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Chemistry · Ch 5 — Thermodynamics

The Relationship between Cp and CV for an Ideal Gas

5.2.2(d)

The Relationship between Cp and CV for an Ideal Gas

The Relationship between Cp and CV for an Ideal Gas

The heat capacity of a system depends on the conditions under which the heating occurs. Two special cases are particularly important:

  • Heat capacity at constant volume, CVC_V: the heat required to raise the temperature by one degree while keeping the volume fixed.
  • Heat capacity at constant pressure, CpC_p: the heat required to raise the temperature by one degree while keeping the pressure fixed.

At constant volume, qV=CVΔT=ΔUq_V = C_V\Delta T = \Delta U (since no work is done). At constant pressure, qp=CpΔT=ΔHq_p = C_p\Delta T = \Delta H.

For an ideal gas, we can derive a simple relationship between CpC_p and CVC_V. Consider one mole of an ideal gas. From the definition of enthalpy:

ΔH=ΔU+Δ(pV)\Delta H = \Delta U + \Delta(pV)

For an ideal gas, pV=RTpV = RT (for one mole), so Δ(pV)=Δ(RT)=RΔT\Delta(pV) = \Delta(RT) = R\Delta T (since RR is constant). Therefore:

ΔH=ΔU+RΔT\Delta H = \Delta U + R\Delta T

Now substitute ΔH=CpΔT\Delta H = C_p\Delta T and ΔU=CVΔT\Delta U = C_V\Delta T:

CpΔT=CVΔT+RΔTC_p\Delta T = C_V\Delta T + R\Delta T

Dividing through by ΔT\Delta T (which is non-zero):

Cp−CV=RC_p - C_V = R

This is a fundamental result for ideal gases. The molar heat capacity at constant pressure is always larger than that at constant volume by exactly the gas constant RR (approximately 8.314 J mol−1K−18.314\ \text{J mol}^{-1}\text{K}^{-1}).

Watch out

This relationship Cp−CV=RC_p - C_V = R holds only for ideal gases. For real gases, solids, and liquids, the difference is more complicated and generally much smaller. …