Thermodynamics of Multicomponent Systems 3C04 Assignment 3 Solutions

1. The molar volumes of solid and liquid lead at the normal melting temperature of lead are respectively, 18.92 cm3 and 19.47 cm3. Calculate the pressure which must be applied to lead in order to increase its melting temperature by 20 centigrade degrees. ANSWER: Thermodynamic Data: H ( s l ) = 4810 J / mol

Ttrans = 600 K
V ( s l ) = 19.47 18.92 = 0.55 cm3 mol

H dP = dT T V P2 P = 1 H T2 ln V T1 4810 620 = ln 0.55 600 = 286.76 J / cm3 82.057 = 286.76 * 8.314 = 2830 atm

2. Measurements of the saturated vapor pressure of liquid NdCl5 give 0.3045 atm at 478K and 0.9310 atm at 520K. Calculate the normal boiling temperature of NdCl5.

ANSWER:
The vapor pressure is given by the following equation: A ln p = + B T For measurement 1 we get: A ln ( 0.3045 ) = +B 478 For measurement 2 we get: A ln ( 0.9310 ) = +B 520
Solving for A and B yields:

A = 6614

B = 12.65
Therefore, at 1 atm pressure the normal boiling point of NdCl5 is:

ln (1) =

6614 + 12.65 T T = 523K

3. One mole of solid Cr2O3 at 2500K is dissolved in a large volume of liquid Raoultian solution of Al2O3 and Cr2O3 in which XCr2O3 = 0.2 and which is also at 2500 K. Calculate the changes in enthalpy and entropy caused by the addition. The normal melting temperature of Cr2O3 is 2538 K, and it can be assumed that the S m , Al2O3 = S m ,Cr2O3 .

ANSWER:
Thermodynamic Data: H m, Al2O3 = 107500 J

Ttrans = 2324 K Sm, Al2O3 = Sm,Cr2O3 = H m,Cr2O3 107500 = 46.25 J / K 2324 = 46.25* 2538 = 117400 J
H = H M = 117400
ID H = H M = 0

Cr( s ) Cr(l )

Cr(l ) Cr( solution ) H Total = 117400 J Cr( s ) Cr(l )

S = S M = 46.25
ID S = S M = R ln X Cr = R ln 0.2 = 13.38

Cr(l ) Cr( solution )

STotal = 46.25 + 13.38 = 59.63 J / K

4. The variation, with composition, of GXS for liquid Fe-Mn alloys at 1863 K is listed below. a. Does the system exhibit regular solution behaviour?
XS XS b. Calculate GFe and GMn at XMn = 0.6.

c. Calculate G M at XMn = 0.4. d. Calculate the partial pressures of Mn and Fe exerted by the alloy of XMn = 0.2.

XMn G ,J
XS

0.1 395

0.2 703

0.3 925

0.4 1054

0.5 1100

0.6 1054

0.7 925

0.8 703

0.9 395

ANSWER:
a)

G = G ID + G EX

G EX = G M G ID = X A X B
Solving for using the data given: XMn XFe XMnXFe GXS, J 0.1 0.9 0.09 395 4389 0.2 0.8 0.16 703 4394 0.3 0.7 0.21 925 4405 0.4 0.6 0.24 1054 4392 0.5 0.5 0.25 1100 4400 0.6 0.4 0.24 1054 4392 0.7 0.3 0.21 925 4405 0.8 0.2 0.16 703 4394 0.9 0.1 0.09 395 4389

Taking the average of above gives 4395J. Therefore, the system exhibits regular solution behaviour. b)
EX GFe = RT ln Fe = X Mn X Mn = 4395 * 0.6 * 0.6 = 1582 J EX GMn = RT ln Mn = X Fe X Fe = 4395 * 0.4 * 0.4 = 703 J

c)

G = G ID + G EX = RT ( X Fe ln X Fe + X Mn ln X Mn ) + RT ( X Fe ln Fe + X Mn ln Mn ) = RT ( X Fe ln X Fe + X Mn ln X Mn ) + X Fe X Mn = 9369 J = 8.314 *1863* ( 0.6 ln 0.6 + 0.4 ln 0.4 ) + 4395 * 0.4 * 0.6

d) At XMn = 0.2

Mn = exp

4395 * 0.82 = 1.2 8.314 *1863

aMn = 1.2 * 0.2 = 0.24

At XMn = 0.2

Fe
aFe

4395 * 0.22 = exp = 1.011 8.314 *1863 = 1.011* 0.8 = 0.809

The vapor pressure of Mn and Fe are determined as (Gaskell appendix):

33440 o pMn = exp 3.02 ln (1863 ) + 37.68 = 0.0493 atm 1863 45390 o pFe = exp 1.27 ln (1863) + 23.93 = 4.55 x105 atm 1863
Using this data the partial pressures can be determined:

aMn =

pMn o pMn pFe o pFe

pMn = 0.24 * 0.0493 = 0.0118atm aFe =

pFe = 0.809 * 4.55 x105 = 3.68 x10 5 atm