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Solubility and Distribution Phenomena

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Solubility
is the property of a solid, liquid, or gaseous chemical substance called solute to dissolve in a solid, liquid, or gaseous solvent to form a homogeneous solution of the solute in the solvent.

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Solubility
solubility can be defined as the quantity of a substance that can be dissolved in a solvent at a certain temperature. Most often, the solvent is a liquid, which can be a pure substance or a mixture. One may also speak of solid solution, but rarely of solution in a gas.
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Listen! A Solution is a HOMOGENOUS MIXTURE

a mixture that is uniform throughout


Look! These are Solutions............. Powerpoint Templates

any combination of substances that has uniform composition and properties


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2 main components of a SOLUTION


is the liquid in which the solute is dissolved is the component in greater amount The component of solution that has the same physical state as the final solution

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2 main components of a SOLUTION


A solute is dissolved in a solvent solute is the substance being dissolved Any component that is dissolved in the solvent

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Importance of Solubility would give the analyst the knowledge to choose the best solvent medium in drug formulation. to avoid certain difficulties in the drug liberation resulting to poor drug absorption. serves as a standard or test of purity.

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Mixtures In chemistry, a mixture is a material system made up by two or more different substances which are mixed but are not combined chemically. refers to the physical combination of two or more substances the identities of which are retained and are mixed in the form of alloys, solutions, suspensions, and colloids.

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Why mixtures mix? because of Intermolecular forces which are forces of attraction or repulsion which act between neighboring particles: atoms, molecules or ions.

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Four types of inter molecular forces are: ionic bond dipole-dipole Hydrogen bonding London force

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Mixtures can be either homogeneous or heterogeneous. A homogeneous mixture is a type of mixture in which the composition is uniform. A heterogeneous mixture is a type of mixture in which the components can easily be identified, as there are two or more phases present.

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Expressing solubility Terms parts solvent to 1 part solute Very soluble <1 part Freely soluble 1-10 parts Soluble 10-30 parts Sparingly soluble 30-100 parts Slightly soluble 100-1000 parts Very slightly soluble 1000-10,000 parts Insoluble >10,000 parts

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Solution In chemistry, a solution is a homogeneous mixture composed of only one phase. In such a mixture, a solute is dissolved in another substance, known as a solvent. The solvent does the dissolving. How Water Dissolves Salt.mp4

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Types of solutions A saturated solution is a solution which contains at a given temperature as much solute as it can hold in presence of dissolving solvent.

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Types of Solution Any solution may contain less solute than would be necessary to saturate it. Such a solution is known as unsaturated solution.

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Types of solutions When the solution contains more solute than would be necessary to saturate it then it is termed as supersaturated solution.

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Examples All the three states of matter (gas, liquid or solid) may behave either as solvent or solute. Depending on the state of solute or solvent, mainly there may be following nine types of binary solutions.

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Among these solutions the most significant type of solutions are those which are in liquid phase and may be categorised as: (1) Solid in liquid solutions, (2) Liquid in liquid solutions (3) Gas in liquid solutions

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Solvent Gas Gas Gas Liquid Liquid Liquid Solid Solid Solid

Solute Gas Liquid Solid Gas Liquid Solid Gas Liquid Solid

Example Mixture of gases, air. Water vapours in air, mist. Sublimation of a solid into a gas, smoke. CO2 gas dissolved in water (aerated drinks). Mixture of miscible liquids, e.g., alcohol in water. Salt in water, sugar in water. Adsorption of gases over metals; hydrogen over palladium. Mercury in zinc, mercury in gold,CuSO4.5H2O. Homogeneous mixture of two or more metals (alloys), e.g., copper in gold, zinc in copper.
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Solvent solute interaction

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-- POLAR SOLVENT -- NON POLAR SOLVENT -- SEMI POLAR SOLVENT

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POLAR SOLVENT -- solubility of a drug is due in large measure to the polarity of the solvent i.e. to its dipole moment. -- polar solvent dissolve ionic solute and other polar substances. -- accordingly, water mixes in all proportions with alcohol and dissolves sugars and other Powerpoint Templates Page 22 polyhydroxy component.

