Problem Set #10

Assigned November 8, 2013 – Due Friday, November 15, 2013
Please show all work for credit

To Hand in

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↓determine size per molecule 4 3 r  V2  M 2  N A  0.02  10 23 ) 3 r  2.02  10 23 / mol  ( 4 )  ( 2. and that the surface area of the protein is reduced by 25% due to the hydrophobic interaction: G       0. 3.52  10 9 m G       0. A least squares fit of ln P versus 1/T gives the result H vaporization = 25. Assuming constant pressure and temperature. but the value seems high 2 .73mL / g  60000 g / mol  (6. 2.25  N A  4   r 2  Convert to per mole.0720 N / m  0.25  6.25  N A  4   r 2  0.28 kJ mol–1.52  10 9 m) 2  865kJ / mol We think this is a reasonable approach.

Calculate H fusion .43  103 J mol –1 R b. Therefore. and the vapor pressure of the liquid phase of the same substance is approximately given by ln(P/Torr) = 18.061  299 Ttp Ttp  73. Calculate the triple point temperature and pressure. a) Calculate H vaporization and H sublimation .22895 Torr 73. c.62 K Ptp 2035 ln  22. a.49  103 J mol –1 c. The vapor pressure of an unknown solid is approximately given by ln(P/Torr) = 22. Calculate the triple point temperature and pressure. K K 22.62 Ptp  5.16) d ln P H sublimation  dT RT 2 d ln P d ln P dT d ln P H sublimation   T 2    1 dT   1 dT R d  d  T  T  For this specific case H sublimation  2035 H sublimation  16. From Equation (8. At the triple point.413   5.36  103 Torr 3 .413  2035  18.352 – 1736(K/T). Calculate Hfusion. Calculate Hvaporization and Hsublimation. b. H fusion  H sublimation  H vaporization  16. the vapor pressures of the solid and liquid are equal. 4.352  1736 Ttp Ttp K 4.413 – 2035(K/T).92  103 J mol –1 R Following the same proedure as above.92  103 J mol –1  14. H vaporization  1736 H vaporization  14.43  103 J mol –1  2.

 K1  R  T2 T1  ??? ( −4 ??? ) ( ) ( ) −5 ??? ∗ ? (?ℎ??ℎ ????? ? ≪ ) And finally we can calculate the Gibbs energy at 335 K: ( ) ( ( ) 4 .5 1.4 Relative Absorbance 1.47 Plotting the relative absorbance versus temperature yields: 1. 5.f) 2 C 2 ??? 2 ∗ ? (?ℎ??ℎ ????? ? ) Then we can calculate the equilibrium constant at 335 K: K  H  1 1  .6 0. Calculate the equilibrium constant and Gibbs energy change for duplex formation at T = 335 K.30 0. where f = 0. Data appear in the following table.5  10000 2 1 .5: −4 ( ??? ) f K .0 0.2 0. and Tm = 311 K for strand concentrations of 1.00  10–4M. the melting ??? temperature.40 1.35 0.0.8 0.2 1. Assume the enthalpy change for duplex formation is constant between T = 311 K and T = 335 K. K311 K   0.75 1.9°C 0. The UV absorbance of a solution of a double-stranded DNA is monitored at 260 nm as a function of temperature. ln  2       .45 1.43 1. first calculate equilibrium constant at 311 K. From the data determine the melting temperature.4 Tm ≈ 355. Temperature (K) 343 348 353 355 357 359 361 365 370 Absorbance (260 nm) 0.0  10-4 M  −4 2(1 .2 kJ mol–1.22 1.50 0.6 1.9°C. For the formation of a self-complementary duplex DNA from single strands H° = –177. 6.0 340 350 360 370 T [degree Celsius] The plot indicates a melting temperature of approximately 355.

0 Torr.387 5 .0Torr and that of ethyl chloride is 40.50 and yEC = 0.80 and then answer these questions: a.00 mol of liquid and 3.80 5  0. If there are 5. tot nliq  Z B  xB   nvap tot  yB  Z B  Z B  xB  1  Z A   1  x A   x A  Z A yB  zB  1  y A   1  z A   Z A  y A Therefore. the vapor pressure of ethyl bromide is 10.50  3 Z EC  0.80  Z EC    Z EC  0. At –47°C. what is the overall composition of the system? (a) what is the overall composition of the system? ∗ ∗ ∗ ( ) 2 b) We use the lever rule. What is the total pressure and the mole fraction of ethyl chloride in the liquid? b. 7. yEC  Z EC 5 tot nliq   ntot vap Z EC  xEC 3 we know that xEC = 0.613 Z EB  1  Z EC   0. Assume that the solution is ideal. Assume there is only a trace of liquid present and the mole fraction of ethyl chloride in the vapor is 0.00 mol of vapor present at the same pressure as in part (a).

