CHEM-E6105 Thermodynamics of Solutions

Exercise 6.2.2020

1. The enthalpies of mixing of Cd-Sn alloys at 500 C (773 K) are given below. Calculate the
values of the partial molar enthalpies of mixing of cadmium and tin in a Cd-Sn alloy
containing 60 at-% cadmium.

xCd ΔΗm, cal/mole ΔΗm, J/mole

0 0 0
0.1 298.2 1247.7
0.3 652.4 2729.6
0.5 800 3347.2
0.7 620.5 2596.2
0.9 251.5 1052.3
1.0 0 0

SOLUTION

Make a plot of Hm vs. xCd. Draw a tangent for the plot at xCd = 0.6. Read the partial molar enthalpy
from the intersects: for tin at x = 0 and for cadmium at x = 1.

ΔΗm, cal/mole
900
800
f(x) = − 3114.09600717811 x² + 3086.25156273366 x + 10.4391356363088
700 R² = 0.996856570883489
600
500
400
300
200
100
0
0 0.2 0.4 0.6 0.8 1 1.2

Derivative = -6228.2x + 3086.3, which gives tangent slope at 0.6 as -650.62

Mixing enthalpy at 0.6 = 741.143
Analysis of linear equation: y = a +bx-  741.143 = a – 650.62*0.6  intercept at x = 0 is
1131.515, this is the molar enthalpy of tin (Cd = 0).
Molar enthalpy of Cd is found at Cd = 1, also 1131.515 - 650.62*1 = 480.895.

Or if you use J/mol data then for tin 4734 J/mol and cadmium 2012 J/mol.
 2. The following values of the activity coefficient of cadmium in zinc-cadmium solutions have
been obtained at 527°C (800 K). Determine whether the Zn-Cd solution exhibits regular
behaviour.

xCd 0.2 0.3 0.4 0.5

Cd 2.153 1.817 1.544 1.352

Solution

For regular solution RT*ln(Cd) = *(xZn)2, and for the binary Cd-Zn solution xZn = 1-xCd.

Therefore, testing can be done using hypothesis RT*ln(Cd) / (1-xCd)2 =  and  should be constant

xCd Cd xZn RT*ln(Cd)/(1-xCd)2

0.2 2.153 0.8 7969.6156
0.3 1.817 0.7 8106.14035
0.4 1.544 0.6 8025.34626
0.5 1.352 0.5 8023.60801

 is quite constant 803156, therefore the system is a regular solution.

 3. The activity coefficient of Zn in liquid Cd-Zn alloys has been measured at 435°C and fitted
by the following equation:

ln γZn = 0.87*XCd2 – 0.30*XCd3

Find an expression for ln γCd as a function of composition.

SOLUTION

From the Gibbs-Duhem equation, XCd d(lnγCd) + XZn d(lnγZn) = 0  XCd d(lnγCd) = - XZn d(lnγZn)

Calculate derivative of the zinc activity coefficient function and arrange the equation

XCd d(lnγCd) = -(1-XCd)*(2*0.87*XCd - 3*0.30*XCd2)d(XCd)

d(lnγCd) = -0.90*(XCd)2 + 2.64 XCd - 1.74 d(XCd)

Integrate

ln(γCd) = -0.30*(XCd)3 + 1.32*(XCd)2 - 1.74*(XCd) + constant

If the equation for lnγZn is valid up to XCd = 1, then we can use the fact that ln γCd = 0.0 or
γCd = 1.0 when XCd = 1.0. This gives constant value C = 0 + 0.3 -1.32 + 1.74 = 0.72.
 4. Al-Zn alloys exhibit the following relation at 750 K:

RT*ln(Zn) = 1750*(1 - xZn)2

Calculate the activity of aluminium at 750 K in an Al-Zn alloy containing 40 at-% zinc.

Solution

The general Gibbs-Duhem equation: dZA*xA = -dZB*xB

The activity coefficient of zinc at 750 K is given by

8.314*750*ln(Zn) = 1750*(1-xZn)2
ln(Zn) = 0.2806*(1-xZn)2
Differentiating
d(ln(Zn)) = -0.5613*(1-xZn) d(xZn)
From Gibbs-Duhem equation
d(ln(Al)) = -(xZn/xAl) * d(ln(Zn))
d(ln(Al)) = (xZn/xAl) * 0.5613*(1-xZn) d(xZn)
As we have a binary solution
d(ln(Al)) = (xZn/(1-xZn)) * 0.5613*(1-xZn) d(xZn)
d(ln(Al)) = 0.5613*xZn d(xZn)
The value of Al at xZn = 0.4 can be obtained by calculating a definite integral.

xAl=0.6 xZn=0.4

∫ d ln ( γ Al )= ∫ 0.5613∗x Zn d ( x Zn )
xAl=1.0 xZn=0

ln ⁡¿

Because at xAl = 1, Al = 1 activity coefficient ln(Al)xAl=0.6 = 0.2806*(0.16-0) = 0.045

Al at xAl = 0.6 is 1.046.

The activity of aluminium in the alloy at xAl = 0.6 is 1.046*0.6 = 0.628.