dissolution and solubilityxx_ppt [compatibility mode]

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    DISSOLUTION AND SOLUBILITY

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    Solutions

    Solutions are homogeneous mixtures of two

    or more pure substances.

    In a solution, the solute is dispersed uniformly

    throughout the solvent.

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    Ways of ExpressingWays of Expressing

    Concentrations ofConcentrations ofSolutionsSolutions

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    Mass Percentage

    Mass % of A =mass of A in solution

    total mass of solution   × 100

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    Molarity (M)

    1-L flask (1000.0 mL)

    Convenient way to prepare solution in lab,

    add 0.5 mol

    solute

    dilute to mark 

    get 0.5 M

    solution

     solutionof liters

    soluteof moles (M)Molarity   =

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    Parts per Million (ppm) and Parts per

    Billion (ppb)

    1 part

    4 parts

    = = 0.25 part per part

     10xsolutionof masstotal

    solutionincomponentof mass

     componentof ppm

    6

    =

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    moles of A

    total moles in solution X  A =

    Mole Fraction ( X )

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    THE PROCESS OF

    DISSOLUTION

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    State of Matter 

    Kinetic theory of matter Gas; molecules move independently

    Solid; thermal motion of molecules is

    restricted to vibration about their mean

    position

    Liquid; thermal motion of molecules is

    intermediate between gas and solid

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    Solutions

    How does a solid dissolveinto a liquid?

    What !drives" thedissolution process?

    What are the energetic of

    dissolution?

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    How Does a Solution Form?

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    How Does a Solution Form?

    1. Solvent molecules attracted to surface ions.2. Each ion is surrounded by solvent molecules.

    3. Energy change

    Ionic solid dissolving in water 

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    How Does a Solution Form

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    Degree of saturation

    Saturated solution

    Ø Solvent holds as muchsolute as is possible at

    that temperature.

    Ø Undissolved solidremains in flask.

    Ø Dissolved solute is indynamic equilibrium

    with solid solute

    particles.

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    Degree of saturation

    Unsaturated Solution

    Ø Less than themaximum amount of

    solute for thattemperature is

    dissolved in the

    solvent.

    Ø No solid remains in

    flask.

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    Degree of saturation

    Supersaturated

    Ø Solvent holds more solute than is normallypossible at that temperature.

    Ø These solutions are unstable; crystallization canoften be stimulated by adding a #seed crystal$ or

    scratching the side of the flask.

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    Crystallization: opposite of the

    solution process (solute becomes

    reattached to surface of crystal)

    Solute + Solvent Solution       ←

        →  

    ecrystalliz

    dissolve

    Saturated solution: no more solid will dissolve and

    a dynamic equilibrium exists between the solution

    and the undissolved solid

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    Degree of saturation

    Unsaturated, Saturated or Supersaturated?

    ⇒ Depends on How much solute can bedissolved in a solution

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    Energy Changes in Solution

    To determine the enthalpy change, we divide theprocess into 3 steps.1. Separation of solute particles ( %H 1).

    2. Separation of solvent particles to make !holes" ( %H 2).

    3. Formation of new interactions between solute andsolvent ( %H 3).

     & We define the enthalpy change in the solutionprocess as

     %H soln =  %H 1 +  %H 2 +  %H 3

     & %H soln can either be positive or negative dependingon the intermolecular forces

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    Energy Changes in Solution (cont.) The reaction may be exothermic when heat is

    released as a result of solubility process, and

    the flask gets warm (less common).e.gcalcium hydroxide , calcium acetate , in this

    case solubility decreases as temperature

    rises.

    The reaction may be endothermic when thesystem consumed heat to do the solubility

    process, and the flask gets cold (more

    common) e.g KNO3 , KBr , in this case

    solubility increases as temperature increases.

    The reaction is neither exothermic nor

    endothermic( %H = 0) e.g NaCl , in this case

    the solubility is not affected by temperature

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    SOLUBILITY OF LIQUID IN LIQUID

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    More Factors Affecting Solubility

    Polar liquids tend to dissolve in polar solvents

    due to dipole-dipole and H-bonding interactions

    CH3CCH3

    acetone

    ||O

    CH3CH2OH

    ethanol

    Miscible: soluble in all proportions (liquids)

    Immiscible: do not dissolve in one another

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    Factors Affecting Solubility (cont.)

