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CM1502 Tutorial 2

1)

For the process going from A to B to C, what is S° at point A, B and C? [C p,m : H 2 O (s) = 37.7 JK -1 mol -1 (273K); H 2 O (l) = 75.3 JK -1 mol -1 (298 K); H 2 O (g) = 37.5 JK -1 mol -1 (373 K) and ∆H° fus at 273 K is 6.0 kJmol -1 and H° vap at 373 K is 40.8 kJmol -1 .] For calculations, assume that point A is 0.1 K.

Point C S° 393 K = S° 298 K + C p,l ln(T 4 /T 3 ) + H/T + C p,g ln(T 5 /T 4 ) = 326.9 + 75.3 x ln (373/298) + 40800/373 K

+ 37.5 x ln (393/373) = 326.9 + 16.9 + 109.4 + 2.0 = 455.2 JK -1

Point B

S° 298 K = C p,s ln(T 2 /T 1 ) + H/T + C p,l ln(T 3 /T 2 )

= 37.7 ln(273/0.1) + 6000/273 + 75.3 x ln(298/273)

= 298.3 + 22.0 + 6.6

= 326.9 JK -1

Point A S° = 0 JK -1

Assume C p constant over the T range

2) A Carnot cycle uses 1.00 mol of a monatomic perfect gas as the working

substance from an initial state of 10.0 atm and 327°C. It expands isothermally to

a pressure of 1.00 atm using 11.49 kJ of heat (step 1), and then adiabatically to a temperature of 27°C (step 2). This expansion is followed by an isothermal compression (step 3) releasing 5.74 kJ of heat, and then an adiabatic compression (step 4) back to the initial state. Determine ΔS for

each stage of the cycle and for the cycle as a whole. Calculate the efficiency of

this cycle. S = q H / T H = 11.49 kJ / (327 + 273) K = 11490 J / 600 K = 19.15 JK -1

11.49 kJ 5.74 kJ
11.49 kJ
5.74 kJ

10.0 atm, 600 K = T H

S = 0 as q = 0

1.0 atm, 600 K

S = 0 as q = 0

300 K = T C

S = q C / T C = -5.74 kJ / (27 + 273) K = -5740 J / 300 K = -19.13 JK -1

3

For whole cycle, ∆S = q H / T H + q C / T C = 19.15 + -19.13 = 0.02 JK -1 ≈ 0 JK -1

Efficiency (ε) = 1 – T C / T H = 1 (27 + 273) / (327 + 273)

= 1 300 / 600 = 0.5

3)

Metallic aluminium is an effective reagent for the reduction of oxides of some other metals, as in the thermite reaction:

2Al (s) + Fe 2 O 3 (s) Al 2 O 3 (s) + 2Fe (s) (∆Gº f (Al 2 O 3 (s))= -1576.5 kJmol -1 )

For each of the following oxides, decide which cannot be reduced by aluminium:

(a)

(b)

(c)

(a)

CuO (∆f = -127.2 kJmol -1 ),

(b)

ZnO (∆f = -318.2 kJmol -1 ),

(c) CaO (∆f = -604.2 kJmol -1 ).

2Al (s) + 3CuO (s) Al 2 O 3 (s) + 3Cu (s)

0

ΔG (1 1576.5 3 0) (3 127.2 2 0)  1194.9 kJ

 

 

 

 

2Al (s) + 3ZnO (s) Al O

2

3 (s) + 3Zn (s)

0

ΔG (1 1576.5 3 0) (3 318.2 2 0)  621.9 kJ

 

 

 

 

2Al (s) + 3CaO (s) Al 2 O 3 (s) + 3Ca (s)

ΔG (1 1576.5 3 0) (3 604.2 2 0)  236.1kJ

 

 

 

 

0

CaO cannot be reduced by Al.

5

4)

Small amounts of hydrogen can safely be removed from gaseous mixtures by reaction with cupric oxide at 200 o C:

CuO (s) + H 2 (g) Cu (s) + H 2 O (g)

Find ΔG o , ΔH o , ΔS o and K for this reaction at 298K using the data in the table. Calculate the equilibrium constant at 200 o C, assuming that ΔH o is independent of temperature.

 

H° f / kJ mol -1

G° f / kJ mol -1

CuO(s)

-155.2

-127.2

H 2 (g)

0

0

Cu(s)

0

0

H 2 O (g)

-241.8

-228.6

0

ΔH (1 0 1 241.8) (1 155.2 1 0)  86.6 kJ

  

 



0

ΔG (1 0 1 228.6) (1 127.2 1 0)  101.4 kJ

  

 



ΔG ΔH TS

0

0

0

101.4   86.6 298S

S

0

49.7 JK

1

0

6

G298 K = RT lnK

-101400 = (8.314 x 298) lnK

K =

5.95 x 10 17

van’t Hoff’s Law is used when we want to calculate K at a different T.

ln (K 2 /K 1 ) = (-∆H°/R)(1/T 2 1/T 1 )

ln (K 2 /5.95 x 10 17 ) = (86600/8.314)(1/473 1/298)

K 2 = 1.44 x 10 12

5)

(a) Describe what is meant by microscopic states of a system.

Each possible arrangement of the positions of particles, in the whole system, is called a microstate ."

(b) Calculate the number of microscopic states present in 1 mole of KCl (s) given that S° m at 298 K is 82.59 JK -1 mol -1 . (Your answer can take the form W = e x )

Boltzmann equation: S = (R/N A ) ln W = k ln W

82.59 JK -1 mol -1 = (8.314 JK -1 mol -1 /6.022 x 10 23 mol -1 ) ln W

ln W = 5.98 x 10 24

W e

5.98x10

24

(c) What does the third law of thermodynamics state about microscopic states at 0 K and hence what is the entropy of a system at 0 K?

Third law: As a system approaches absolute zero temperature (0 K), all processes cease and the entropy (disorder) of the system approaches a minimum value (zero).

There is only one microstate at 0 K.