B18PA1/B18AP1 Chemical Thermodynamics Lecture 15 & 16

Dr N Hendrik Nahler 3rd December 2012

Introduction
During this lecture the following examples will be discussed in reference to previous lectures. These are worked examples to support your understanding of Chemical Thermodynamics. This is not a revision class and the examples are not purposely linked to past or future exam questions. Please, as always take notes during this lecture. Problems for which you see the solution almost always appear logical and easy. You will only understand the subject properly by attempting additional problems yourself e.g. from Elements of Physical Chemistry, Atkins & de Paula, without the answer at hand.

Lecture 1 & 2
1. 1.95 mol of an ideal gas (CV,m = 3/2R) undergo the following changes starting from T = 290 K and p = 1.00 bar. Calculate q , w, U , H , and S . a) The gas is heated to T = 520 K at constant pressure. b) The gas is heated to T = 520 K at constant volume. c) The gas undergoes a reversible isothermal expansion at T = 290 K until the pressure is half of its initial value. 2. Calculate r H and r U at T = 298.15 K for the following reactions using the data provided below and assuming ideal gas behaviour. a) OH(g) b) H2 O(g) c) H2 O H(g) + O(g) 2 H(g) + O(g) H(g) + OH(g)

1 1 2 H2 (g) + 2 O2 (g) 1 H2 g + 2 O2 (g)

OH(g) H2 O(g)

H2 (g) O2 (g)

2 H(g) 2 O(g)

f H /kJmol1 38.95 241.814 435.994 498.34 C6 H12 O6 (s)+6 O2 (g)

3. Consider the photosynthetic process 6 CO2 (g)+6 H2 O(l) with the data given at T = 298 K. CO2 (g) H2 O(l) C6 H12 O6 (s) O2 (g) a) H b) Ssys c) Ssurr d) Stot f H /kJmol1 393.5 285.8 1273.1 0.0 S /JK1 mol1 213.8 70.0 209.2 205.2

/JK1 mol1 Cp,m 37.1 75.3 219.2 29.4

Calculate the following, both at T1 = 298 K and T2 = 330 K

Lecture 3 & 4
4. An ice cube with a mass of 17.5 g at a temperature of Tice = 273 K is added to 125 g of liquid water at Twater = 325 K at constant pressure. a) Is the nal state of the system ice or liquid water? b) Calculate S for the process. c) Is the process spontaneous? 5. Calculate G for the isothermal expansion in 1c.

Lecture 5 & 6
6. Carbon tetrachloride melts at Tfus = 250 K. Phase Solid Solid Liquid Liquid Temperature / K 232 250 290 340 Vapour pressure / Pascal 270 1092 10 539 74 518

a) Calculate vap Hm and sub Hm . b) Calculate fus Hm .

c) Calculate the normal boiling point and vap Sm at the boiling point. d) Calculate the triple point temperature and pressure. 7. Use the following vapour pressures of 1-butene to calculate the enthalpy of vaporisation using a graphical method of best t. Temperature / K 273.15 275.21 277.60 280.11 283.15 Pressure / bar 1.252 1.349 1.471 1.607 1.787

8. Consider the phase transition between two forms of solid tin, Sn(s, grey) Sn(s, white). The two phases are in equilibrium at 1 bar and 18 C. The densities for grey and white tin are 5750 kgm3 and 7280 kgm3 respectively. The molar entropies for grey and white tin are 44.14 JK1 mol1 and 51.18 JK1 mol1 , respectively. Calculate the temperature at which the two phases are in equilibrium at a pressure of 200 bar.

Lecture 7 & 8
9. Consider the equilibrium CO(g) + H2 O(g) f CO2 (g) H2 (g) CO(g) H2 O(g) H /kJmol1 393.5 110.5 241.8 Mole fraction 0.271 0.271 0.229 0.229 CO2 (g) + H2 (g) at T1 = 1000 K.

a) Calculate Kp and r G at 1000 K. b) Use your answer from part (a) to calculate r G at 298 K. 10. Ca(HCO3 )2 (s) decomposes when heated following this equation: Ca(HCO3 )2 (s) CaCO3 (s) + H2 O(g) + CO2 (g). a) Pure Ca(HCO3 )2 (s) is put into a reaction vessel, the vessel is then evacuated and its contents heated, the total pressure is 0.235 bar. Calculate the equilibrium constant Kp . b) Pure Ca(HCO3 )2 (s) is put into a reaction vessel, the vessel is then evacuated. 0.105 bar of water vapour is added before the vessel is heated to the same temperature as in (a). What is the partial pressure of CO2 (g) at equilibrium?

Lecture 9 & 10
11. At high altitudes the absorption of oxygen into the bloodstream is reduced making exercising a lot harder and may lead to altitude sickness. At a pressure of 1.00 bar at sea level, blood is typically 95% saturated with O2 while at 0.50 bar at 5400 m, blood is typically 71% saturated with O2 . Assuming that the Henrys law constant O for blood is the same as for water (kH2 = 4.95 104 bar) calculate the amount of O2 dissolved in 1.0 l of blood at 1.00 bar and 0.50 bar. Air contains 20.99% O2 by volume and the density of blood is 998 kgm3 . 12. At 10 C the vapour pressure of ethyl bromide is 90.0 torr and that of ethyl chloride is 302.5 torr. A solution of the two solvents is prepared which is considered ideal and only a trace of liquid is present. The mole fraction of ethyl chloride in the vapour is 0.82. a) What is the total pressure and the mole fraction of ethyl chloride in the liquid? b) If there are 6.50 mol of liquid and 3.80 mol of vapour present at the same pressure as in part (a), what is the overall composition of the system? 13. At 39.9 C a solution of ethanol (xe = 0.9006, p e = 130.4 torr) and iso-octane (p = 43 . 9 torr) forms a vapour phase with y = 06667 at a total pressure of e i 185.9 torr. a) Calculate the activity and activity coecient of each component. b) Calculate the total pressure that the solution would have if it were ideal.

Lecture 11 & 12 and Lecture 13 & 14

Examples have been given for lectures 11 & 12 and 13 & 14 at the time it was given. The worked examples for lecture 13 & 14 are available on VISION due to the interruption we had caused by the re alarm.