MSE 102A THERMODYNAMICS PROBLEM SHEET 1 1 The potential energy E (Joules) of a ball on a curved surface is given as a function of its

horizontal position coordinate x (metres) by E = 6 + 3( x 1)2 (a) (b) (c) Derive an expression for the horizontal component of force on the ball in the x direction. At what position is the horizontal force on the ball zero and is this a position of stable or unstable equilibrium? Calculate the potential energy of the ball at the point x = 3. If the ball is released at this point what will it do? Where will it eventually come to rest and, when it does, how much energy will it have lost? What has happened to the lost energy? Suppose that the surface is curved in 3 dimensions so that the potential energy is given by E = 6 + 3( x 1)2 + 2( y 2 )2 where x and y are two orthogonal horizontal coordinates. Derive an expression for the horizontal component of force on the ball in the y direction. What is the expression for the total horizontal force on the ball? At what coordinates of x and y will the horizontal force on the ball be zero? 2 (a) The force required to keep a spring of initial length lo at a length l is given by the expression, F = k (l lo), where k is the spring constant. Calculate the reversible work done on a spring with k = 10 MN m-1 when it has been stretched from its original length by 1 cm. Calculate the electrical work done by the charger on a capacitor of 1 mF when it has charged the capacitor reversibly to a voltage of 1 V. Calculate the work done on a vehicle starter motor when a fully charged 12 V lead-acid battery with a capacity of 55 A h is completely discharged into it (assume the voltage provided by the battery remains constant). Show that the work done on the gas when n moles of a perfect gas at temperature T are expanded isothermally and reversibly from a volume V1 to a total volume V2 is V2 won = nRT ln V 1 Hence calculate the work done in compressing one mol of an ideal gas at 27C isothermally and reversibly from 1 atm to 10 atm. What is the magnitude and direction of heat flow between the gas and its surroundings during the compression? A waterfall flows slowly over a cliff edge into a pool 30 m below. What will be the average difference in temperature between the water in the pool and that at the top of the cliff if no heat is lost or gained by the water from its surroundings? (The heat capacity of water is 75.5 J mol-1.)

(d)

(b) (c)

(a)

(b) (c) 4

MSE 102A THERMODYNAMICS PROBLEM SHEET 2 1 (a) Calculate the work done on the steam when 1 mole of water is vaporised reversibly at 100C and 1 atm pressure (The steam can be assumed to behave as a perfect gas and the molar volume of water is negligible compared with that of steam). Calculate the change in internal energy of the system in this process (The latent heat of vaporisation of water at 100C is 41 kJ mol-1) Why does the heat entering the system not raise the temperature of the system during this process? Calculate the heat required to convert 1 mole of water at 25C to steam at 100C and a pressure of 1 atm (CP for H2O(l) = 75.5 J K-1 mol-1) Calculate the heat required to convert 1 mole of water at 25C to steam at 200C and a pressure of 1 atm (CP for H2O(g) = 35 J K-1 mol-1).

(b) (c) (d) (e)

The standard enthalpy change for the reaction Al4C3 + 6 O2 2 Al2O3 + 3CO2 is -4340 kJ per mol of aluminium carbide at 298 K. If the standard enthalpies of formation at 298 K are -1670 kJ mol-1 for Al2O3 and -393 kJ mol-1 for CO2 find the standard enthalpy of formation for aluminium carbide at 298 K.

Calculate the enthalpy change of 1 mol of Fe when it is heated from 500 K to 1200 K using the following information: The stable phase of Fe is alpha-Fe below 900 K and gamma-Fe above 900 K. The enthalpy change for the alpha to gamma phase change is 920 J mol-1. o CP (alpha-Fe) = 17.5 + 0.024 T J K-1 mol-1.
o CP (gamma-Fe) = 7.7 + 0.02 T J K-1 mol-1. (where T is absolute temperature)

Calculate the standard entropy of steam at 300C from the following: So298(H2O vapour) = 200 J K-1 mol-1.
o CP (H2O vapour) = 30 + 0.015 T J K-1 mol-1. (where T is absolute temperature)

MSE 102A THERMODYNAMICS PROBLEM SHEET 3 1 Calculate the entropy change of 1 mol of Fe when it is heated from 500 K to 1200 K using the following information: The stable phase of Fe is alpha-Fe below 900 K and gamma-Fe above 900 K. The enthalpy change for the alpha to gamma phase change is 920 J mol-1. o CP (alpha-Fe) = 17.5 + 0.024 T J K-1 mol-1.
o CP (gamma-Fe) = 7.7 + 0.02 T J K-1 mol-1. (where T is absolute temperature)

2 3

Calculate the entropy change when 0.4 mol of gas A is mixed with 0.6 mol of gas B, assuming ideal gases. Why does mixing increase entropy? A 2 kW electric heater, with a constant element temperature of 800C runs for an hour and a half in a room which it keeps at an approximately constant temperature of 20C. Calculate the change in entropy of the room (assume no heat is lost from the room), the change in entropy of the heating system and the change in total entropy. Why is the total entropy change positive? What would you expect the entropy changes of the following reactions to be? (positive, negative, or negligible) (a) Fe + 1/2 O2 FeO (b) Fe + CO2 FeO + CO (c) BaCO3 BaO + CO2 (d) Silica glass quartz 1 mol of liquid Au is supercooled (meaning it does not solidify) and maintained at a constant temperature 100C below its equilibrium melting temperature of 1063C. Some small seed crystals are then added to the melt so that nucleation of solid gold crystals can take place. How much heat is liberated when all the gold has become solid at 963C? What is the change in entropy of the gold when it has all solidified at 963C? What is the change in entropy of the surroundings? What is the total entropy change and why is it positive? Standard enthalpy of melting of Au is 12.7 kJ mol-1. o CP (liquid Au) = 29.3 J K-1 mol-1.
o CP (solid Au) = 30.3 J K-1 mol-1. (Hint: construct a reversible process between the same initial and final states as this irreversible process.)

