Notice that the stoichiometry is not correct in option b. In option c, everything works! (x = 6)

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1 1. Rearrange the Gibbs free energy equation ( G = H - T S) to solve for the temperature at a phase transition. a. T = ( H - G)/ S b. T = H/ S c. T = - G d. T = - G/ S At a phase transition delta G = 0. The temperature dependence at a phase transition can be determined from thermodynamics. 2. What will happen to vapor pressure when non-volatile solute A is added to a pure solution B? a. Vapor pressure of A increases b. Vapor pressure of B decreases c. Vapor pressure doesn't change d. Boiling point decreases of A inrcreases. e. Boiling point of B decreases Adding a non-volatile solute (its vapor pressure is essentially zero) to any solvent, will decrease the measured vapor pressure of the solvent, by a factor equal to the solvents new mole fraction. 3. Rank the following salts from least to most soluble based on their H hydration : Al 3+, 4800 kj; I -, 244 kj; K +, 350 kj; Br -, 284 kj. a. K + < I - < Br- < Al3+ b. Al 3+ < K+ < Br- < I- c. I - < Br - <K + <Al 3+ d. All ions are equally soluble. A higher charge density corresponds to a higher heat of hydration. The stronger the charge density of an ion the stronger the IMF, so it is going to be harder to pull it away from an ion of opposite charge. Hence, ions with large charge densities are harder to dissolve. 4. Which of the following is always true for phase diagrams? a. The slope of the melting curve is always positive b. The critical point will have a lower pressure than the triple point c. Only one phase exists on a phase boundary d. When going from left to right on the graph, pressure and temperature both increase along the condensation curve e. The critical point can be reached at 0K Melting curves can have a negative slope (ie water). The supercritical region is defined by an increase and pressure and temperature beyond the limits of the normal 3 phases. Phase boundaries represent equilibriums between two phases. 5. At what temperature will water boil on top of a mountain when normal boiling point is 100C at 1 atm. (You should not need to look at this graph to answer the question)

2 a. Below 100C b. 100C c. Above 100C d. Water will not boil Pressure is lower at higher altitudes. Following the evaporation curve on the phase diagram from 1 atm to a lower pressure you see that temperature decreases. 6. Consider a 27 g sample of ice at 1 atm. Initially, the sample is frozen at -20 C. How much heat must be added to the sample for it to become a liquid at 78 C. Heat capacity of ice: 2 J/gK. Heat capacity of water: 4 J/gK. H of melting: 330 J/g a. 9.5 kj b kj c. 5.3 kj d kj q = mc T (for the ice) + m H (for melting) + mc T (for the water) q = 27 g * 2 J/gK * 20 K + 27 g * 330 J/g + 27 g * 4 J/gK * 78 K q = 18.4 kj 7. As the temperature of a solvent (increases/decreases), the solubility of (some/all) gases increases. a. decreases, all b. increases, some c. decreases, some d. increases, all Dissolution of all gases is exothermic. 8. Rank the following liquids from least to most miscible in H 2 O 2 : H 2 O, C 2 H 6, CH 2 Cl 2. a. H 2 O, CH 2 Cl 2, C 2 H 6 b. CH 2 Cl 2, C 2 H 6, H 2 O c. C 2 H 6, H 2 O, CH 2 Cl 2 d. C 2 H 6, CH 2 Cl 2, H 2 O Like dissolves like. Water is most similar to hydrogen peroxide. Both are polar and can form hydrogen bonds. CH2Cl2 is polar but can't form hydrogen bonds. It is small and has a small dispersion part. C2H6 is nonpolar and can only participate in dispersion forces when

3 dissolving in water. 9. If a liquid has a vapor pressure of 13.5 atm at 10C what will the temperature be when it has a vapor pressure of 5 atm? a. Below 10C b. Above 283K c. 283K d. Cannot determine without heat of vaporization ln(p2/p1) =(Hvap / R)(1/T1-1/T2) Higher temperatures have higher vapor pressures. 10. Which solution will have a higher boiling point elevation: 2 moles glycerine in 500g water, 16.4g Ca(NO 3 ) 2 in 0.1 kg water,.0746 kg KCl in 1L water. a. KCl b. Ca(NO3)2 c. Glycerine d. All raise BP equally e. KCl and Ca(NO 3 ) 2 equally raise BP Delta T = ik b m Glycerine solution: i=1, m= 2moles/0.5 kg = 4; Delta T = 4K b Ca(NO3)2 solution: i=3, m= (16.4g/164gmol - )/0.1kg = 1; Delta T =3K b KCl solution: i=2, m= (74.6g/74.6gmol - )/1kg = 1; Delta T = 2K b Water is the solvent in each mixture, so the K b will be the same for each solution. 11. If.5 moles of compound A are added to a liter of gas with 2 moles of compound B how will the total vapor pressure change? The pure vapor pressures for A and B are 100 torr and 50 torr respectively. a. Increase by 100 torr b. Decrease by 20 torr c. Will remain the same d. Increase by 70 torr e. Decrease by 100 torr f. Increase by 20 torr Solution of A only: P tot = 50 torr P tot = P a + P b P tot = [.5/(.5 + 2)]*100 torr + [2/(.5+2)]*50 torr =0.2(100) + 0.8(50) = 20 torr + 50 torr = 70 torr 70 torr - 50 torr = 20 torr increase 12. Calculate the molar mass of a mysterious substance if a sample of 10g has an osmotic pressure of 2 atm in 2L of water at room temperature. (RT = 25) a. 0.1 g/mol b. 1 g/mol c. 10 g/mol d. 100 g/mol pi = MRT 2 atm = [(10g/(x g/mol))/2l][25] 100 = 10g/(x g/mol) x =0.1 g/mol 13. Which of the following concerning the boiling point elevation of water mixtures is correct? (K b = 0.5 K/molal) a. 1 mole of CaCl 2 in 1 kg of water boils at 98.5 C b. 2 moles of urea in 400 g of water boils at 101 C

