 Solution

The given binding energy $ϵ$ belongs to the formation of two carbon-dioxide molecules. Relative to the reference used in (a), the internal energy offset of one carbon-dioxide molecule is therefore $-ϵ/2$, not $-ϵ$. Its mass is $m_c=m_{\mathrm{CO}}+m_{{\mathrm{O}}_2}/2$ and its thermal de Broglie wavelength is ${\lambda }_c=h/\sqrt{2\pi m_c{k}_{B}T}$, where the subscript $c$ denotes $\mathrm{C}{\mathrm{O}}_2$.

The single-molecule canonical partition function is $(V/{\lambda }_c^3)e^{\beta ϵ/2}$. For $N_c$ indistinguishable noninteracting molecules,The corresponding Helmholtz free energy, using Stirling's approximation, isThe negative sign in the last term expresses the stabilizing binding energy and ensures that low temperature favors association.