(a) (b) (c) (d)

MSE 102A THERMODYNAMICS PROBLEM SHEET 4 1

o o o From thermodynamic data tables find values for H , S and G for the following reactions: (a) Cu (solid) + 1/2 O2 (gas) CuO (solid) at 25C (b) H2 (gas) + 1/2 O2 (gas) H2O (liquid) at 25C (c) H2 (gas) + 1/2 O2 (gas) H2O (gas) at 25C (d) H2O (liquid) H2O (vapour) at 25C

A gas mixture of molar composition 49% H2, 49% steam and 2% O2 is heated to 1000C at a total pressure of 1 atm. (a) What is the reaction quotient in this mixture for the reaction H2 + 1/2 O2 H2O (all gases)? What is the molar free energy change of the above reaction in this mixture if Go = -246,400 + 54.8T J mol-1 (H2O) for the above reaction? In which direction will the reaction proceed and what will be the partial pressure of oxygen when it reaches equilibrium? (Assume that the final oxygen pressure is much less than 1 atm.)

(b) (c)

Calculate the oxygen activity at equilibrium when carbon dioxide is heated to 1000C at a total pressure of 1 atm. (Assume that the partial pressures of O2 and CO at equilibrium are much less than 1 atm).

Go = 282,400 - 86.8T J mol-1 for the reaction CO2 1/2 O2 + CO (all gases).
4 a) b) What is the pressure of CO2 in equilibrium with a mixture of solid CaCO3 and CaO at 900C (both solids being pure)? Above what temperature will CaCO3 become unstable in air containing CO2 at a partial pressure of 10-2 atm?

Go = 168,000 - 144T J mol-1 for the reaction CaCO3(s) CaO(s) + CO2(g).

5 a) b) c) Use an Ellingham diagram to estimate the oxygen activity in equilibrium with a mixture of Cr and Cr2O3 at 1000C. From the diagram estimate the concentration of water vapour in hydrogen above which the gas mixture will be unable to reduce Cr2O3 to Cr at 1000C. Similarly find the concentration of CO2 in a mixture with CO above which the gas mixture will be unable to reduce Cr2O3 to Cr at 1000C.

MSE 102A THERMODYNAMICS PROBLEM SHEET 5 1 The vapour pressure of zinc (measured relative to that of pure solid Zn) over a dilute solid solution of Zn in Cu at 200C varies with mol fraction of Zn according to the equation (for XZn< 5 atom %) PZn = 0.85X Zn + 13 X 2 Zn PZn, pure (a) (b) (c) (d) (e) Does the solution obey Raoults law? Above what concentration of Zn does the vapour pressure deviate by more than 10% from Henrys law? What is the activity of Zn when its mole fraction is 3%? What is the activity coefficient for this concentration of Zn? What is the chemical potential of Zn at this concentration (relative to that of pure Zn)?

A PtNi alloy containing 65 atomic% Ni is to be used for the anode of a fuel cell running at 500C where it will be exposed to a mixture of steam and hydrogen at a total pressure of 1 atm. What is the minimum concentration of hydrogen necessary to prevent the formation on NiO on the anode? The activity coefficient of Ni in the alloy is 0.45. The standard free energy for the formation of steam at 500C is -204,935 J mol-1 The standard free energy for the formation of NiO(s) at 500C is -169,429 J mol-1

A gas mixture containing H2 and CH4 in the mole ratio 10:1 at 10 atm total pressure is passed over iron at 900C until the gas mixture and the iron both reach equilibrium. a) What is the equilibrium activity of solid carbon in the gas mixture and the iron? b) Will Fe3C be formed as a separate solid phase? c) What would happen if the pressure was reduced to 1 atm? Go(900C) = 40 kJ mol-1 for C(s) + 2 H2(g) CH4(g) Go(900C) = -2 kJ mol-1 for 3 Fe(s) + C(s) Fe3C(s)

An excess of an alloy of Fe containing 0.001 atom fraction of Mn is equilibrated with an oxygen-containing gas at 1000 K to form a solid solution of FeO and MnO existing in equilibrium with un-oxidised Fe-Mn alloy. Calculate the equilibrium oxygen pressure and the composition of the oxide solid solution assuming all solid solutions are ideal (Raoultian). Go(1000K) = - 197,050 J mol-1 for Fe(s) + 1/2 O2(g) FeO(s) Go(1000K) = - 311,900 J mol-1 for Mn(s) + 1/2 O2(g) MnO(s)