HILDEBRAND showed that ability of the solute to form hydrogen bonds is a far more significant factor than is polarity as reflected in high dipole moment. --water dissolves phenols, alcohols, aldehyde, ketons , amines , and other oxygen and nitrogen containing compound that can form hydrogen bonds with water H H R---O-----H---O--alcohol
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Polar solvent such as water act as solvent according following mechanisms--owing to their high dielectric constant , namely about 80 for water polar solvent break covalent bonds of potentially strong electrolytes by acid- base reaction cause these solvents are amphiprotic. Page 24 HClPowerpoint Templates + H2O H3O + Cl

NON POLAR SOLVENTS Non polar solvents are unable to reduce the attraction between the ions of strong and weak electrolytes because of solvents low dielectric constant. They belong to group aprotic solvents Non polar compound can dissolve non polar solutes with similar internal pressure through induced dipole interaction.
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SEMI POLAR SOLVENTS Semipolar solvents can induce a certain degree of polarity in nonpolar solvent molecules. e.g. ketones, alcohols benzene which is readily polarizable becomes soluble in alcohol In fact, semipolar compound can act as intermediate solvent to bring miscibility of polar and non polar liquids. e.g. propylene glycol increase the mutual solubility of water and peppermint oil and of water and Powerpoint Templates Page 26 benzyl benzoate

Solubility of gases in liquids, liquid in liquid, solids in liquid

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Solubility
is the property of solid, liquid or gaseous chemical substance called solute to dissolve in a solid, liquid or gaseous solvent to form a homogeneous solution of the solute in the solvent. Solubility depends on temperature, partial pressure of the gas over the liquid and the nature of solvent. Most common solvent is water
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The solubility of a substance fundamentally depends on the used solvent as well as on temperature and pressure. The extent of the solubility of a substance in a specific solvent is measured as the saturation concentration where adding more solute does not increase the concentration of the solution.
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Solubility of gases in liquids


Gas solubility is always limited by the equilibrium between the gas and a saturated solution of the gas. The dissolved gas will always follow Henry's law.

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Temperature
As the temperature of a liquid increases, the solubility of gas in the liquid will also decrease. As temperature increases, the kinetic energy of the solute gas increase and the gas escape.

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Heating a solution of a gas enables the particles of gas to move more freely between the solution and the gas phase.

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Pressure
When pressure increases over the solvent, the solubility of the gas is increase. Pressure increases as gas molecules strike the surface to enter solution is increased. Controls the number of gas molecule collisions with the surface of the solution. If the partial pressure is doubled the number of collisions with the surface will double.
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The increased number of collisions produce more dissolved gas. The dissolving process for gases is an equilibrium.

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At equilibrium the number of molecules leaving the gas phase to enter the solution equals the number of gas molecules leaving the solution. If the temperature stays constant increasing the pressure will increase the amount of dissolved gas.
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Low pressure equilibrium Low concentration

Double the pressure equilibrium Double the concentration

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Henrys law

C1_concentration P1 _gas partial pressure. C2 _concentration P2 _ gas partial pressure


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Solubility of liquid in liquids


The mixing of two or more substances of the same chemistry but different concentrations to form a constant. Ex: Alcoholic beverages ( ethanol in water) When the property of liquids is mix in all portion forming a homogeneous solution is called miscible.
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liquid water at high temperatures, the solubility of ionic solutes tends to decrease due to the change of properties and structure of liquid water. The lower dielectric constant results in a less polar solvent

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The pressure at a point in a liquid depends on its vertical distance from the surface of the liquid. A liquid with a higher density exerts a higher pressure.

