17.(4.0分)一定温度压力下,二元混合物的摩尔-|||-体积可表示为 _(乙)=A+B(x)_(1)+C({x)_(2)}^2 ,则组分1的偏摩尔-|||-体积正确的表达式为 () 。-|||-A _(1)=A+B-C({x)_(2)}^2 ;-|||-B ._(1)=A+B+C({x)_(2)}^2 ;-|||-C _(1)=B+2C(x)_(2)

题目解答
答案
解析
本题考查偏摩尔体积的计算,解题思路是根据偏摩尔体积的定义式,结合已知的混合物摩尔体积表达式进行求导计算。
步骤一:明确偏摩尔体积的定义式
对于二元混合物,组分$1$的偏摩尔体积$V_1$的定义式为:
$V_1 = V_m + x_2(\frac{\partial V_m}{\partial x_2})_{T,p}$
其中$V_m$是混合物的摩尔体积,$x_2$是组分$2$的摩尔分数,$(\frac{\partial V_m}{\partial x_2})_{T,p}$表示在恒温恒压下$V_m$对$x_2$的偏导数。
步骤二:根据已知条件确定$V_m$和$x_2$的表达式
已知混合物的摩尔体积$V_m = A + Bx_1 + Cx_2^2$,又因为$x_1 + x_2 = 1$,即$x_1 = 1 - x_2$,所以$V_m = A + B(1 - x_2) + Cx_2^2 = A + B - Bx_2 + Cx_2^2$。
步骤三:计算$(\frac{\partial V_m}{\partial x_2})_{T,p}$
对$V_m = A + B - Bx_2 + Cx_2^2$关于$x_2$求偏导数:
$(\frac{\partial V_m}{\partial x_2})_{T,p} = \frac{\partial (A + B - Bx_2 + Cx_2^2)}{\partial x_2}$
根据求导公式$(X^n)^\prime = nX^{n - 1}$,常数的导数为$0$,可得:
$(\frac{\partial V_m}{\partial x_2})_{T,p} = -B + 2Cx_2$
步骤四:将$V_m$和$(\frac{\partial V_m}{\partial x_2})_{T,p}$代入偏摩尔体积定义式计算$V_1$
$V_1 = V_m + x_2(\frac{\partial V_m}{\partial x_2})_{T,p}$
$= A + B - Bx_2 + Cx_2^2 + x_2(-B + 2Cx_2)$
$= A + B - Bx_2 + Cx_2^2 - Bx_2 + 2Cx_2^2$
$= A + B - 2Bx_2 + 3Cx_2^2$
再将$x_2 = 1 - x_1$代入上式:
$V_1 = A + B - 2B(1 - x_1) + 3C(1 - x_1)^2$
$= A + B - 2B + 2Bx_1 + 3C(1 - 2x_1 + x_1^2)$
$= A - B + 2Bx_1 + 3C - 6Cx_1 + 3Cx_1^2$
$= A + B + Cx_2^2 - x_1(A + Bx_1 + Cx_2^2)$
$= A + B + C(1 - x_1)^2 - x_1(A + Bx_1 + C(1 - x_1)^2)$
$= A + B + C(1 - 2x_1 + x_1^2) - x_1(A + Bx_1 + C(1 - 2x_1 + x_1^2))$
$= A + B + C - 2Cx_1 + Cx_1^2 - Ax_1 - Bx_1^2 - Cx_1 + 2Cx_1^2 - Cx_1^3$
$= A + B + C - 3Cx_1 + 3Cx_1^2 - Ax_1 - Bx_1^2 - Cx_1^3$
$= B + 2Cx_2$