MSE 3001: Applied Thermodynamics Homework Set #8 Due November 16 (Tuesday), 2010

1) For the oxidation reaction of pure Ta, 2Ta + 2.5O2 = Ta2O5 determine the standard Gibbs free energy of the reaction at a temperature T according to the following steps: (i) Determine H0(T) and S0(T) according to the loop calculations (ii) From (i) determine G0(T) (iii) Use the result of (ii) to obtain G0(T) in the form G0(T) = A + BTlnT + CT (iv) Use the result of (iii) to obtain G0(T) in the form G0(T) = D + ET, where A,B,C,D,E are constants. (v) Plot the three G0(T) functions obtained from (ii)-(iv) as a function of temperature. Data: Heat of formation of Ta2O5: H0298K = 488.5 kcal/mol Entropy of formation of Ta2O5: S0298K = 34.2 cal/mol*K cp(T) Ta = 5.8 + 0.71*10-3 T + 0.05*10-6 T2 cal/mol*K cp(T) Ta2O5 = 29.2 + 10-2 T cal/mol*K cp(T) O2 (gas) = 7.16 + 10-3*T 0.4*T-2 cal/mol*K 2) Gaskell #12.3 (i) Define a solution When pure solid silver is heated in an atmosphere containing oxygen such as pure oxygen or air, silver will be stable below a critical temperature while silveroxide is stable above the critical temperature. The critical temperature depends on the partial pressure of oxygen in the atmosphere surrounding the silver. We calculate the critical temperature for the case of a pure oxygen atmosphere and air. (ii) Plan a solution The reaction is: 4Ag(s) + O 2 (g) = 2Ag 2 O(s) , G 0 (T ) = 61,080 + 132.22T . We furthermore know that G 0 (T ) = RT ln(1 / p equ ) = RT ln(p equ ) O2 O2 (iii) Execute the solution Pure oxygen atmosphere: pO2 = 1atm Air: pO2 = 0.22 atm (iv) Evaluate solution ln(pO2) = -1.51 ln(pO2)=0 T = 422 K -61,080+132.22T = 0 T = 462K.

The result shows that pure silver should not tarnish below 422 K in air. Experience shows, however, that it does. The tarnish on silver is a silver sulfide, Ag2S. At room temperature, following the same calculation as above for the sulfidation of silver, any partial vapor pressure of sulfur higher than 10-33 atm causes silver to form the sulfide. 3) Gaskell #12.4

4) Gaskell #12.11 (i) Define a solution: A mixture of water vapor and argon gas streams over CaF and reacts to form CaO and HF gas. Based on the gas flow rate at 298 K and the weight changes of the system at two

different temperatures we calculate the temperature dependence of the standard Gibbs free energy for the reaction between CaF, water vapor, CaO and Hf gas. (ii) Plan a solution: From the gas flow rate at 298 and the partial pressure of H2O we can determine the number of mol of H2O that participate in the reaction. From the weight loss at the two different temperatures we can determine the number of mol of HF gas formed and H2O gas consumed. From that information we can determine the partial pressures of HF and H2O at the two temperatures and thus determine the value of G0 at two temperatures. Assuming a linear temperature dependence for G0, i.e., G0 = H0 TS0 we can determine the standard enthalpy and entropy. (iii) Execute the solution: 60 l of gas in one minute at a pressure of 0.9 atm and 298K:
n H 2O = 0.9 atm 60 l mol = 2.2 mol 0.082 atm l 298

According to the reaction: CaF + H2O = CaO + 2HF and the molar weight of CaF and CaO the transformation of one mol of CaF to one mol of CaO reduces the weight by 22 g. Per one mol of CaF transforming, or a weight loss of 22 g, two mol of HF form. For 1 g of CaF transforming, then, 2/22 or 1/11 mol of HF forms and 1/22 mol of H2O is consumed. Therefore, for a weight loss of 2.69*10-4 g, 1/11*2.69*10-4 mol of HF form and 2/22*2.69*10-4 mol of H2O are consumed. 1/11*2.69*10-4 mol of HF in a volume of 60 l and a temperature of 900 K relate to a partial pressure of HF of
p HF = 1/11 * 2.69 * 10 - 4 0.082 900 atm = 9.94 * 10 6 atm 60