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Solubility of solids in liquids


Opposite to gas in liquid. The solubility of a solids increases as the temperature increases.

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Solubility Rules!

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Solubility Rules!
Rule 1. All compounds of Group IA elements (the alkali metals) are soluble.

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Calculating the Ksp from the Molar Solubility Back to Equilibrium Menu The molar solubility of a substance is the number of moles that dissolve per liter of solution. For very soluble substances (like sodium nitrate, NaNO3), this value can be quite high, exceeding 10.0 moles per liter of solution in some cases. For insoluble substances like silver bromide (AgBr), the molar solubility can be quite small. In the case of AgBr, the value is 5.71 x 107 moles per liter. Given this value, how dos one go about calculating the Ksp of the substance? Here is a skeleton outline of the process: 1) Write the chemical equation for the substance dissolving and dissociating. 2) Write the Ksp expression. 3) Insert the concentration of each ion and multiply out.

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Problem #1: Determine the Ksp of silver bromide, given that its molar solubility is 5.71 x 107 moles per liter. When AgBr dissolves, it dissociates like this: AgBr (s) <===> Ag+ (aq) + Br (aq) The Ksp expression is: Ksp = [Ag+] [Br] There is a 1:1 ratio between AgBr and Ag+ and there is a 1:1 ratio between AgBr and Br. This means that, when 5.71 x 107 mole per liter of AgBr dissolves, it produces 5.71 x 107 moles per liter of Ag+ and 5.71 x 107 moles per liter of Br in solution. Putting the values into the Ksp expression, we obtain: Ksp = (5.71 x 107) (5.71 x 107) = 3.26 x 1013 Video: Calculating the Ksp from the Molar Solubility
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Problem #2: Determine the Ksp of calcium fluoride (CaF2), given that its molar solubility is 2.14 x 104 moles per liter. When CaF2 dissolves, it dissociates like this: CaF2 (s) <===> Ca2+ (aq) + 2 F (aq) The Ksp expression is: Ksp = [Ca2+] [F]2 There is a 1:1 ratio between CaF2 and Ca2+, BUT there is a 1:2 ratio between CaF2 and F. This means that, when 2.14 x 104 mole per liter of CaF2 dissolves, it produces 2.14 x 104 moles per liter of Ca2+, BUT 4.28 x 104 moles per liter of F in solution. Putting the values into the Ksp expression, we obtain: Ksp = (2.14 x 104) (4.28 x 104)2 = 3.92 x 1011 Please note, I DID NOT double the F concentration. I took the Ca2+ concentration and doubled it to get the F concentration. Powerpoint Templates Page 47

For example, NaNO3, KCl, and LiOH are all soluble compounds. This means that an aqueous solution of KCl really contains the predominant species K+ and Cl- and, because KCl is soluble, no KCl is present as a solid compound in aqueous solution: KCl(s) => K+(aq.) + Cl-(aq.)

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Solubility Rules!
Rule 2. All ammonium salts (salts of NH4+) are soluble

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For example, NH4OH is a soluble compound. Molecules of NH4OH completely dissociate to give ions of NH4+ and OH- in aqueous solution.

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Rule 3. All nitrate (NO3-), chlorate (ClO3-), perchlorate (ClO4-), and acetate (CH3COO- or C2H3O2-, sometimes abbreviated as Oac-) salts are soluble.

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For example, KNO3 would be classified as completely soluble by rules 1 and 3. Thus, KNO3 could be expected to dissociate completely in aqueous solution into K+ and NO3- ions:
KNO3 => K+(aq.) + NO3-(aq.)

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Solubility Rules!
Rule 4. All chloride (Cl-), bromide (Br-), and iodide (I-) salts are soluble except for those of Ag+, Pb2+, and Hg22+.

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For example, AgCl is a classic insoluble chloride salt: AgCl(s) <=> Ag+(aq.) + Cl(Ksp = 1.8 x 10-10). (aq.)