4 c. 0.5 moles of sucrose in 2.5 kg of water boils at 99.9 C d. 116 g NaCl in 200 ml water boils at 110 C 116 g NaCl = 2 moles of NaCl m eff = 2(2/0.2) = 20 molal T b = m eff (K b ) = 20(0.512) = Determine the correct equilibrium expression for the reaction of hydrogen gas with nitrogen gas to produce ammonia. a. K p = {P (N2) P 2 (H2)} / P 3 (NH3) b. K p = P 3 (NH3) / {P (N2) P 2 (H2)} c. K c = [NH 3 ] 2 / {[N 2 ][H 2 ] 3 } d. K c = {[N 2 ][H 2 ] 2 } / [NH 3 ] 3 3H 2 (g) + N 2 (g) 2NH 3 (g) Products over reactants. Coefficients are exponents. 15. Consider the following reaction: C 2 H 4 (g) + 3 O 2 (g) --> 2 CO 2 (g) + 2 H 2 O(l) Initial concentrations of C 2 H 4, O 2, and CO 2 are 7, 20 and 188 M, respectively. If K = 5 x 10 3, calculate the equilibrium concentrations for the compounds C 2 H 4, O 2 and CO 2, respectively. a. 1, 12, and 192 M b. 2, 4, and 800 M c. 1, 2, and 200 M d. 2, 5, and 198 M First, establish an equation for K. Remember that pure liquids are ignored. K = [CO 2 ] 2 / [C 2 H 4 ][O 2 ] 3 Next, realize that the concentrations given in A and D will not give you a K equal to Then, set up a RICE diagram to see which option makes the most sense. R C 2 H 4 (g) + 3 O 2 (g) --> 2 CO 2 (g) + 2 H 2 O(l) I C -x -3x +2x +2x E 7-x 20-3x 188+2x 2x Notice that the stoichiometry is not correct in option b. In option c, everything works! (x = 6) 15, Consider the following reaction: CH 3 OH(l) + O 2 (g) --> CO(g) + 2 H 2 O(g) There is excess methanol and the initial partial pressures of O 2, CO, and H 2 O are 11, 0, and 0 atm. If K = 4000, calculate the equilibrium pressures for the compounds O 2, CO, and H 2 O. a. 1, 10, and 20 atm b. 11, 0, 0 atm c. 5, 6, 12 atm d. 0, 11, 22 atm e. 6, 5, 10 atm First, establish an equation for K. Remember that pure liquids are ignored. K = [CO 2 ][H 2 O] 2 / [O 2 ] 2 Next, realize that the concentrations given in A and D will not give you a K equal to Then, set up a RICE diagram to see which option makes the most sense. R CH 3 OH(l) + 2 O 2 (g) --> CO(g) + 2 H 2 O(g) I ~ C ~ -x +x +2x E ~ 10-x x 2x

5 Notice that the stoichiometry is not correct in option b. In option c, everything works! (x = 6) 17. Consider the following reaction: A(aq) + 2 B(g) --> 3 C(aq) + 4 D(s) The equilibrium constant, K, is 50. If the initial concentrations of A, B, C, and D are 10, 10,.1, and 100, respectively, which of the following will occur? a. The reaction will proceed to the right. b. The reaction will proceed to the left. c. Nothing will happen because the reaction is already at equilibrium d. Not enough information has been give Q = [C]^3 = [.1]^3 = 10^-6 [A][B]^2 [10]^3 Q < K, so the reaction proceeds to the right 18. Let's reconsider the combustion of ethene from question 16. H for this reaction is -42 kj/mol. Which of the following statements is/are true? I. Increasing the concentration of water will shift the reaction to the left. II. Increasing the pressure will shift the reaction to the right. III. Increasing the temperature will shift the reaction to the left. IV. Increasing the concentration of O2 will shift the reaction to the right. a. I only b. II only c. III only d. II, III, and IV e. II and III f. I and IV The concentration of water is a constant and does not affect the direction of the reaction. 19. Consider the following endothermic reaction: O2 (aq) --> O2(g) Choose the best option. a. Changing the volume of the system will not affect equilibrium. b. Increasing the pressure will shift the reaction to the left. c. Increasing the temperature will shift the reaction to the right. d. a and c e. b and c Because the reactant is aqueous and the product is a gas, changing the volume of the system will affect the equilibrium. Equilibrium favors non-gaseous products under high pressure. Increasing the temperature of any endothermic reaction will shift equilibrium to the right 20. For any endothermic reaction, K (increases/decreases) as temperature increases. For any exothermic reaction, K (increases/decreases) as the temperature increases. a. increases, increases b. increases, decreases c. decreases, decreases d. increases, decreases For any endothermic reaction, H is positive, so K and T will have a direct relationship. For any exothermic reaction, H is negative, so K and T will have an inverse relationship. This is quantified by the Van't Hoff equation.