The consumption of H2O of the order of 10-5 mol is negligible compared to the 2.2 mol, therefore K(900K) = p2HF/pH2O = 1.1*10-10. Thus G0 (900K) = -R*900K*ln(1.1*10-10) = 171,596 J. The same approach at 1100 K leads to G0 (1100K) = -R*1100K*ln(1.0*10-7) = 146,926 J. From G0 = A + BT and the two data points we obtain: G0 = 282,000 123T J.
p H 2O = 0.9 atm

(iv) Evaluate the solution: The standard Gibbs free energy of the reaction CaF2 + H2O = CaO + HF can be obtained from four separate reactions:

1. 2. 3. 4.

CaF2(s) = Ca(s) = F2(g) Ca(s) + O2 = CaO(s) H2O(g) = H2(g) + O2(g) F2(g) + H2(g) = 2HF(g)

Using the data from Kubaschewskis book (Metallurgical Thermochemistry) a fair agreement is obtained. 5) Gaskell #7.3 (i) Define a solution: One mol SiCl4 vapor is contained in a closed container at 350 K and 1 atm pressure. The temperature is lowered until the vapor condenses. We determine the onset temperature for condensation and the fraction condensed at 280 K. (ii) Plan a solution: Since the container is closed, cooling of the vapor causes a decrease in the vapor pressure, which can be calculated with the ideal gas law. At the same time we know that liquid SiCl4 has a certain vapor pressure that is uniquely fixed with temperature. At condensation the vapor pressure of the liquid equals the actual vapor pressure in the container (above that temperature the vapor pressure of the liquid is less than that of the vapor). To find the condensation temperature, we need to know the temperature dependence of the vapor and that of the liquid vapor pressure. For the SiCl4 vapor we have: p = nRT/V, i.e., a linear temperature dependence for fixed n and V. The volume of the container can be found from this equation of state, since all other data is given. For the liquid vapor pressure of SiCl4 we find from the textbook (appendix):

ln p(atm ) =

3620 + 10.96 , for 273 < T < 333 (Tboil) T

For the second part of the problem we recognize that at any temperature the saturated vapor pressure (in this case of the liquid SiCl4) is uniquely fixed. If we know the pressure then at 280 K and the volume of the container we can determine the number of mol in the gas phase from the equation of state for an ideal gas. The main assumption in this problem is thus that the SiCl4 vapor behaves ideally. With the initial number of mol of SiCl4 being one mol and knowing the number of mol in the vapor phase at 280 K we can determine the fraction of the vapor that has condensed.

(iii) Execute the solution: Step 1: Determine the volume of the container V = nRT/p = (1mol * 0.082 atm*l/(mol*K) * 350 K) / 1 atm = 28.7 l. Step 2: Determine the temperature dependence of the vapor from the ideal gas equation of state p(T) = nRT/V = (1 mol * 0.082 atm*l/(mol*K) * T) / 28.7 l = c Step 3: Determine the onset of condensation 2.85*10-3*T (atm) = exp[-3620/T + 10.96] (atm) Step 4: Fraction condensed at 280 K p(280 K) = exp[-3620/280 + 10.96] (atm) = 0.14 atm n = p*V/R*T = 0.14 * 28.7 / (0.082*280) mol = 0.175 mol condensed. 82.5 % has condensed at 280 K. 1 0.175 = 0.825 T = 328 K

(iv) Evaluate the solution: The normal boiling point of SiCl4 liquid is 333 K, i.e, the vapor pressure is 1 atm at 333 K. The condensation temperature in our case should be slightly below that temperature, since we start at 1 atm pressure, but due to the cooling and the fixed volume the pressure slightly drops and hence the boiling or condensation temperature must decrease as well. We thus expect an onset of condensation just below 333 K.

