Chapter 17 Properties of Solutions

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							                  Chapter 17
            Properties of Solutions
17.1: Define solutions and the different
 mathematical methods for describing solution
 composition.
17.2: Provide a qualitative and pictorial
 description of vapor pressure.
17.3: Discuss Raoult’s Law in a quantitative and
 qualitative method for describing vapor
 pressure.
17.4: Outline the role of colligative properties and
 provide mathematical and qualitative
 descriptions for colligative properties.

5/25/2012            Zumdahl Chapter 17           1
     Solution Composition                  The solute and solvent can be any
                                           combination of solid (s), liquid (l),
                                           and gaseous (g) phases.




Dissolution:   There is an equal distribution of two unlike molecules




Solution: A homogeneous mixture
              Solvent: The major component
5/25/2012
              Solute: The minor component
                        Zumdahl Chapter 17                                         2
       Mathematical Descriptions for Composition

Define: Mass Fraction, Mole Fraction, Molality
and Molarity
Mass percentage (weight percentage):
 mass percentage of the component =
 mass of solute/mass of solution *100



Mole fraction:




5/25/2012                      Zumdahl Chapter 17   3
Molality
     m = mol of solute/ Kg of solvent




 Molarity




Why do we use molality? Why is it important?
5/25/2012                         Zumdahl Chapter 17   4
What is Vapor Pressure?




5/25/2012
            Important to Understand!
                    Zumdahl Chapter 17   5
Water at 20oC
Water at 30oC
Water at 50oC
Water at 80oC
Water at 100oC
             Factors Affecting Solubility
 Factors Affecting Solubility
1. Structure Effects
     ◦ Review chapter 4 – “Like Dissolves Like” concept
     ◦ Polar molecules, water soluble, hydrophilic
       (water loving)
               E.g., Vitamins B and C; water-soluble
     ◦ Non-polar molecules, soluble in non-polar
       molecules, hydrophobic (water fearing)
               E.g., Vitamins A, D, K and E; fat-soluble




5/25/2012                            Zumdahl Chapter 17     11
                    Factors Affecting Solubility
1. Structure Effects
2. Pressure Effects                       P = kH X
     Henry’s Law (for dilute solutions)
            The vapor pressure of a volatile solute (gas) in a
            sufficiently dilute solution is proportional to the
            mole fraction of the solute in the solution.
kH is Henry’s Law
constant
f (Temp, and the solute-
solvent interactions)



5/25/2012                       Zumdahl Chapter 17                12
                    Factors Affecting Solubility
   1. Structure Effects
   2. Pressure Effects
   3. Temperature Effects for Aqueous Solutions
               The solubility of several
                solids as a function of
                          temperature.
The aqueous solubilities of a majority of
solids increase with increasing
temperature, some decrease with temp.
 Endothermic – heat is added to a system
 Exothermic – heat is removed from a
 system
   5/25/2012                  Zumdahl Chapter 17   13
                   Factors Affecting Solubility
  1. Structure Effects
  2. Pressure Effects
  3. Temperature Effects for Aqueous Solutions
       The solubility of several gases
             in water as a function of
           temperature at a constant
      pressure of 1 atm of gas above
                           the solution.


Endothermic – heat is added to a system
Exothermic – heat is removed from a
system
  5/25/2012                   Zumdahl Chapter 17   14
                                       Mixtures

  Raoult’s Law
     ◦ Ideal Solutions
             One volatile (the solvent)
             One non-volatile (the solute)


             P1 = X1 P°1




5/25/2012                              Zumdahl Chapter 17   15
              Ideal Solutions and Raoult’s Law
   Consider a non-volatile solute (component 2)
    in a solvent (component 1) which has a vapor
    pressure
   X1 = mole fraction of solvent           Ideal



                                             P1=X1 P°1
                                               Raoult’s Law


                                        Non-ideal solutions

Positive deviation is ____            Negative deviation is _


5/25/2012               Zumdahl Chapter 17                      16
                                       Mixtures

   Raoult’s Law                       P1 = X1 P°1
      ◦ Ideal Solutions
             One volatile (the solvent)
             One non-volatile (the solute)

       What happens if both are
        volatile?
              • One volatile (the solvent)
              • One volatile (the solute)



                P1 =X1 P°1
                P2 =X2 P°2

5/25/2012
                Ptot =P1 + P2         Zumdahl Chapter 17   17
Vapor pressure for a solution of two volatile liquids.




