4.1.

  Sensible Heat Effects 139

Gas mixtures of constant composition behave exactly as do pure gases. In the ideal-gas
state, molecules in mixtures have no influence on one another, and each gas exists independent
of the others. The ideal-gas-state heat capacity of a mixture is therefore the mole-fraction-
weighted sum of the heat capacities of the individual gases. Thus, for gases A, B, and C, the
molar heat capacity of a mixture in the ideal-gas state is:
ig ig ig ig
​​C​​P​ m ​
ixture ​ 
​ = ​y​ A​C​​P​ A ​ ​ ​ + ​y​ B​C​​P​ B ​ ​ ​ + ​y​ C​C​​P​ C ​​ ​ ​ (4.7)
ig ig ig
where ​​C​​P​ A ​,​​  ​C​​P​ B ​,​​   and ​C​​P​ C ​​​​  are the molar heat capacities of pure A, B, and C in the ideal-gas state,
and yA, yB, and yC are mole fractions. Because the heat-capacity polynomial, Eq. (4.5), is lin-
ear in the coefficients, the coefficients A, B, C, and D for a gas mixture are similarly given by
mole-fraction weighted sums of the coefficients for the pure species.

Evaluation of the Sensible-Heat Integral

Evaluation of the integral ∫ CPdT is accomplished by substitution for CP as a function of T
by Eq. (4.4), followed by formal integration. For temperature limits of T0 and T the result is:

( T ​T​ 0​ )
T ​C​  ​ T − ​T​ 0​
∫​T​ 0​ R
B C
​   ​  ​ ___
​   ​  dT = A(T − ​T​ 0​) + ​__
   ​  (​T​ 2​ − ​T​02​  ​) + ​__
   ​  (​T​ 3​ − ​T​03​  ​)  + D​​ _
P
​ ​     ​ ​​ (4.8)
2 3
Given T0 and T, the calculation of Q or ΔH is straightforward. Less direct is the calcula-
tion of T, given T0 and Q or ΔH. Here, an iteration scheme may be useful. Factoring (T − T0)
from each term on the right side of Eq. (4.8) gives:

[ T ​T​ 0​]
T ​C​  ​

∫​T​ 0​ R
B C D
​   ​  ​ ___
​   ​  dT = ​​ ​A + ​_
   ​    (T + ​T​ 0​) +  ​_
   ​    (​T​ 2​ + ​T​02​  ​ + T ​T​ 0​) +  ​_
P
​      ​ ​(T − ​T​ 0​)​
2 3
We identify the quantity in square brackets as ​〈​CP​  ​〉​ H​ / R​, where ​〈​CP​  ​〉​ H​is defined as a mean heat
capacity for the temperature range from T0 to T:
​〈​CP​  ​〉​ H​
________ B C D
​
​      ​  = A + ​__
   ​  (T + ​T​ 0​) + ​__
   ​   (​T​ 2​ + ​T​02​  ​ + T ​T​ 0​) +  ​____
     ​​   (4.9)
R 2 3 T ​T​ 0​
Equation (4.2) may therefore be written:

ΔH = ​〈​CP​  ​〉​ H​(T − ​T​ 0​)​
​ (4.10)

The angular brackets enclosing CP identify it as a mean value; subscript H denotes a mean
value specific to enthalpy calculations and distinguishes this mean heat capacity from a simi-
lar quantity introduced in the next chapter.
Solution of Eq. (4.10) for T gives:
ΔH
T = ​________
​     ​  
+ ​T​  ​​ (4.11)
​〈​CP​  ​〉​ H​ 0
With a starting value for T, one can first evaluate ​⟨​​CP​  ​⟩​ H​​by Eq. (4.9). Substitution into
Eq. (4.11) provides a new value of T from which to reevaluate ​⟨​CP​  ​⟩​ H​. Iteration continues to
convergence on a final value of T. Of course, such iteration is readily automated with built-in
functions in a spreadsheet or a numerical analysis software package.