dissolution and solubilityxx_ppt [compatibility mode]
TRANSCRIPT
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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.