable is in the numerator, and the algebra required to predict a final temperature is simpler.