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Henry’s Law equilibrium vapor Henry’s Law continued of a gas in solution with its Pgas = kX dissolved _ gas K orange dot (g) ' orange dot (sol’n) k (atm × 10-3) 0 °C 25 °C 37 °C He 133 141 140 N2 51 85 99 O2 26 43 51 CH4 23 39 46 CO2 0.72 1.61 2.16 ... - ⌧ 2 Example: dissolved CO2 ... - ⌧ 3 Osmotic pressure What is the amount of CO2 dissolved in the oceans? Atmospheric PCO2 = 3.85 × 10-4 atm, Vocean = 1.37 × 1015 m3 and kCO2 = 2 × 103 atm. atm ... - ⌧ 4 ... - ⌧ 5 Example: osmotic pressure of a 100 mM solution What is the osmotic pressure of a 100 mM sucrose solution at T = 25 °C? ... - ⌧ 6 Example: osmotic pressure of a 100 mM solution ... - Molecular weight determination What is the osmotic pressure of a 100 mM NaCl solution at T = 25 °C? ... - ⌧ 7 ⌧ 8 Π = cRT ... - ⌧ 9 Example: using osmotic pressure Phase partitioning A 0.1 g/L solution of creatine is placed in an osmometer against pure water at 25 °C. The osmotic pressure is measured at 0.0187 0 0187 atm. atm What is the MW of creatine? ... - ⌧ 10 μ°(hepta ane) - μ°(aq) (kJ/m mol) -50 Standard Gibbs free energy of transfer from water to heptane O n O ... - ⌧ 11 Example: Gibbs free energy of transfer Aliphatic carboxylic acids -60 60 Two different solvents, each making a fully saturated solution with the same solid. The concentration of creatine in blood is 20 mg/mL and in urine is 750 mg/mL. What is the Gibbs free energy of transfer per mole from blood to urine at 37 °C? C? -40 -30 -20 -10 8 12 16 20 No. of carbon atoms ... - 24 ⌧ 12 ... - ⌧ 13 Example: amino acid solubility Example: amino acid solubility The solubilities of glycine and valine in water and ethanol at 25 °C are given below. What is the standard state Gibbs free energy of transfer per mole of glycine f from solid lid to t aqueous solution? l ti ? Gly: 3.09 M in water, 4.04 × 10-4 M in EtOH Val: 0.60 M in water, 1.32 × 10-4 M in EtOH ... - ⌧ 14 Example: amino acid solubility Gly: 3.09 M in water, 4.04 × 10-4 M in EtOH Val: 0.60 M in water, 1.32 × 10-4 M in EtOH ⌧ Gly: 3.09 M in water, 4.04 × 10-44 M in EtOH Val: 0.60 M in water, 1.32 × 10-4 M in EtOH ... - ⌧ 15 Example: protein stability upon G → V mutation What is the standard state Gibbs free energy of transfer per mole of the Val side chain from ethanol to aqueous solution at 25 °C? ... - What is the standard state Gibbs free energy of transfer per mole of glycine from ethanol to aqueous solution? Suppose a glycine residue in the hydrophobic interior of a protein is mutated to a valine. Will this mutation make the protein more stable at 25 °C? C? Gly: 3.09 M in water, 4.04 × 10-4 M in EtOH Val: 0.60 M in water, 1.32 × 10-4 M in EtOH 16 ... - ⌧ 17 Boiling point increase continued P ∗ Psolvent = solvent X solvent Boiling point increase Show that the BP of a solvent increases as solute l t concentration t ti increases. Let the pure solvent boiling T be called T0 and the solution boiling T be called Tboil Start from Raoult’s law: Apply the Clausius-Clapyron equation: ∗ Psolvent = X solvent Psolvent ln ... - ⌧ 18 P2,vap P1,vap ... - =− 0 ΔH vap ⎛1 1⎞ ⎜ − ⎟ R ⎜⎝ T2 T1 ⎟⎠ ⌧ 19