Specific heat data input

cpTa T_ : 5.8 0.71 10
3

0.05

10

T2

cpO2 T_

: 7.16

10

0.4

105

cpTa2O5 T_

: 29.2

10

cp T_

: cpTa2O5 T

2.5

cpO2 T

cpTa T

H0

488 500

488 500

Calculation of standard enthalpy, entropy, Gibbs free energy

T

H T_

: H0
298

cp Temp

Temp

S0

34.2

2.5

49.1

9.9

108.35

S T_

: S0
298

cp Temp

Temp

Temp

G T_

: H T

S T

Problem1.nb

Plot G T , T, 298, 1000

390 000 400 000 410 000 420 000 430 000 440 000 400 500 600 700 800 900 1000

$OutputSizeLimit

1000

1000

Fit standard free energy with equation of the type a + bTlnT + cT

Temperature Table i, i, 298, 1000

A very large output was generated. Here is a sample of it:

298, 315, 331, 954, 970, 986, 299, 316, 332, 955, 971, 987, 300, 317, 333, 956, 972, 988, 301, 318, 334, 957, 973, 989, 302, 319, 335, 958, 974, 990, 303, 320, 336, 959, 975, 991, 304, 321, 337, 960, 976, 992, 305, 322, 338, 961, 977, 993, 306, 323, 339, 962, 978, 994, 307, 324, 340, 963, 979, 995, 308, 325, 341, 964, 980, 996, 309, 326, 342, 965, 981, 997, 310, 327, 343, 966, 982, 998, 311, 328, 344, 967, 983, 999, 312, 313, 314, 329, 330, 609 , 968, 969, 984, 985, 1000

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Set Size Limit...

Gibbs1

Function T, G T

Temperature

A very large output was generated. Here is a sample of it:

456 212., 455 562., 382 306., 456 103., 455 453., 382 202., 455 995., 455 345., 382 098., 455 887., 455 778., 455 670., 685 , 382 617., 382 513., 382 410., 381 994., 381 890., 381 786.

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Problem1.nb

Dimensions Temperature

703

Riffle Temperature, Gibbs1

A very large output was generated. Here is a sample of it:

298, 456 212., 302, 455 778., 1374 , 993, 997, 382 098., 299, 456 103., 303, 455 670., 382 513., 994, 998, 381 994., 300, 455 995., 304, 455 562., 382 410., 995, 999, 381 890., 301, 455 887., 305, 455 453., 382 306., 996, 382 202., 1000, 381 786.

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Data

Partition Riffle Temperature, Gibbs1 , 2

A very large output was generated. Here is a sample of it:

298, 301, 689 997, 456 212. 455 887. , 994, 382 098. , 299, , 302, 382 410. , 998, 456 103. 455 778. , 995, 381 994. , 300, , 303, 382 306. , 999, 455 995. 455 670. , 996, 381 890. , , 304, 455 562. , 382 202. , , 1000, 381 786.

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FindFit Data, a

Log T

T, a, b, c , T

A very large output was generated. Here is a sample of it:

a 489 795., b 3.78203, c 134.158

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Fit a+bTlnT+c with an equation of the type A + BT

G2 T_ : 489 795 3.78 T Log T 134.158 T

Problem1.nb

Gibbs2

Function T, G2 T

Temperature

A very large output was generated. Here is a sample of it:

456 233., 455 581., 382 270., 456 125., 455 472., 382 165., 456 016., 455 363., 382 061., 455 907., 455 798., 455 689., 685 , 382 583., 382 478., 382 374., 381 957., 381 853., 381 748.

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Data3

Partition Riffle Temperature, Gibbs2 , 2

A very large output was generated. Here is a sample of it:

298, 301, 689 997, 456 233. 455 907. , 994, 382 061. , 299, , 302, 382 374. , 998, 456 125. 455 798. , 995, 381 957. , 300, , 303, 382 270. , 999, 456 016. 455 689. , 996, 381 853. , , 304, 455 581. , 382 165. , , 1000, 381 748.

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FindFit Data3, d

T, d, e , T

487 543., e

106.02

Graphical representation of the results

G3 T_ : 487 543 106 T

Plot

G T , G3 T , G2 T

, T, 298, 1000 , AxesLabel

"Temperature K", " G0

cal"

G0 380 000 390 000 400 000 410 000 420 000 430 000 440 000 Temperature K 400 500 600 700 800 900 1000

The graph shows a perfect overlap between the three graphs. This means that the linear dependence of the standard Gibbs free energy of reaction is a very good approximation of the actual temperature dependence.

Problem1.nb

The graph shows a perfect overlap between the three graphs. This means that the linear dependence of the standard Gibbs free energy of reaction is a very good approximation of the actual temperature dependence.