CHEM 131

FINAL EXAM F. Paesani Winter 2011

NAME

STUDENT ID

1. 2. 3. 4. TOTAL FINAL

/25 /10 /12 /8 /115

5. 6. 7. 8.

/20 /15 /13 /12

NOTE: Your REASONING and ANSWERS MUST be clear to me. Guesswork, or apparent guesswork, will not earn credit. TOTAL NUMBER OF PAGES INCLUDING THIS COVER PAGE: 21.

CHEM 131 1. 25 points This problem has ve parts, one part for each of Chapters 6-10. YOU NEED ONLY ANSWER T OR F. Correct choice = 1 points, no choice = 0 points, incorrect choice = -0.25 points. Be careful: pure guessing is a very bad idea because you lose points for incorrect choices. Chapter 6 - Reaction Equillbirum in Ideal Gas Mixtures. The chemical potential of ideal gas i in an ideal gas mixture at temperature T and partial pressure Pi equals the chemical potential of pure gas i at temperature T and pressure Pi . of a pure ideal gas goes to as P 0 and goes to + as P . The entropy of a mixture of N2 and O2 gases (assumed ideal) is equal to the sum of the entropies of the pure gases, each at the same temperature and volume as the mixture. When the ideal-gas reaction A + B C + D has reached equilibrium, it must hold that nC + nD = nA + nB .
For an ideal-gas reaction KP for the reverse reaction is the negative of KP for the forward reaction. KP for a particular ideal-gas reaction is a function of temperature but is independent of pressure and of the initial composition of the reaction mixture.

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Chapter 7 - One Component Phase Equilibrium. Since the three possible phases are solid, liquid, and gas, the maximum possible value of the number of phases p in the phase rule is 3. The number of degrees of freedom f is the number of variables needed to specify the thermodynamic state of a system. The normal boiling point is the temperature at which the vapor pressure of a liquid equals 1 atm. The enthalpy of vaporization of a liquid becomes zero at the critical point. When three phases coexist in equilibrium in a one-component system, one must be a gas, one must be a liquid, and one must be a solid. For a one-component system, the most stable phase at a given T and P is the phase with the lowest Gm .

Chapter 8 - Real Gases. The parameters a and b in the van der Waals equation for CO2 have the same values as in the Redlich-Kwong equation for CO2 .

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Chapter 9 - Solutions. The volume of a solution at T and P equals the sum of the volumes of its pure components at T and P . i is a partial molar quantity. Intermolecular interactions are negligible in an ideal solution. If B is a component of a solution, B cannot be greater than B. For equilibrium between an ideal solution and an ideal vapor, the mole fraction xB of component B in the solution must be equal to the mole fraction yB of B in the vapor. In an ideally dilute solution, i = i + RT ln xi for all components.

Chapter 10 - Nonideal Solutions. When a solution component is in its standard state, its activity is 1. ai and i are extensive properties. For a solute in a solution, II,B = I,B . The activity ai is never negative. Activity coecients may be positive or negative. The ionic charge z+ in an electrolyte solution does not aect the value of the mean ionic activity coecient .

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2. 10 points - Problems about ideal gas equilibria (a) 5 points For the gas-phase reaction 2SO2 + O2 2SO3 , observed mole fractions for a certain equilibrium mixture at 1000 K and 1767 torr are xSO2 = 0.310, xO2 = 0 0.250, and xSO3 = 0.440. Find Kp and G0 at 1000 K, assuming ideal gases. (R = 8.314 J/mol-K, 1 bar = 0.987 atm = 750 torr.)

CHEM 131 (b) 5 points For the ideal-gas reaction A + B 2C + 2D, it is given that G0 500 = 1250 cal/mol. If 1.000 mol of A and 1.000 mol of B are placed in a vessel at 500 K and P is held xed at 1200 torr, nd the equilibrium amounts ni of all the components. 0 R = 1.987 cal/mol-K. If H 0 = 2000 cal/mol, calculate Kp at 800 K when P is held xed at 1200 torr (H 0 can be assumed to be constant in this temperature range). Will the equilibrium amount of C be larger than at 500 K? (1 bar = 750 torr.)

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3. 12 points - Problems about one-component phase equilibria (a) 4 points At the normal melting point of Hg, -38.9 C, its enthalpy of fusion is 2.82 cal/mol, the density of the solid is 14.193 g/cm3 , and the density of the liquid is 13.690 g/cm3 . Find the melting point of Hg at 500 atm. (R = 1.987 cal mol1 K1 = 82.06 cm3 atm mol1 K1 ).

CHEM 131 (b) 4 points The normal boiling point of diethyl ether is 34.5C and its vap Hm at the normal boiling point is 6.38 kcal/mol. Find the vapor pressure of ether at 25.0 C using appropriate approximations. (R = 1.987 cal mol1 K1 , 1 atm = 760 torr.)

