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Chemistry · Ch 5 — States of Matter

Charles' Law (Temperature - Volume Relationship)

5.5.2

Charles' Law (Temperature - Volume Relationship)

Discovering the volume-temperature relationship

Charles and Gay Lussac, working independently while trying to improve hot-air-balloon technology, ran a series of experiments on gases. They found that for a fixed mass of gas at constant pressure, volume increases on heating and decreases on cooling. More precisely, for each degree rise in temperature, a gas's volume grows by 1273.15\dfrac{1}{273.15} of its volume at 0 ∘C0\,^{\circ}\text{C}. If V0V_0 and VtV_t are the volumes at 0 ∘C0\,^{\circ}\text{C} and t ∘Ct\,^{\circ}\text{C} respectively:

Vt=V0(1+t273.15)=V0(273.15+t273.15)V_{t} = V_{0}\left(1+\frac{t}{273.15}\right) = V_{0}\left(\frac{273.15+t}{273.15}\right)

Introducing the Kelvin scale

This pattern motivates a new temperature scale: define T=273.15+tT = 273.15 + t, so that 0 ∘C0\,^{\circ}\text{C} corresponds to T0=273.15T_0 = 273.15. This is the Kelvin (absolute) temperature scale, also called the thermodynamic scale, and it is the scale used throughout scientific work — note that no degree sign is written with a Kelvin value. Substituting Tt=273.15+tT_t = 273.15+t and T0=273.15T_0 = 273.15 gives:

VtV0=TtT0⟹V2V1=T2T1⟹VT=constant=k2⟹V=k2T\frac{V_{t}}{V_{0}} = \frac{T_{t}}{T_{0}}\qquad\Longrightarrow\qquad \frac{V_{2}}{V_{1}}=\frac{T_{2}}{T_{1}}\qquad\Longrightarrow\qquad \frac{V}{T} = \text{constant} = k_{2}\qquad\Longrightarrow\qquad V = k_{2}T

This final relationship — at constant pressure, the volume of a fixed mass of gas is directly proportional to its absolute temperature — is Charles' Law. The constant k2k_2 depends on the gas's pressure, its amount, and the units used for VV.

Isobars and absolute zero

Charles found that, for any given pressure, a plot of volume against temperature (in ∘C^{\circ}\text{C}) is a straight line; extending each such line — called an isobar — to zero volume, every line meets the temperature axis at the same point, −273.15 ∘C-273.15\,^{\circ}\text{C} (Fig. 5.6), regardless of the pressure used. …

Figure 5.6Volume vs Temperature (°C) graph

What this figure shows. A pale-yellow-shaded graph with vertical axis 'Volume' (upward arrow) and horizontal axis 'Temperature (°C)' (rightward arrow) marked at -300, -200, -100, 0, 100; a vertical dashed line and small downward arrow mark '-273.15' on the temperature axis. Four straight lines (isobars) of different slopes, labelled p1, p2, p3, p4 from steepest to shallowest with the relation 'p1 < p2 < p3 < p4' written above them (p1 the leftmost/steepest solid+dashed line in blue, p2 red, p3 green, p4 cyan/lowest slope) all converge (when extrapolated, shown as dotted line segments) to meet the temperature axis at the single point -273.15°C, illustrating that at …