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Solubility Rules!
Rule 5. All sulfate ( SO4=) compounds are soluble except those of Ba2+, Sr2+, Ca2+, Pb2+, Hg22+, and Hg2+, Ca2+ and Ag+ sulfates are only moderately soluble.

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For example, BaSO4 is insoluble (only soluble to a very small extent): BaSO4(s) <=> Ba2+(aq.) + SO42(Ksp = 1.1 x 10-10). (aq.) Na2SO4 is completely soluble: Na2SO4(s) => 2 Na+(aq.) + SO42(aq.).

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Solubility Rules!
Rule 6. All hydroxide (OH-) compounds are insoluble except those of Group I-A (alkali metals) and Ba2+, Ca2+, and Sr2+.

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For example, Mg(OH)2 is insoluble (Ksp = 7.1 x 10-12). NaOH and Ba(OH)2 are soluble, completely dissociating in aqueous solution: NaOH(s) => Na+(aq.) + OH-(aq.), a strong base Ba(OH)2(s) => Ba2+(aq.) + 2OH(Ksp = 3 x 10-4) (aq.)

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Solubility Rules!
Rule 7. All sulfide (S2-) compounds are insoluble except those of Groups I-A and II-A (alkali metals and alkali earths).

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For example, Na2S(s) <=> 2Na+(aq.) + S2-(aq.) MnS is insoluble (Ksp = 3 x 10-11).

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Solubility Rules!
Rule 8. All sulfites (SO3=), carbonates (CO3=), chromates (CrO4=), and phosphates (PO43-) areinsoluble except for those of NH4+ and Group I-A (alkali metals)(see rules 1 and 2).

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For example, calcite, CaCO3(s) <=> Ca2+(aq.) + CO3=(aq.) (Ksp = 4.5 x 10-9).

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Distribution of Solutes between immiscible solvents

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Distribution of Solutes between Immiscible Solvents


If an excess of liquid or solid is added to a mixture of two immiscible liquids, it will distribute itself between the two phases so that each becomes saturated.
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Distribution of Solutes between Immiscible Solvents


If the substance is added to the immiscible solvent in an amount insufficient to saturate the solutions, it will distribute between the two layers in a define concentration ratio
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Distribution of Solutes between Immiscible Solvents


At constant temperature, a solute distributes itself between two immiscible solvents only in a particular ratio This is known as the Distribution Law
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Distribution of Solutes between Immiscible Solvents


If a solute X distributes itself between two non miscible solvents A & B at constant temperature & X is in the same molecular condition in both the solvents, then: concentration of X in A / Concentration of X in B = Kd" Where Kd is called the distribution coefficient or the partition coefficient.
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Distribution of Solutes between Immiscible Solvents


If C1 denotes the concentration of solute in solvent A & C2, the concentration of X in B; Nersts distribution law can be expressed as C1/C2 = Kd Partition Coefficient is the ratio of concentrations of a compound in the two phases of a mixture of two immiscible solvents at equilibrium.
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Distribution of Solutes between Immiscible Solvents


This law was given by Nernst in the year 1891. As the name suggests, it is related to the distribution of a solute(solid or liquid) in two non-miscible solvents. However, it dissolves in both of them.
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Distribution of Solutes between Immiscible Solvents


For example, Iodine a violet cyrstalline solid when added to a mixture of two immiscible liquids water and carbon tetrachloride, distributes in both of them. The value of K in this case is 85 at room temperature i.e. 298 K.
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Distribution of Solutes between Immiscible Solvents

The priniciple of distribution law is quite helpful in metallurgical operations. A popular example is Desilverisation of Lead(Parkes process).

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Distribution of Solutes between Immiscible Solvents


Limitations There are basically two limitations. They are : 1. The solute which is to be distributed should not react with any of the solvents. 2. The solute should not undergo any change in its molecular state in the solvents i.e. it should neither dissociate nor associate.
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