17 April 2011

20102 PHYSICAL CHEMISTRY CHEM 252 Second Midterm Examination Surname and Name : Section : Signature : 1A 1B 2 3 _____________________________ _____________________________ _____________________________ 4 5 6 7 8 Total

Some Possibly Useful Information and Related Equations:

dU = TdS PdV, dH = TdS + VdP, dA = SdT PdV, dG = SdT + VdP

(T/V)S = (P/S)v, (S/V)T = (P/T)v,

(T/P)S = (V/S)P (S/P)T = (V/T)p

For a monatomic gas, Cv = 3/2 R ; Cp = 5/2 R R = 8.314 J/K.mol = 0.08206 L.atm/mol.K = 0.08315 bar dm3/mol.K 1 atm = 101305 Pa; 1 bar = 105 Pa; 1 Pa = 1 kg /m.s2

1A. (6 pts) Fill in the BLANKS. a. For any isolated system equilibrium corresponds to the position of ___MAXIMUM____________ entropy of the system. b. Freezing of supercooled water at -10C and 1 atm is a(n) ____SPONTANEOUS______ process. c. The efficiency of any heat engine that operates on a reversible Carnot cycle is independent of the nature of the working substance but depends only on the ___TEMPERATURES_______ of the reservoirs. d. Efficiency of a reversible engine is ____GREATER______ than efficiency of any engine if both engines work between the same pair of temperatures of TC and TH. e. Second law of thermodynamics states that: ___Entropy of universe increases during a spontaneous process. f. The temperature of an expanding gas ____INCREASES_________ if its Joule-Thomson coefficient, JT , is negative over the range of T and P involved.

1B. (4 pts) State whether w,q, H, U and S for the following process involving an ideal gas are; + , 0 , or . w Reversible compression at constant pressure. Irreversible adiabatic expansion. Irreversible heating at constant V. Reversible expansion at constant T. q U S

+ 0

0 + +

+ 0

+ + +

For q and w any correct answer with respect to your w, and DS is accepted.

ID:______________________

2. (9 pts) A reversible heat engine having 45.0 % efficiency operates between two heat reservoirs. During the isothermal expansion the engine absorbs 1000 J of heat from the reservoir at 1000K. Calculate; a) Temperature of the second reservoir.

b) Heat given to the cold reservoir.

c) Work done in one cycle.

3. (16 pts) Calculate S for the following processes: a) Isothermal expansion of 5 moles of an ideal gas against zero opposing pressure from 20 to 40 L.

)(

b) 1 mole of ideal monoatomic gas initially at 2.5 atm and 20.0 L heated and expanded to 2.0 atm and 30.0 L. T1 = 2.5 (20) / (0,082) = 609.8 K and T2 = (2) (30) / (0.082) = 731.7 K ( ) ( ) ( )( ( ) ( )( ( )

c) Mixing of 1 mol of O2(g) with 1 mole of N2 (g) at 25C, assuming that they are ideal gases. XO2 = = 0.5 and XN2 = 0.5

)(

)(

d) Heating 1.0 mol chloroform, CHCl3(l) from 285 to 310 K, if its temperature dependent heat capacity is; Cp = 91.5 + 7.5 x10-2 T, where T is the temperature in Kelvin ( ) ( )

ID:______________________

4. (12 pts) One mole of H2O (l) is supercooled to -5 C at 1 bar pressure. The transformation; H2O (l) H2O (s) is suddenly observed to occur. (Cp,water= 75.3 J/K.mol, Cp,ice= 37.7 J/K.mol, and fusionH= 5020 J/mol) a) Calculate Ssystem , Ssurroundings and Stotal and show that the transformation is spontaneous at -3 C and 1 bar. {-3 oC, 1 bar, H2O (l) } { 0 oC, 1 bar, H2O (l)} I { 0 oC, 1 bar, H2O (s)} II { -3 oC, 1 bar, H2O (l)} III

b) Calculate G for the transformation and show that the transformation is spontaneous at -3 C and 1 bar.

)(

5. (12 pts) 1.00 mol of ideal gas molecules at 27C is expanded isothermally from an initial pressure of 3.00 atm to a final pressure of 1.00 atm against a constant external pressure of 1.00 atm. Determine the values of q, w, U, H, S, Ssur, Stotal, and G for the process. V2 = 1*0.082*300/3 = 8.2 L and V2 = 24.6 L

w = -Pext V = - (1 atm 101325 Pa/atm) (24.6 x10-3 8.2 x10-3 ) = -1661.7 J q = - w =1661.7 J ( ) ( ) ( )( )

ID:______________________

6. (12 pts) Using the Maxwell relations show that a) The equation (U/V)T= (U/S)v(S/V)T + (U/V)S can be expressed as (U/V)T= T(S/V)T - P From dU = TdS PdV ( ) ( ) ( ) and ( ) and ( ) ( ) ( b) (U/V)T= 0 for an ideal gas, ) ( )

c) (U/V)T= a(n2/V2) for a van der Walls gas (P + an2/V2)(V-nb)=nRT

) )

7. (9 pts ) The standard entropy of liquid methanol at 298.15 K is 126.8 J/K.mol and its heat capacity is 81.6 J/K.mol. Methanol boils at 337.22K with an enthalpy of vaporization at that temperature of 35.270 kJ/mol. The heat capacity of the vapor is 43.9 J/K.mol. Calculate the entropy of methanol vapor at 800 K. (So (H2O) = 126.8 J/mol.K)

ID:______________________

8. (20 pts) A Carnot cycle uses 1.00 mol of a monatomic ideal gas as the working substance and undergoes following reversible steps. STEP I: Isothermal expansion from an initial state of of 10.0 atm and 600 K to a pressure of 1.00 atm. STEP II: Adiabatic expansion to a temperature of 300 K. STEP III: Isothermal compression. STEP IV: Adiabatic compression to the initial state. Determine the values of q, w, U, H, S, G, and A for each stage of the cycle and for the cycle as a whole. Express your answer as a table of values with units. Initial state: (1 mol, 10 atm, 600K) q (J)
( )

STEP I 11486 -11486 0 0 19.14 -11486 -11482 w (J) U (J) H (J) S (J/K) G (J) A (J)

STEP II 0 -3741.3 -3741.3 -6235.5 0 -6235.5 -3741.3

STEP III -5744 5744 0 0 -19.14 5744 5744

STEP IV 0 3741.3 3741.3 6235.5 0 6235.5 3741.3

CYCLE 5742 -5742 0 0 0 0 0

From two adiabatic process and isothermal processes calculate the volumes of V3 and V4. then ( )

From the first adiabatic expansion process (starts from the end point of the STEP I isothermal expansion T2 = 600 K, V2 = 49.2 L) to a final T3 = 300K . ( ) ( )

The last step an adiabatic compression starts from the end of isothermal expansion (at 300 K) and ends at the initial state (T1 = 600 K and, V1=4.92 L) Then ( ) ( )

STEP I Isothermal expansion to a pressure of 1 atm ( )( )

STEP II Adiabatic expansion to a temp 300 K then ( )

( then

STEP III Isothermal compression ( )( )

STEP IV Adiabatic compression to initial state then ( )

( then