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Exercises of thermodynamics

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1) Gaskell #12.6 (i) Define a solution: Solid iron and ironoxide, FeO, are in equilibrium with a mixture of CO and CO2 gases at 1273 K. Upon decreasing the temperature we have to find out which of the two solid phases disappears first. (ii) Plan a solution: Since we start at equilibrium and change one of the independent variables the equilibrium will shift. If we know the direction in which the equilibrium will shift we can predict, which phase will disappear first. Say, the reaction shifts toward the side of the reaction with pure iron then FeO will disappear first and vice versa if the composition of the gas is kept constant. We can determine the change in the reaction equilibrium with LeChateliers principle. If the reaction is endothermic then a decrease in temperature will shift the reaction in the direction that releases energy and vice versa. The statement that the composition of the gas mixture remains constant at the equilibrium pressures at 1273 K is important because if the composition is allowed to equilibrate at any temperature, specifically upon lowering the temperature then there will always be some Fe and FeO. Only if the composition remains fixed does one of the two solid phases disappear since the system then tried to reach the new equilibrium by either oxidizing or reducing the solids. We have to assume, though, that upon reducing the temperature the amount of Fe and FeO is finite and equilibrium can not be reached before one of the two solid phases has disappeared. (iii) Execute the solution: I. Fe(s) + O2(g) = FeO(s); G0I = -263,700 + 64.35T J II. CO2(g) = CO(g) + O2(g); G0II = 282,400 - 86.81T J I. + II.: Fe(s) + CO2(g) = FeO(s) + CO(g); G0 = 18,700 22.46T J The reaction is endothermic since H0 = 18,700 J > 0 J. Upon lowering the temperature at constant composition the reaction will shift from the FeO + CO side to the Fe + CO2 side to release heat that could counter the lowering of the temperature. Therefore FeO will disappear first. 2) 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. CaF2(s) = Ca(s) = F2(g) 2. Ca(s) + O2 = CaO(s) 3. H2O(g) = H2(g) + O2(g)

4. F2(g) + H2(g) = 2HF(g) Using the data from Kubaschewskis book (Metallurgical Thermochemistry) a fair agreement is obtained. 3) 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 Entropy of formation of Ta: S0298K = 9.9 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

In[5]:=

cpTa T_

: 5.8

0.71

10

0.05

10

T2

In[17]:=

cpO2 T_

: 7.16

10

0.4

105

In[4]:=

cpTa2O5 T_

: 29.2

10

In[18]:=

cp T_

: cpTa2O5 T

2.5

cpO2 T

cpTa T

In[20]:=

H0

488 500

Out[20]=

488 500

T

In[21]:=

H T_

: H0

298

cp Temp

Temp

In[22]:=

S0

34.2

2.5

49.1

9.9

Out[22]=

108.35

In[23]:=

S T_

: S0

298

cp Temp

Temp

Temp

In[24]:=

G T_

: H T

S T

Problem3.nb

In[25]:=

Out[25]=

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

In[27]:=

$OutputSizeLimit

1000

Out[27]=

1000

In[50]:=

Temperature

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

Out[50]=

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In[51]:=

Gibbs1

Function T, G T

Temperature

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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Problem3.nb

In[52]:=

Dimensions Temperature

Out[52]=

703

In[53]:=

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

Out[53]=

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In[54]:=

Data

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.

Out[54]=

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In[55]:=

FindFit Data, a

Log T

T, a, b, c , T

a

Out[55]=

489 795., b

3.78203, c

134.158

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In[56]:=

G2 T_

489 795

3.78

Log T

134.158

Problem3.nb

In[57]:=

Gibbs2

Function T, G2 T

Temperature

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.

Out[57]=

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In[58]:=

Data3

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.

Out[58]=

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In[59]:=

FindFit Data3, d

T, d, e , T

Out[59]=

487 543., e

106.02

In[60]:=

G3 T_

487 543

106

Plot

G T , G3 T , G2 T

cal"

Out[62]=

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.

Problem3.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.

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