(1).

For the reaction:

Co(s) + O2(g) = CoO(s)

Grxn
o
= 59,850 + 19.6T, where Grxn
o
is in calories and T is in kelvin.

(a) Calculate the oxygen equilibrium pressure (atm) over Co and CoO at 1000oC.

Ans: (a) 1.044610-12 atm

Solution:
(a) At 1000C,
Grxn = -59,850 Cal +19.6TK
= -59,850+19.6 (1,000+273.15K)
= -34,896.26 cal
= -146103.66 J
= -146.1 kJ/mol
At equilibrium:
CoO
Grxn = -RTLnCo.O
1
= -RT Ln PO
1
-146.1kJ/mol = RT Ln PO
2
Ln PO = -27.6
PO = 1.026610-12 atm

(2) Calculate the temperature at which silver oxide (Ag2O) begins to decompose into silver and
oxygen upon heating:

(a) in pure oxygen at P = 1 atm.

(b) in air at Ptotal = 1 atm.

Data: hof for Ag2O = 7300 cal/mol

Standard Entropies at 298oK [cal/(molK)]

Ag2O O2 Ag
29.1 49.0 10.2

Assume that Cp = 0 for the decomposition reaction.

Ans: (a) 462oK (b) 420.8oK
Solution:
(a) Ag2O= 1/2O2 + 2Ag
H = -HfAgO = 7300cal / mol = 30563.64J/mol
1
S = 2SAg,298 + SO2,298 - SAg2O,298
2
1
= 2x10.2+ 49-29.1
2
= 66.044J/mol.K
G = H-TS
= 30563-TS
= 30563-66.044T
 When Ag2O begins to decompose,
G = G+ RT Ln J = 0
= 30563-66.044T + RT Ln PO2 = 0
In pure oxygen at 1 atm,
RTLnPO2 =0
30563-66.044T = 0
T = 462.767K
(b) In air at Ptotal = 1 atm, PO2 = 0.21 atm
30563-66.044T + RT Ln PO2 = 0
30563-66.044T + RT Ln 0.21 = 0
T = 386 K

(3) Pack cementation is a process where a pure element or master alloy is deposited on the surface of
a superalloy to extend its life in corrosive and oxidizing environments at high temperature. There
are four constituents to this process: a filler, a pure element or master alloy, an activator, and a
substrate. The inert or filler provides a medium for vapor transport, e.g., aluminum oxide Al2O3.
The pure element or master alloy will be deposited on the substrate. The activator is used to
transport the master alloy through the filler to the substrate, which is the surface of the
superalloy. We will consider the case where aluminum with AlF3 activator will be mixed with
aluminum oxide powder in a pack cementation process at 1300oK. A schematic of the process is
shown in Figure 8-1 where the system is maintained at 1 atm in an environment of Argon gas.
The bulk pack is the region where aluminum and activator exist within the filler. In the depleted
zone, there is no aluminum or activator. For this process aluminum is transferred from the bulk
pack to the substrate in the form of aluminum flouride vapor, under the action of the
thermodynamic activity gradient that exists between the pack and substrate.
Substrate
Coating

Bulk Depleted
pack zone

Figure 8-1 Schematic of pack aluminizing process.

At the bulk pack the following reactions will occur

AlF3(s) = AlF3(g) (8-1)

2Al(l) + AlF3(s) = 3AlF(g) (8-2)

Al(l) + 2AlF3(s) = 3AlF2(g) (8-3)

2AlF3(g) = Al2F6(g) (8-4)

Since the melting point of pure aluminum is 933.6oK, aluminum will exist in the bulk pack as a
liquid. The five partial pressures (PAlF, PAlF2, PAlF3, PAl2F6, and PAr) in the bulk pack can be
obtained from the four equilibrium conditions above and the assumption that
 PAlF + PAlF2 + PAlF3 + PAl2F6 + PAr = 1 atm (8-5)

Table 8-1 provides data for the Gibbs energies of formation for the species present in the
process.
(T is in K and log is natural log [ln])
Species g rxn
o

AlF3(c) dGAlF3c = -364.127-2.148e-3*T*log(T)-.695e-6*T^2+75.825/T+80.828e-3*T;

AlF(g) dGAlF = -64.681+3.384e-3*T*log(T)-.111e-6*T^2+16.925/T-41.184e-3*T;
AlF2(g) dGAlF2 = -167.465+3.113e-3*T*log(T)-0.109e-6*T^2+47.250/T-26.530e-3*T;
AlF3(g) dGAlF3 = -291.345+2.282e-3*T*log(T)-.323e-6*T^2+79.025/T+0.712e-3*T;
Al(c,l) 0
Al2F6(g) dGAl2F6 = -633.645+0.566e-3*T*log(T)-.608e-6*T^2+242.500/T+68.953e-3*T;
Determine the partial pressures PAlF, PAlF2, PAlF3, PAl2F6, and PAr in the bulk pack at 1300 K.

>> s10p8
Partial pressure in atm, diffusion in argon
T(K) = 1300
PAlF3 PAlF PAlF2 PAl2F6 PAr
1.680e-002 7.938e-002 4.959e-003 3.176e-004 8.985e-001

(T is in K and log is natural log [ln])

Species g o
rxn

AlF3(c)
AlF(g)
AlF2(g)
AlF3(g)
Al(c,l) 0
Al2F6(g)