0053 g  / 10083 g mol  -1 msolute 100 g   9. ΔTf  K f msolute  K f m protein / M protein   1860 K g mol-1    0.053 g of beef heart myoglobin dissolved in 50. Calculate the change in the freezing point of water if 0.78 106 K 10.9 kg per mole.0 ml of water at T = 298 K generates sufficient osmotic pressure to support a column of solution of height d.81 m s-2  9. h:  msolutes  RT n solutes RT  M solutes  h  V g V g  1.053 g      -1   8. 6 . If the molar mass of myoglobin is 16.0053 g of a protein with molecular weight 10083 g mol–1 is dissolved in 100.8. calculate d. We set the osmotic pressure equal to the pressure of the column: n RT π  solutes  gh V We can now solve for the height. 1. mL of water.00005 m3   1000 kg m-3    9.314472 J K mol-1    298 K  16900 g mol     0.315 m  0.

11. 12. 7 .

( ) 2 (2 2 ) 2 ( 22 ) 8 . ( ) − (2 ) ( ∗ ) ∗ 2 Assume we have 5g cholesterol dissolved in 95g Dipalmitoyl phosphatidylcholine.13.

Liquid –33.9  103 J mol –1    Ttp  32.314 J mol K –1  221. take Tsolid .4 K  1 2  760 Torr  8. Ttp  240.ref  100 Torr Tliquid .7 40.00416 K –1 .0 400.314 J mol –1 K –1  ln   400 Torr  H vaporization   26.314 J mol –1 K –1  ln   400 Torr   1  0. Liquid –21. P  100 Torr  R ln 2 8. vaporization.9 kJ mol –1  5.4 K 240. and sublimation. Phase T (°C) P (Torr) Solid –62.ref  221.6 kJ mol –1 To calculate the triple point temperature.ref  240.6 kJ mol –1 1 1  1 1    T  T   210.6  26.Extra practice for exam.2 K  100 Torr   + 8.0 Solid –51.3 K Ttp  32.6  103 J mol –1  1 1  Ptp  100 Torr  exp     402 Torr –1  8.9  103 J mol-1  221. do not hand in Phase equilibrium 1.8 100.2 K  H fusion   32.6  103 J mol –1 26.6  26.5 K 221.ref  400 Torr 1 1  32.4 K 240.0 Torr  H sublimation    32.0 760.2 K Pliquid .9 kJ mol –1  1 1     240.3 K   9 .2 K 252.314 J mol –1 K –1  ln  P1  40. Use the vapor pressures for C2N2 given in the following table to estimate the temperature and pressure of the triple point and also the enthalpies of fusion.4 K Psolid .

Use the vapor pressures of Cl2 given in the following table to calculate the enthalpy of vaporization using a graphical method or a least-squares fitting routine. the density of ice is 920 kg m–3.105 272.566 305.982 294.934 238.32 kJ mol–1. and that the length of the contact area is 15 cm. T (K) P (atm) T (K) P (atm) 227.8 1. 2.7 0. 3.6 0.0°C? b.676 A least squares fit of ln P versus 1/T gives the result H vaporization = 20.6 15. what pressure is exerted at the interface of the skate and the ice? 10 .173 260. and the density of liquid water is 997 kg m–3.807 249. a.3 6. It has been suggested that the surface melting of ice plays a role in enabling speed skaters to achieve peak performance.483 327. Carry out the following calculation to test this Hfusion = 6010 J mol–1. Assume that the width of the skate in contact with the ice has been reduced by sharpening to 25  10–3 cm. What pressure is required to lower the melting temperature by 5. If a skater of mass 85 kg is balanced on one skate.5 12.388 316.9 2.585 283.0 3.4 9.15 4.

44 10 Pa K  144 bar K 7 –1 –1 The pressure must be increased by 720 bar to lower the melting point by 5.5ºC  dP  fusion 144 bar d) No. gray) Sn(s. and the unknown temperature T G gray  Vmgray P  S gray T G white  Vmwhite P  S white T At equilibrium G gray  G white  0  Vmgray  Vmwhite  P   S gray  S white  T  1 1  M Sn    P T  V m V gray m  white P     gray  white   S gray  S white  Stransition  1 1  118.02 10 –3 kg 18.5 C .20 102 bar  1. Calculate the temperature at which the two phases are in equilibrium at 200 bar. Consider the transition between two forms of solid tin. do you expect melting of the ice at the ice–skate interface to occur? a)  dP  Smfusion Smfusion 22. The two phases are in equilibrium at 1 bar and 18°C.l 2 997 kg m –3 920 kg m –3  1. white). Sn(s.81 ms –2 b) P   = 2.l 2  H O .8 J K–1 mol–1.8 J K –1mol –1 T f  8.2  102 bar A 15 10 m  25 10 m –2 –5  dT  1C c) T    P   2. In going from 1 atm. 18 C to 200 atm.0 J mol –1K –1       dT  fusion Vm fusion M  M 18. What is the melting point of ice under this pressure? d. If the temperature of the ice is –5.0ºC. c.71  10–3 kg mol –1   –3  –3   199 x105 Pa   5750 kg m 7280 kg m   9.2  107 Pa = 2. Tm = – 1. F 85 kg  9.0°C.02 10–3 kg   H O .8 C 8. because the lowering of the melting temperature is less than the temperature of the ice. The densities for gray and white tin are 5750 and 7280 kg m–3 Htransition = 8.2 C 11 . 4.

