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GAS PHASE THERMOCHEMISTRY

(TABULAR DATA AVAILABLE)

Shomate equation gives molar heat capacity as a function of temperature.


𝐽 𝐸 𝑇[𝐾]
𝐶𝑃0 [ ] = 𝐴 + 𝐵𝑡 + 𝐶𝑡 2 + 𝐷𝑡 3 + 𝑤𝑖𝑡ℎ 𝑡= … (1)
𝑚𝑜𝑙.𝐾 𝑡2 1000

When tabular data for molar heat capacity versus temperature are available, coefficients of Shomate equation can be
estimated through regression using the method of least squares. The objective function can be written as
2
𝑚𝑖𝑛𝑖𝑚𝑖𝑧𝑒 𝐹(𝑡) = ∑𝑛𝑖=1[𝐶𝑃,𝑖
0
− 𝐶𝑃0 (𝑡𝑖 )] 𝑤𝑖𝑡ℎ 𝑛 = 𝑛𝑜. 𝑜𝑓 𝑑𝑎𝑡𝑎 𝑝𝑜𝑖𝑛𝑡𝑠 … (2)
0 2
⇒ 𝑚𝑖𝑛𝑖𝑚𝑖𝑧𝑒 𝐹(𝑡) = ∑[𝐶𝑃,𝑖 − (𝐴 + 𝐵𝑡𝑖 + 𝐶𝑡𝑖2 + 𝐷𝑡𝑖3 + 𝐸𝑡𝑖−2 )] … (3)
Analytical solution can be easily determined using Microsoft Excel. Once a polynomial for molar heat capacity is
obtained, molar enthalpy and molar entropy can be obtained by integration.
𝑘𝐽 𝐵𝑡 2 𝐶𝑡 3 𝐷𝑡 4 𝐸
(𝐻0 − 𝐻𝑅0 ) [ ] = 𝐴𝑡 + + + − +𝐹−𝐻 𝑤𝑖𝑡ℎ 𝐻 = ∆𝑓 𝐻0 | … (4)
𝑚𝑜𝑙 2 3 4 𝑡 𝑇𝑟𝑒𝑓

𝐽 𝐶𝑡 2 𝐷𝑡 3 𝐸
𝑆0 [ ] = 𝐴 ln 𝑡 + 𝐵𝑡 + + − +𝐺 … (5)
𝑚𝑜𝑙.𝐾 2 3 2𝑡 2

The unknown constants F and G can be evaluated by using the specified values of molar enthalpy and molar entropy
at the reference temperature, respectively.
𝐵𝑡 2 𝐶𝑡 3 𝐷𝑡 4 𝐸
𝐹 = (𝐻0 − 𝐻𝑅0 )| 𝑇𝑟𝑒𝑓 − (𝐴𝑡 + + + − − 𝐻)|
2 3 4 𝑡 𝑇𝑟𝑒𝑓
… (6)
𝑘𝐽
𝑤𝑖𝑡ℎ (𝐻0 − 𝐻𝑅0 )| 𝑇𝑟𝑒𝑓 = 0.0 [ ]
𝑚𝑜𝑙
𝐶𝑡 2 𝐷𝑡 3 𝐸
𝐺 = 𝑆 0 | 𝑇𝑟𝑒𝑓 − (𝐴 ln 𝑡 + 𝐵𝑡 + + − )| … (7)
2 3 2𝑡 2 𝑇𝑟𝑒𝑓

The calculated values of molar enthalpy and molar entropy can be used to evaluate the enthalpy, entropy and Gibbs
free energy of formation of a substance at any given temperature.
𝑘𝐽
∆𝑓 𝐻0 [ ] = ∆𝑓 𝐻0 | + ∑𝑃(𝐻0 − 𝐻𝑅0 ) − ∑𝑅(𝐻0 − 𝐻𝑅0 ) … (8)
𝑚𝑜𝑙 𝑇𝑟𝑒𝑓

𝐽
∆𝑓 𝑆 0 [ ] = ∑𝑃 𝑆 0 − ∑𝑅 𝑆 0 … (9)
𝑚𝑜𝑙.𝐾

𝑘𝐽 𝑇∆𝑓 𝑆 0
∆𝑓 𝐺 0 [ ] = ∆𝑓 𝐻0 − … (10)
𝑚𝑜𝑙 1000

Note that a factor of 1000 appears in Eqn. 10 for unit consistency.