              Positive deviation
              = solute-solvent attractions < solvent-solvent attractions
                                                             For non-ideal Solutions




                Negative deviation
  5/25/2012                             Zumdahl Chapter 17                             18
                = solute-solvent attractions > solvent-solvent attractions
                   Colligative Properties of Solutions
   •        For some properties, the amount of
            difference between a pure solvent and dilute
            solution depend only on the number of
            solute particles present and not on their
            chemical identify.
   •        Called Colligative Properties
   •        Examples
            –   Vapor Pressure             One’s we will observe

            –   Boiling Point
            –   Melting Point
            –   Osmotic Pressure

5/25/2012                      Zumdahl Chapter 17                  19
Elevation of Boiling Point
         – The boiling point of a solution of a non-volatile
           solute in a volatile solvent always exceeds the
           boiling point of a pure solvent
Lowering of Vapor Pressure
         – Vapor Pressure of a solvent above a dilute
           solution is always less than the vapor pressure
           above the pure solvent.
Boiling
     •       liquid in equilibrium with                                GAS
             gas
Boiling Point
     •       Vapor press = external
             pressure                                          SOLID   Melting    LIQUID
Normal boiling point
                                                                       Freezing
     •       Vap press. = 1 atm
 5/25/2012                                Zumdahl Chapter 17                           20
Elevation of Boiling                ΔT  K m
                                          b solute
Point
and
                                    ΔT is the boiling point elevation
Lowering of Vapor
Pressure                            Kb is molal boiling - point elevation constant
                                    m              molality
                                            is the molarlity of the solute in solution
                                     solute




Phase diagrams for pure water (red
                lines)
    and for an aqueous solution
       containing a nonvolatile
5/25/2012solution (blue lines).   Zumdahl Chapter 17                           21
            ΔT  K m
                  b solute
                                    ΔT  K m
                                          f solute
                  Should be
                  negative
5/25/2012      Zumdahl Chapter 17                22
                        EXAMPLE
What is the minimum mass of ethylene glycol (C2H6O2) that
must be dissolved in 14.5 kg of water to prevent the solution
from freezing at -10oC?            Kf = 1.86 oC/m (water)




5/25/2012                 Zumdahl Chapter 17                    23
                                  EXAMPLE
The boiling point of ethanol (C2H5OH) is 78.5oC. What is the boiling
point of a solution of 3.4 g of vanillin (Molar Mass = 152 g/mol) in
50.0 g of ethanol (Kb ethanol = 1.22oC/m).


  Vanillin = solute                 moles of vanillin = 3.4g / 152(g/mol) = .022 mol
  Ethanol = solvent
                                 molality = .022mol / .050kg = .44m

            delta [T] = .44m * 1.22 = .5


  Tf = Ti + delta [T]

  =79oC



5/25/2012                            Zumdahl Chapter 17                          24
                  Osmotic Pressure
            Fourth Colligative Property
            • Important for transport of
              molecules across cell membranes,
              called semipermeable
              membranes
PV = nRT
               • Osmotic Pressure = Π = g d h
                           Π = c RT
                          ΠV = n RT
                         ΠV = i n RT

                                       c = Molarity or
                                       moles/L or n/V
5/25/2012         Zumdahl Chapter 17                 25
                          Osmotic Pressure

            The normal flow of solvent into the solution (osmosis) can be
             prevented by applying an external pressure to the solution.


                                           Osmotic Pressure useful for
                                            Determining the Molar Mass of
                                           protein and other macromolecules
                                                  small concentrations cause
                                                 large osmotic pressures
                                            Can prevent transfer of all solute
                                           particles
                                                  Dialysis at the wall of most
                                                 plant and animal cells

5/25/2012                         Zumdahl Chapter 17                              26
         Dialysis: Representation of the
        functioning of an artificial kidney
                                          A cellophane (polymeric)
                                          tube acts as the semi-
                                          permeable membrane
                                           Purifies blood by
                                          washing impurities
                                          (solutes) into the
                                          dialyzing solution.




5/25/2012            Zumdahl Chapter 17                         27
A dilute aqueous solution of a non-dissociating compound
contains 1.19 g of the compound per liter of solution and
has an osmotic pressure of 0.0288 atm at a temperature
of 37°C. Compute the molar mass of the compound.




 5/25/2012              Zumdahl Chapter 17            28
    Van’t Hoff Correction Factor
               Colligative Properties of Electrolyte Solutions
               Elevation of Boiling Point
                        ΔTb = m Kb
                      Where m = molality
      (Molality is moles of solute per kilogram of solvent)
               The Effect of Dissociation
                     ΔTb = i m Kb
   i = the number of particles released into the
         solution per formula unit of solute
e.g., NaCl dissociates into i = 2
e.g., Na2SO4 dissociates into i = 3                                also
        (2 Na+ + 1 SO4-2)                                     Depression of
                                                                Freezing Point
e.g., acetic acid (a weak acid and weak
     electrolyte) does not dissociate i = 1                    ΔTf = − m Kf
   5/25/2012                          Zumdahl Chapter 17
                                                               ΔTf = − i m Kf
                                                                           29

						
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