    Nonpolar liquids tend to be insoluble in polar

    liquids; e.g. hexane (C6H14) does not dissolve inwater. Increasing the nonpolar character of a

    substance will decrease its solubility in water.

    Solubility and Polarity Solubility in Solubility inAlcohol H2O C6H14 

    CH3CH2OH ∞  0.12

    CH3CH2CH2OH ∞  ∞ 

    CH3CH2CH2CH2OH 0.11 ∞ 

    CH3CH2CH2CH2CH2OH 0.030 ∞ CH3CH2CH2CH2CH2CH2OH 0.0058 ∞ 

    mol alcohol/100 g solvent 

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    SOLUBILITY OF SOLIDS IN LIQUID(SOLUTE SOLVENT

    INTERACTION)

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    DISSOLUTION MECHANISM

    1. Interfacial reaction that results in liberationof solute molecule from the solid phase, Thesolution in contact with solid will becomesaturated (Cs).

    2. The solute molecules migrate through theboundary layers surrounding the crystal to thebulk of solution, at which concentration is (C).

    Boundary layer is nearly static and surroundall wetted surface of the solid.

    Mass transfer is slowly through the boundarylayer to the bulk of solution.

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    DISSOLUTION MECHANISM

    H= unstirred layer

    Small film of liquidsurrounding drug particle

    Bulk solution

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    DISSOLUTION MECHANISM

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    Plot of concentration gradient

    Concentration

    h  thickness of the

    stagnant layer 

    Distance from surface

    h

    Cs

    Cb

    Csat

    C = C b

    stagnant

    water layer

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    DISSOLUTION RATE

    • NOYES-WHITNEY EQUATION

    dm/dt= DACs /h

    'where dm/dt is the rate of mass transfer of

    solute molecule through the diffusion layer  Cs is the concentration of the solute at

    surface available for migration

    D is the diffusion coefficient (m2/s)

    A is the area available for molecularmigration

    H is the thickness of the boundary layer 

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    SOLUBILITY OF GASES IN LIQUID

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    SOLUBILITY OF GASES IN LIQUID

    In general, the solubility of

    gases in water increases

    with increasing mass.

    Why?

    Larger molecules have

    stronger dispersion

    forces.

    Usually, increase

    pressure will increasegas solubility

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    1.Effect of Structure

    Chemists use the axiom

    #like dissolves like$:

    Ø Polar substances tend

    to dissolve in polarsolvents.

    ØNonpolar substancestend to dissolve in

    nonpolar solvents.

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    1. Effect of Structure (cont.)

    The stronger the

    intermolecular

    attractions between

    solute and solvent,

    the more likely thesolute will dissolve.

    Example: ethanol in water 

    Ethanol = CH3CH2OH

    Intermolecular forces = H-bonds; dipole-dipole; dispersion

    (Van der Waal bond)

    Ions in water also have ion-dipole forces.

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    1. Effect of Structure (cont.)

    Glucose (which has

    hydrogen bonding)

    is very soluble in

    water.Cyclohexane (which

    only has dispersion

    forces) is not water-

    soluble.

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    1. Effect of structure (cont.)

    Vitamins A, D, K and E is soluble in nonpolarcompounds (like fats).

    Vitamins B and C is soluble in water.

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    Which

    vitamin is

    water-solubleand which is

    fat-soluble?

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    2. Effect of Pressure on solubility

    Increasing pressure above solution forces more gas todissolve.

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    2. Effect of Pressure (cont.)

    The solubility of liquids and solids

    does not change appreciably with

    partial pressure.

    But, the solubility of a gas in a liquid isdirectly proportional to the partial

    pressure above that gas. Effect of

    pressure is significant.

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    2. Effect of Pressure (cont.)

    Solubility of a gas in a liquid is a function of thepressure of the gas.

    The higher the pressure, the more molecules ofgas are close to the solvent and the greater thechance of a gas molecule striking the surface and

    entering the solution. & Therefore, the higher the pressure, the greaterthe solubility.

     & The lower the pressure, the fewer molecules ofgas are close to the solvent and the lower the

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    2. Effect of Pressure (cont.)

    Henry"s LawThe amount of a gas diss olved in a

    so lut ion is di rect ly proport ion to the

    pressu re of the gas above the solut ion

    W = kP where

    W is the mass of gas dissolved in thesolvent (Mol fraction);

    k is the Henry"s law constant for that gas

    in that solvent;

    P is the partial pressure of the gas abovethe liquid.