9.

3 Consider a system with components Cu, Ni and Zn that contains four phases: , ,
and L.
(a) List the variable required to specify the state of each phase; count them.
(b) List the conditions for equilibrium for this system; count them.
(c) From these counts, compute the number of degrees of freedom.
(d) Compare this result with the number of degrees of freedom computed from the
Gibbs phase rule.
Solution:
(a) No. of components(c) = 3
No. of phases(P)= 4
Degree of freedom: F = c+2-P
F = 3+2-1= 4
So, for each phase the variables required to specify the state is 4.
Example; for the state of Cu the variables are: T, P, XNi, XZn.
(b) The conditions for equilibrium for the system are:
T=T=T=TL
P=P=T=TL
Cu= Cu=Cu=CuL
Ni=Ni=Ni=NiL
Zn=Zn=Zn=ZnL
The total no. of conditions are (c+2)x(P-1) = 15

(c) Degree of freedom is = (Total no. of variables in the system) (No. of equations
relating to the variables)
F= 16 -1 5= 1

(d) From Gibbs phase rule:

F+P= C+2
F= 3+2-4= 1

10.1 Replot the G-X curves shown in Figure 10.2 for the following choices of reference
states for components 1 and 2.
a. {L;L}
b. {L;}
 c. {;}
curves are computed with the following information: solution models are simple
regular solutions. Tm1 = 1500K; Tm2 = 850K; DSm1= 9 J/mol k; DSm2= 7J/mol k; a0 =
8400 J/mol; a0L= 10,500 J/mol.
Solution:
Given: components: 1 & 2 are in phases and L.
For regular solution model:
DGmix{;}=aoX1X2+RT(X1lnX1+X2lnX2)
DGmix{;}=8400X1X2+RT(X1lnX1+X2lnX2)
DGmix{;}=8400X1X2+8.314x1000(X1lnX1+X2lnX2)
DGmix{;}=8400(1-X2) X2+8.314x1000[(1-X2) ln(1-X2) +X2lnX2]

DGmixL{L;L}=aoLX1LX2L+RT(X1LlnX1L+X2LlnX2L)
DGmixL{L;L}=10,500X1LX2L+RT(X1LlnX1L+X2LlnX2L)
DGmixL{L;L}=10,500X1LX2L+8.314x1000(X1LlnX1L+X2LlnX2L)
DGmixL{L;L}=10,500(1-X2L) X2L+8.314x1000[(1-X2L)ln(1-X2L)+X2LlnX2L)

a. For reference state {L;L}:

Gibbs free energy of mixing of Liquid Phase taken {L;L} as reference.
DGmixL{L;L}= DGmixL{L;L}
DGmixL{L;L}=10,500(1-X2L) X2L+8.314x1000[(1-X2L)ln(1-X2L)+X2LlnX2L)

Gibbs free energy of mixing of phase taken reference as {L;L}

DGmix{L;L}=X1(G1-G1oL) + X2(G2-G2oL)
DGmix{L;L}=X1(G1-G1o+ G1o -G1oL) + X2(G2 -G2o+ G2o -G2oL)
DGmix{L;L}= X1(G1-G1o)+ X1(G1o -G1oL)+ X2(G2 G2o)+ X2(G2o -G2oL)
DGmix{L;L}=DGmix{;} + X1(G1o -G1oL)+ X2(G2o -G2oL)
DGmix{L;L}=DGmix{;}-X1DSm1(Tm1-T) -X2DSm2(Tm2-T)
DGmix{L;L}=DGmix{;}-X19(1500-1000) -X27(850-1000)
 DGmix{L;L}=DGmix{;}-X19(500) +X27(150)
DGmix{L;L}=8400(1-X2) X2+8.314x1000[(1-X2) ln(1-X2) +X2lnX2] - (1-X2)
9(500) +X27(150)

b. For reference state {L;}:

DGmix{L;}=DGmix{;} -X1DG1oL
DGmix{L;}=DGmix{;} -X1DSm1(Tm1-T)
DGmix{L;}=DGmix{;} -X19(1500-1000)
DGmix{L;}=DGmix{;} -X19(500)
DGmix{L;}=8400(1-X2) X2+8.314x1000[(1-X2) ln(1-X2) +X2lnX2]- (1-X2)9(500)
 DGmixL{L;}=DGmixL{L;L} +X2LDG2oL
DGmixL{L;}=DGmixL{L;L}+X2LDSm2(Tm2-T)
DGmixL{L;}=DGmixL{L;L}+X2L7(850-1000)
DGmixL{L;}=DGmixL{L;L}-X2L7(150)
DGmixL{L;}=10,500(1-X2L) X2L+8.314x1000[(1-X2L)ln(1-X2L)+X2LlnX2L) -X2L7(150)

c. For reference state {;}:

DGmix{;}= DGmix{;}
DGmix{;}= 8400(1-X2) X2+8.314x1000[(1-X2) ln(1-X2) +X2lnX2]
 DGmixL{;}= DGmixL{L;L}+X1LDG1oL+X2LDG2oL
DGmixL{;}= DGmixL{L;L}+X1LDSm1(Tm1-T) + X2LDSm2(Tm2-T)
DGmixL{;}= DGmixL{L;L}+ X19(1500-1000)+ X2L7(850-1000)
DGmixL{;}= DGmixL{L;L}+ X19(500) -X2L7(150)
DGmix {;}=10,500(1-X2L) X2L+8.314x1000[(1-X2L)ln(1-X2L)+X2LlnX2L) -X2L7(150)+ (1-X2)
L

9(500)

10.2 The A-B system forms regular solutions in both the and liquid phase forms.
Parameters for the heat of mixing for these phases are a 0= -8200 J/mol and a0L =
-10,500 J/mol.
a. Compute and plot curves for DGmix for the and liquid phases for these models
at 800K. Pure A melts at 1050K with a heat of fusion of 8200 J/mol. Pure B melts at
660K with a heat of fusion of 6800 J/mol.
b. Change the reference states appropriately to plot and compare DG mix{;L} and
DGmixL{;L}.
Neglect differences in heat capacities for the phases for the pure components.
Solution:
a. For regular solution model, we have the A-B system in phase:

DGmix{;} = a0XAXB + RT(XAlnXA+XBlnXB)

DGmix{;} = -8200XAXB + RT(XAlnXA+XBlnXB)

Similarly, for the system A-B in L phase, we have:

DGmixL{L;L} = a0LXALXBL + RT(XALlnXAL+XBLlnXBL)
DGmixL{L;L} = -10,500XALXBL + RT(XALlnXAL+XBLlnXBL)

b. DGmix{;L} = DGmix{;} -XBDG0L

= DGmix{;} -XB(GA0L-GA0)
= DGmix{;} -XBDSm0(TmB-T)
= DGmix{;} -XBDHm0(TmB-T)/ TmB
=DGmix{;} -XB 6800 (660-T)/660
DGmix{;L} = -8200XAXB + RT(XAlnXA+XBlnXB) - XB 6800 (660-
T)/660
DGmixL{;L} = DGmixL{L;L} + XALDG0L
= DGmixL{L;L} + XALDSm0(TmA-T)
= DGmixL{L;L} + XALDHm0(TmA-T)/ TmA
DGmixL{;L} = -10,500XALXBL + RT(XALlnXAL+XBLlnXBL) +
XAL8200(1050-T)/ 1050