6 21. If G is negative, as the magnitude of G increases, K (increases/decreases) with a (linear/exponential) relationship to G. If G is positive, K will always be (greater/less) than 1. a. increases, linear, less b. increases, exponential, less c. decreases, exponential, greater d. decreases, linear, greater K = e^ (- G/RT) Because of this relationship, K will increase exponentially as the magnitude of a negative value for G increases. Also, K will always be less than 1 if G is positive. 22. Which of the following statements is false? a. Auto-protolysis of water results in the formation of a hydronium ion and a hydroxide ion. b. Auto-protolysis of water increases as temperature increases c. The ph of water is 7 only when the temperature is near 25 C. d. As the temperature of pure water is increased, the ph of the water increases. As temperature increases, more water molecules will dissociate, so the ph of the water will decrease. 23. At 25 C, the equilibrium constant, Kw, is about equal to x 10^-14. Which of the following values for Kw is plausible at 100 C? a x 10^-14 b..681 x 10^-14 c x 10^-14 d x10^-14 As the temperature of water increases, more water molecules will dissociate. In other words, Kw increases at temperature increases, so option d is the only plausible value. 24. Determine the molar solubility of calcium fluoride, CaF 2, if K sp = 4 x 10^-27. a. 10^-9 M b. 4 x 10^-27 M c. 10^-15 M d. 4 x 10^-15 M CaF2 is a salt of the form AB2. So we can simplify its Ksp in the following way: Ksp = [A++][B-]^2 = [x][2x]^2 = 4x^3 where x is the molar solubility. x = (Ksp/4)^1/3 = (4x10^-27/4)^1/3 = (10^-27)^1/3 = 10^-9 M 25. Consider the following table of salts and their Ksp values at 25 C. Salt K sp PbS CaCO MgF Fe(OH) Rank the salts by increasing solubility in water. a. MgF 2 < CaCO3 < PbS < Fe(OH)3 b. Fe(OH) 3 < PbS < CaCO3 < MgF2 c. Fe(OH) 3 < CaCO3 < MgF2 < PbS d. PbS < MgF 2 < CaCO3 < Fe(OH)3 Solubility increases as K sp increases. 26. Which set of ph and [OH-] values is possible?

7 a. ph = 6, [OH-] = 10^-6 b. ph = 5, [OH-] = 10^9 c. ph = 4, [OH-] = 10^-10 d. ph = 3, [OH-] = 10^3 14 = ph + poh [OH] = 10^-pOH 27. Consider the following table of bases and their K a values. Base Ka HCOO- 10^-3 C5H5N 10^-5 NH3 10^-9 CH3COO- 10^-4 Rank the compounds by increasing basicity. a. CH3COO- < HCOO- < C5H5N < NH3 b. NH3 < C5H5N < CH3COO- < HCOOc. NH3 < C5H5N < HCOO- < CH3COOd. HCOO- < CH3COO- < C5H5N < NH3 The weakest acid is going to make the strongest conjugate base. The lower the Ka, the weaker the acid, so the lower the Ka, the stronger the base. 28. You have g of HCl. How much water would you dissolve the hydrochloric acid in to make a solution with a ph of 2? a. 150 L b. 1.5 L c. 300 L d. 100 L g (1 mol/36.5g) = 3 mol [H+] = 10^(-pH) = 10^-2 3 mol of HCl/x L of water =.01 M 3 mol/.01 M = 300 L of water 29. At 30 C, what is the ph of a.5 M solution of ammonia? The Kb of ammonia at 30 C is 2 x 10^-8. a. 4 b. 10 c. 5 d. 9 [OH-] = (Kb * Cb)^1/2 = (2 x 10^-10 *.5)^1/2 = 10^-4 poh = -log[oh-] = -log(10^-4) = 4 ph = pkw - poh = 14-4 = At 30 C, you dissolve 1 mole of acetic acid in 10 L of water. What is the ph of the solution? The pka of acetic acid at 30 C is 3. a. 2 b. 12 c. 1.5 d Ca = 1 mole / 10 L =.1 M Ka = 10^-pKa = 10^-3 [H+] = (Ka*Ca)^1/2 = ( 10^-3 *.1)^1/5 = 10^-2 ph = -log[h+] = -log(10^-2) = 2

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