Obtain an expression for the equilibrium constant at a point where the fraction of the total strand concentration C that is duplex is defined as f.0 = CB.015  K  345 K     65. By DSC.67 fN fN 0. Suppose a DNA duplex is not self-complementary in the sense that the two polynucleotide strands composing the double helix are not identical. At T = 315 K. A and B have equal concentrations. At T = 345.5. indicating that the denaturation process is not accurately described by a two-state model.965 K315 K      0. Call these strands A and B.314472 J mol K  -1 -1 K  315 K    0.67   ln    R  ln    8. 12 .965 f D 1 . 6. initially. determine the enthalpy of denaturation. K.015 K345 K      65. UV absorbance determines that the fraction of native protein is fN = 0. Assuming a two-state model and assuming also that the enthalpy is constant between T = 315 and 345 K. Also. If the strand concentration is 1. calculate the equilibrium constant at the melting temperature.2 kJ mol-1  1 1  1 1         T2 T1    345 K   315 K   This result deviates from the DSC result.0.036   H      226.0 = C/2. the enthalpy of denaturation was determined to be 251 kJ mol–1. Call the duplex AB. determine the entropy of denaturation at T = 335 K.036 fN fN 0. CA. Consider the association equilibrium of A and B to form duplex AB Assume the total strand concentration is C and.0. Is this denaturation accurately described by the two-state model? We first calculate the equilibrium constants at 315 K and 345 K: f D 1 . fN = 0.f N  1 .965.00  10–4 M. A protein has a melting temperature of Tm = 335 K.015. that is.f N  1 .

We make the table of concentrations: Cinitial Cequilibrium AB 0 fC A=B C/2 C/2 – 2f C The equilibrium constant at the melting temperature with f = 0. 13 .2 kJ mol−1. Predict the ideal solubility of lead in bismuth at 280°C given that its melting point is 327°C and its enthalpy of fusion is 5.5 is given by: C AB fC 2 K  2  CACB  C  C   2 f C 2  And for C = 1.00  10–4 M: 2 2 K   20000  C 1  10 4 M  Ideal and Real Solutions 1.

Calculate the molar mass of the compound. 14 . The osmotic pressure of an aqueous solution at 288 K is 99. The addition of 5.8°C.00 g of a compound to 250 g of naphthalene lowered the freezing point of the solvent by 0. but it fell to 49. Calculate the molar mass of the compound.0 kPa. The vapour pressure of 2-propanol is 50.62 kPa when 8. 3. Calculate the freezing point of the solution.00 kPa at 338.780 K. 4.69 g of an involatile organic compound was dissolved in 250 g of 2-propanol.2.

6. and extrapolating the data to zero concentration.5.990 Calculate the molar mass of the enzyme.238 9.221 4.722 h/cm 5. measuring the osmotic pressure at 20°C.119 11.618 5. a 15 . The following data were obtained: c/(mg cm−3) 3. The molar mass of an enzyme was determined by dissolving it in water.746 8.112 6.

7. a 16 .

a 17 .8.

650.02  10–3 kg mol –1   273.27 PA* 0. Using this information.15 K. 8.008  103J mol –1 K f  1.650  PB*  1. At a total pressure of 0.314 J mol –1K –1  18.450    2.650  PA*  0. calculate the vapor pressure of pure A and of pure B. A and B form an ideal solution. Ptotal  x A Pa*  yB Ptotal Ptotal  yB Ptotal 0.650 y A PB* xA  Pa*   PB*  PA*  y A 0.450  1  0.900 bar. Calculate the freezing point depression constant Kf.414 bar 10. The heat of fusion of water is 6. yA = 0.008  103 J mol–1 at its normal melting point of 273.450  PB*  PA*  PB* 0.15 K 2 2 RM solventT fusion Kf   H fusion 6.9.550  Pa*    0.900 barx 1  0.86 K kg mol –1 11.650  1  0. 18 .450 and xA = 0.623 bar xA 0.450 PB* 0.

12. 19 .