CHEM 131

MIDTERM EXAM F. Paesani Winter 2011

NAME

STUDENT ID

1. 2. 3. 4. 5. 6. TOTAL MIDTERM

/22.5 /20 /20 /25 /7.5 /5 /100

TOTAL NUMBER OF PAGES INCLUDING THIS COVER PAGE: 13. NOTE: Your answers must be clear. Make sure to oset your answer clearly if it is lost amidst a lot of other stu I may not nd it. If you have more than one answer I wont know which one you want me to use. NOTE: This exam is based entirely on the homework and Levines problems. ANOTHER NOTE: Unless told otherwise, you can assume, without further justication, that all gases are ideal.

CHEM 131 1. TRUE AND FALSE. 22.5 points max, -9 points min YOU NEED ONLY ANSWER T OR F. Correct choice = 0.5 points, no choice = 0 points, incorrect choice = -0.2 points.

(1) The P V work in a mechanically reversible process in a closed system always equals P V . (2) The innitesimal P V work in a mechanically reversible process in a closed system always equals P dV . (3) For every process, Esyst = Esurr . (4) For every cyclic process, the nal state of the surroundings is the same as the initial state of the surroundings. (5) H is dened only for a constant-pressure process. (6) For a constant-volume process in a closed system, H = U . (7) A thermodynamic process is dened by the nal state and the initial state. (8) T = 0 for every adiabatic process in a closed system. (9) If neither heat nor matter can enter or leave a system, that system must be isolated. (10) Since a Carnot cycle is a cyclic process, the work done in a Carnot cycle is zero. (11) A change of state from state 1 to state 2 produces a greater increase in entropy when carried out irreversibly than when done reversibly. (12) The heat q for an irreversible change of state from state 1 to state 2 might dier from the heat for the same change of state carried out reversibly. (13) The systems entropy change for an adiabatic process in a closed system must be zero.

(14) For a reversible process in a closed system, dq = T dS . (15) For a closed system, S can never be negative. (16) For an adiabatic process in a closed system, S cannot be negative. (17) For a process in an isolated system, S cannot be negative. (18) For an adiabatic process in a closed system, S must be zero. (19) For any closed system, equilibrium corresponds to the position of maximum entropy of the system. (20) The entropy of an isolated system can never decrease. (21) For every process in an isolated system, T = 0. (22) If a closed system undergoes a reversible process for which V = 0, then the P V work done on the system in this process must be zero. (23) S when 1 mol of N2 (g) goes irreversibly from 25 C and 10 L to 25 C and 20 L must be the same as S when 1 mol of N2 (g) goes reversibly from 25 C and 10 L to 25 C and 20 L. (24) For a closed system with P V work only, the cyclic integral is equal to zero. (25) For a closed system with P V work only, the cyclic integral is equal to zero. (26) For a closed system with P V work only, the cyclic integral is equal to zero. (27) The relation G = H T S is valid for all processes. (28) Always, G = A + P V . (29) The chemical potential i is a state function. (30) i is an intensive property. (31) i in a phase must remain constant if T , P , and xi remain constant in a phase. P dV

dqrev /T

dqrev

(32) The chemical potential of benzene in a solution of benzene and toluene must equal the chemical potential of toluene in that solution. (33) The chemical potential of sucrose in a saturated solution of sucrose in water at 300 K and 1 bar must be equal to the molar Gibbs energy of solid sucrose at 300 K and 1 bar. (34) G is always zero for a reversible process in a closed system capable of P V work only. (35) The work done by a closed system can exceed the decrease in the systems internal energy. (36) Gsyst + Gsurr is constant for any process. (37) Ssyst + Ssurr is positive for every irreversible process. (38) The term standard state implies that the temperature is 0 C. (39) The term standard state implies that the temperature is 25 C. (40) Doubling the coecients of a reaction doubles its H . (41) The reaction N2 + 3H2 2NH3 has
i

i = 2.

(42) The reaction N2 (g) + 3H2 (g) 2NH3 (g) has HT < UT .

(43) When an exothermic reaction in a closed system with P V work only is run under isobaric and adiabatic conditions, H = 0. (44) When a substance is in its thermodynamic standard state, the substance must be at 25 C. (45) G of an element in its stable form and in its standard state at 25 C is taken to be zero.

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2. 20 points total, 4 points each part Consider a perfect gas contained in a cylinder and separated by a frictionless adiabatic piston into two sections, A and B. Section B is in contact with a water bath that maintains it at constant temperature. Initially TA = TB = 320K, VA = VB = 1.50 L, and nA = nB = 1.75 mol. Heat is supplied to Section A and the piston moves to the right reversibly until the nal volume of Section B is 1.00 L. Calculate the following. Assume CV,m = 20.0 J K1 mol1 . Also, R = 8.314 J K1 mol1 . (a) The work done by the gas in Section A.

(b) U for the gas in Section B.

CHEM 131 (c) q for the gas in B.

(d) U for the gas in A.

(e) q for the gas in A.

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3. 20 points total, 10 points each part Data for this problem: Cp,m = 75.291 J/mol K for water. Hm for melting of ice is 6020 J/mol. The molecular weight of water is 18 g/mol. (a) Calculate the change in entropy when 95 g of water at 0 C is added to 195 g of water at 95 C in an insulated container.

CHEM 131 (b) Repeat the calculation when, instead, 95 g of ice at 0 C is added to 195 g of water at 95 C in an insulated container.

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4. 25 points total 5 point each part For each of the following processes, deduce whether each of the quantities q , w , U , H , A, and G is positive, zero, or negative. (a) Reversible melting of solid benzene at 1 atm and the normal melting point.

(b) Reversible melting of ice at 1 atm and 0 C.

CHEM 131 (c) Reversible isothermal expansion of a perfect gas.

(d) Adiabatic expansion of a perfect gas into a vacuum (Joule experiment).

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CHEM 131 (e) Joule-Thomson adiabatic throttling of a perfect gas.

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CHEM 131

5. 10 points total Given the following information at 298K: Heats of formation : CO2 (g) CH3 COOH(liq) H2 O(g) -393kJ/mol -487kJ/mol -242kJ/mol

Heat of combustion of CH4 (g) to give CO2 (g) and H2 O(g) -806kJ/mol Calculate the heat of reaction at 298K for the decomposition of liquid acetic acid, CH3 COOH(liq) CH4 (g) + CO2 (g)

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CHEM 131

6. 7.5 points The Gibbs free energy of a certain gas is given by 1 1 Gm = RT ln p + A + Bp + Cp2 + Dp3 2 3 where p is the pressure and A, B , C , and D are constants (independent of T and p). Obtain the equation of state of the gas.

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