题目
某二元系的汽相可是为理想气体,液相为非理想溶液,溶液的超额Gibbs自由能的函数表达式为(G^E)/(RT) = Ax_1x_2。在某一温度下,该系统有一共沸点,共沸组成为x_1 = 0.7826,纯组分1, 2的饱和蒸气压分别是p_1^s = 59.66kPa和p_2^s = 17.82kPa,试求该二元系在此温度下,当x_1 = 0.35时的汽相组成和平衡压力。
某二元系的汽相可是为理想气体,液相为非理想溶液,溶液的超额Gibbs自由能的函数表达式为$\frac{G^E}{RT} = Ax_1x_2$。在某一温度下,该系统有一共沸点,共沸组成为$x_1 = 0.7826$,纯组分1, 2的饱和蒸气压分别是$p_1^s = 59.66kPa$和$p_2^s = 17.82kPa$,试求该二元系在此温度下,当$x_1 = 0.35$时的汽相组成和平衡压力。
题目解答
答案
根据题目给出的超额Gibbs自由能公式 $ \frac{G^E}{RT} = A x_1 x_2 $,可得:
\[
\ln \gamma_1 = A x_2^2, \quad \ln \gamma_2 = A x_1^2
\]
在共沸点 $ x_1 = 0.7826 $,由 $ \gamma_1 x_1 p_1^s = \gamma_2 x_2 p_2^s $,可解得:
\[
A = \frac{\ln \left( \frac{x_1 p_1^s}{x_2 p_2^s} \right)}{x_1^2 - x_2^2} = \frac{2.49}{0.56513} \approx 4.406
\]
当 $ x_1 = 0.35 $ 时:
\[
\gamma_1 = e^{4.406 \times 0.65^2} = e^{1.861} \approx 6.43
\]
\[
\gamma_2 = e^{4.406 \times 0.35^2} = e^{0.5397} \approx 1.715
\]
平衡压力:
\[
p = \gamma_1 x_1 p_1^s + \gamma_2 x_2 p_2^s = 6.43 \times 0.35 \times 59.66 + 1.715 \times 0.65 \times 17.82 \approx 154.1 \, \text{kPa}
\]
汽相组成:
\[
y_1 = \frac{\gamma_1 x_1 p_1^s}{p} = \frac{134.2}{154.1} \approx 0.871
\]
\[
y_2 = 1 - y_1 = 0.129
\]
答案:
$ p \approx 154.1 \, \text{kPa} $,$ y_1 \approx 0.871 $,$ y_2 \approx 0.129 $。