CHEM 131 (c) 4 points The vapor pressure of water at 25 C is 23.76 torr. Suppose that 0.360 g of H2 O is placed in an empty rigid container at 25 C. What phase(s) are present at equilibrium if the volume of the container is V = 10.0 L? What phase(s) are present at equilibrium if the volume of the container is V = 20.0 L? Assume the vapor to be an ideal gas. Make sure I understand how you get your answers. (R = 82.06 cm3 atm mol1 K1 , 1 atm = 760 torr.)

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4. 8 points - Problem about real gases For ethane, Pc = 48.2 atm and Tc = 305.4 K. Calculate the pressure exerted by 74.8 g of C2 H6 (molar mass = 30 g/mol) in a 200-cm3 vessel at 37.5 C using (a) 3 points the ideal-gas law

(b) 5 points the van der Waals equation P = a RT 2 Vm b Vm

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5. 20 points total Throughout this problem the temperature is kept at T = 308K. Also, I want numerical answers for all parts. A container is divided into two separate compartments. One contains liquid acetone (A) in equilibrium with its vapor. The vapor pressure is 347 torr. The other compartment contains liquid chloroform (C) in equilibrium with its vapor at 273 torr. (R = 8.314 J/mol-K.) (a) 3 points We now remove the partition so that the liquids mix. The composition of the resulting solution in mole fractions is 80% acetone and 20% chloroform, xA = 0.8 and xC = 0.2. If this were an ideal solution, what would be the partial vapor pressures of each component and the total vapor pressure in equilibrium with the liquid solution?

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CHEM 131 (b) 3 points Suppose that the vapor also behaves ideally. What are the mole fractions of acetone and chloroform in the vapor?

(c) 3 points Calculate the molar free energy of mixing of the ideal solution. R = 8.314 J/molK.

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CHEM 131 (d) 3 points The solution with 80% acetone and 20% chloroform is not really ideal. Instead, it is better described as ideally dilute. The Henrys Law constant for chloroform is K = 165 torr. Calculate the partial vapor pressures of each component and the total vapor pressure in equilibrium with the liquid solution.

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CHEM 131 (e) 4 points Calculate the molar free energy of mixing of this ideally dilute solution.

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CHEM 131 (f) 4 points Alas, the solution is neither ideal nor ideally dilute, since one observes nonnegligible deviations from both behaviors. The actual ratio of partial pressure to Henrys constant for the chloroform in this solution is pc /K = 0.21 and the ratio of the partial pressure to the vapor pressure of pure liquid acetone is pA /p A = 0.72. Calculate the activity coecients for acetone and for chloroform in this solution according to convention II (for the chloroform, use the mole fraction convention, i.e., dont change to molality units).

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6. 15 points - Problems about real solutions (nonelectrolytes) At 35 C the vapor pressure of chloroform is 295.1 torr and that of ethanol is 102.8 torr. A chloroform-ethanol solution at 35 C with xeth = 0.200 has a vapor pressure of 304.2 torr and a vapor composition of yeth = 0.138. R = 8.314 J/mol-K. (a) 5 points Calculate I and aI for chloroform and for ethanol in this solution.

(b) 5 points Calculate i i for each component in this solution in J/mol.

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CHEM 131 (c) 5 points Calculate G for the mixing of 0.200 mol of liquid ethanol and 0.800 mol of liquid chloroform at 35 C.

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CHEM 131

7. 13 points - Problems about real solutions (electrolytes) Consider the strong electrolyte MgCl2 . (a) 4 points Give the following numerical values (rather than a formula) for this electrolyte: + , , z+ , z , .

(b) 4 points Express in terms of + and , and ai in terms of and mi , exhibiting explicit exponents and coecients.

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CHEM 131 (c) 5 points Calculate the ionic strength of a 0.2-mol/kg aqueous solution of MgCl2 at 25 C knowing that the fraction of Mg2+ ions that associate with Cl ions to form ion pairs is 1 = 0.35. Note that the ion pair is charged. Useful equation for this problem: Im = 1 2
2 zj mj j

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8. 12 points total Short unrelated questions. (a) 4 points Suppose that the ideal-gas reaction A+B C+D has reached equilibrium. All quantities below are the values at equilibrium. Only two of the following relations are true. Tell me which ones. (1) nC + nD = nA + nB ; (2) PC + PD = PA + PB ; (3) nA = nB ; (4) nC = nA ; (5) nC = nD ; (6) if only A and B are present initially, then nC = nA ; (7) if only A and B are present initially, then nC = nD ; (8) if only A and B are present initially, then nC + nD = nA + nB ; (9) A + B = C + D .

(b) 4 points Which has the higher vapor pressure at -20C, ice or supercooled liquid water? Explain using quantitative arguments.

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CHEM 131 (c) 4 points Consider an aqueous solution of the weak acid HCN. The system has ve chemical species, H2 O, HCN, H+ , OH , and CN , and two independent reactions: H2 O H+ + OH HCN H+ + CN Find the number of degrees of freedom f for this system, and tell me which intensive variables you would use to specify the state of the system. I must understand your reasoning.

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