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Solubility Product Constant. Ksp Chapter 17. I. BaSO 4(s) Ba 2+ (aq) + SO 4 2- (aq). Barium Sulfate has a certain solubility in water. At some point when enough is added the solution will become saturated, and some solid will remain. Ksp = [ Ba 2+ ] [SO 4 2- ] solubility product
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Solubility Product Constant Ksp Chapter 17
I. BaSO4(s) Ba2+(aq)+ SO42-(aq) • Barium Sulfate has a certain solubility in water. At some point when enough is added the solution will become saturated, and some solid will remain. • Ksp = [Ba2+] [SO42-] solubility product constant • Even though the concentration the solid is omitted for the equilibrium to exist some must exist.
II. Solubility and Ksp • The smaller the value of Ksp the lower the solubility • Solubility – the amount of a substance that dissolves when producing a saturated solution is often expressed in grams of solute /liter of solution at saturation point. • Solubility product constant (Ksp) – describes the concentrations) of dissolved ions, or substances at saturated equilibrium and is a unit less expression.
Solubility and Ksp • Solubility of a substance may change as the concentrations of various ions change ( including H+), however the value of Ksp is unique for a given solute at a specific temperature.
III. Calculating Ksp from the solubility • Ex. A liter of a solution saturated at 25OC with calcium oxalate, is evaporated to dryness, giving a 0.0061 g residue. Calculate the solubility product constant for this salt. • CaC2O4(s) Ca+2(aq) + C2O42-(aq) 0.0061g CaC2O4 (1 mole/128 g) = 4.8x10-5 mol 1mol CaC2O4 = 1 mol Ca+2 = 1 mol C2O42- Ksp = [Ca+2] [C2O42-] = [4.8x10-5]2 = 2.3x10-9
More complicated example • By experiment, it is found that 1.2 X10 -3 moles of lead II iodide dissolves in 1 liter of aqueous solution at 25oC. What is the Ksp of PbI2 at this temperature? • PbI2(s) Pb2+(aq) + 2I(Aq) • Ksp = [Pb2+] [ I ] 2 [1.2 X10 -3] [1.2 X10 -3]2
Calculate the solubility (in grams per liter) of calcium fluoride in water Ksp = 3.4 X 10-11 Calcium fluoride is commonly used as a window material for both infrared and ultraviolet wavelengths, since it is transparent in these regions (about 0.15 µm to 9 µm) and exhibits extremely weak birefringence. IV. Calculating Solubility from Ksp
Calculating Solubility from Ksp • CaF2(s) Ca+2(aq) + 2F- St 0 0 Ch +x +2X Eq +x +2X Ksp 3.9 X 10-11 = [Ca+2] [2F-]2 3.9 X 10-11 = [x] [2x]2 3.9 X 10-11 = 4x3 x = 2.1 x 10-4(78.1g/mol) = 1.6X10-2g/liter
V. Factors Effecting Solubility • There are five main factors that control solubility of a solute. (1) Temperature (2) Nature of solute or solvent (3) Pressure (4) common ion effect (5) pH
Temperature • Generally solubility increases with the rise in temperature and decreases with the fall of temperature but not in all cases. • In endothermic process solubility increases with the increase in temperature and vice versa. • In exothermic process solubility decrease with the increase in temperature. • Gases are more soluble in cold solvent than in hot solvent.
NATURE OF SOLUTE AND SOLVENT • A polar solute dissolved in polar solvent. • Solubility of a non-polar solute in a solvent is large. • A polar solute has low solubility or insoluble in a non-polar solvent. • In general like dissolves like
EFFECT OF PRESSURE • The effect of pressure is observed only in the case of gases. • An increase in pressure increases of solubility of a gas in a liquid. • For example carbon dioxide is filled in cold drink bottles (such as coca cola, Pepsi 7up etc.) under pressure.
Common Ion Effect • The presence of other solutes can also influence solubility – although they do not effect Ksp • CaF2(s) Ca+2(aq) + 2F- addition of calcium or fluoride ion will shift the equilibrium left favoring solid formation and decreasing solubility of the compound
Cal the sol of CaF2 at 25oc in a) 0.01 M Ca(NO3)2 b) 0.01M NaF • Ksp 3.4 X 10-11 = [Ca+2] [2F-]2 • CaF2(s) Ca+2(aq) + 2F- St 0 0 Ch +x +2X Eq 0.10+x +2X 3.9 X 10-11 = [0.010+x] [2X]2 assume that X is very small compared to 0.01 so
3.9 X 10-11 = (0.010) 4x2 3.9 X 10-11/ (0.010) 4 = x2 x = 3.1x10-5 mol/L In pure water the molar sol of CaF2 was 2.0 x 10-4 mol/L so we see the sol has decreased with the addition of a common ion. Learning check calc part b). Answer 3.9 x 10-7 mol/L
b) 0.01M NaF • CaF2(s) Ca+2(aq) + 2F- St 0 0 Ch +x +2X Eq +x 0.1+2X • Assume x is small ignore 2X • 3.9 X 10-11 = x(0.010) 2 • X = 3.9 X 10-11 / (0.010) 2 • X = 3.9 x 10-7 seems correct because Fion conc. is squared and has more of an effect