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    Prentice Hall 2003 Chapter 13

    Chapter 4_3

    Physical Transformation of

    Pure Substances

    David P. White

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    Prentice Hall 2003 Chapter 11

    Viscosity

    Viscosity is the resistance of a liquid to flow.

    A liquid flows by sliding molecules over each other.

    The stronger the intermolecular forces, the higher the

    viscosity.

    Example: glycerol C3H8O3(1.49 Ns/m2) and water

    (1.01x10-3Ns/m2)

    Some Properties of Liquids

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    Surface Tension

    Surface Tension

    Bulk molecules (thosein the liquid) are

    equally attracted to

    their neighbors.

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    Surface Tension

    Surface molecules are attracted downwards and sideways by other

    molecules but not upwards away from the surface.

    Therefore, the surface to tighten like an elastic film Surface tension is the amount of energy required to stretch or

    increase the surface area of a liquid.

    Liquids with strong intermolecular forces have higher surface

    tension Cohesive forcesbind molecules to each other.

    Adhesive forcesbind molecules to a surface.

    Some Properties of Liquids

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    Surface Tension

    Meniscusis the shape of the liquid surface.

    If adhesive forces are greater than cohesive forces, the liquid

    surface is attracted to its container more than the bulkmolecules. Therefore, the meniscus is U-shaped (e.g. water in

    glass).

    If cohesive forces are greater than adhesive forces, the meniscus

    is curved downwards. (e.g mercury) Capil lary Action: When a narrow glass tube is placed in

    water, the meniscus pulls the water up the tube.

    Some Properties of Liquids

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    Transformation from one phase to another,

    Occur when energy (usually heat) is added or removed from a

    substance Sublimation: solid gas. Hsub> 0 (endothermic).

    Vaporization: liquid gas. Hvap> 0 (endothermic).

    Melting orfusion: solid liquid. Hfus> 0 (endothermic).

    Deposition: gas solid. Hdep< 0 (exothermic).

    Condensation: gas liquid. Hcon< 0 (exothermic).

    Freezing: liquid solid. Hfre< 0 (exothermic).

    Phase Changes

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    Phase Changes

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    Liquid-vapor equilibrium

    Collision rate higher in liquid phase.

    Molecules in liquid phase have sufficient energy to escapefrom the surface a phase change occurs

    evaporation/vaporization.

    Evaporation depends on temperature: higher T, greater kinetic

    E, hence more molecules leave the liquid.

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    Phase Changes

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    Explaining Vapor Pressure on the

    Molecular Level

    Some of the molecules on the surface of a liquid have

    enough energy to escape the attraction of the bulk liquid.

    These molecules move into the gas phase.

    As the number of molecules in the gas phase increases,

    some of the gas phase molecules strike the surface and

    return to the liquid. After some time the pressure of the gas will be constant

    at the vapor pressure.

    Vapor Pressure

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    Explaining Vapor Pressure on the

    Molecular Level

    Vapor Pressure

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    Explaining Vapor Pressure on the

    Molecular Level

    Dynamic Equilibrium: the point when as many molecules

    escape the surface as strike the surface.

    Vapor pressure is the pressure exerted when the liquidand vapor are in dynamic equilibrium.

    Volatility, Vapor Pressure, and Temperature

    If equilibrium is never established then the liquidevaporates.

    Volatile substances evaporate rapidly.

    Vapor Pressure

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    Vapor Pressure and Boiling Point

    Liquids boil when the external pressure equals the vapor

    pressure.

    Vapor pressure of a liquid increases with increasingtemperature

    Vapor Pressure

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    Molar heat of vaporization and boiling point

    A measure of strength of intermolecular forces in a liquid is the

    molar heat of vaporization Energy required to vaporize 1 mole of a liquid

    Strong intermolecular forces in liquid, high molar heat of

    vaporization, low vapor pressure

    Vapor pressure of a liquid increases with increasing temperature Relationship between vapor pressure of a liquid and the absolute

    temperature is given by the Clausius-Clapeyron equation

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    Phase Changes

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    Clausius-Clapeyron equation

    Can determine heat of vaporization by slope.

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    Phase Changes

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    If we know the values of Hvap and P of a liquid at one

    T, can use Clausius-Clapeyron equation to calculate the

    vapor pressure of liquid at different T

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    Phase Changes

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    Example 1

    Diethyl ether is a volatile, highly flammable organic

    liquid that is used mainly as a solvent. The vapor

    pressure of diethyl ether is 401 mmHg at 18o

    C. Calculateits vapor pressure at 32oC. Hvap = 26.0 kJ/mol

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    Boling point

    At boiling point, bubbles form within liquid

    When bubble forms the liquid originally occupying that space ispushed aside and level of liquid in container is forced to rise.

    The P exerted on the bubble is largely atmospheric pressure.

    The P inside bubble is due solely to the vapor pressure of liquid.

    when vapor pressure = external pressure, bubble rise to surface ofliquid and burst.

    If vapor pressure in bubble lower than external pressure bubble

    collapse before it could rise

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    Phase Changes

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    We can conclude that boiling point of liquid depends on

    external pressure.

    Bcoz boiling point defined in terms of vapor pressure ofliquid, we expect boiling point to be related to the molar

    heat of vaporization.

    Higher heat of vaporization, higher boiling point

    Both determined by strength of intermolecular forces

    Ar and methane (weak dispersion forces) low bp and Hvap

    Ethanol and water (H-bonding) high bp and HvapPrentice Hall 2003 Chapter 13

    Phase Changes

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    Molar heat of fusion- energy required to melt 1 mole of a

    solid

    Molar heat of sublimation- energy required to sublime 1mole of a solid

    Hsub= Hfus+ Hvap

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    Phase Changes

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    Example 2

    Calculate the amount of energy needed to heat 346 g of

    liquid water from 0oC to 182oC. Assume that the

    specific heat of water is 4.184 J/go

    C over the entireliquid range and that the specific heat of steam is 1.99 J/goC.

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    Phase diagram: plot of pressure vs. Temperature

    summarizing all equilibria between phases.

    Given a temperature and pressure, phase diagrams tell uswhich phase will exist.

    Any temperature and pressure combination not on a

    curve represents a single phase.

    Phase Diagrams

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    Features of a phase diagram:

    Triple point: temperature and pressure at which all three phases

    are in equilibrium. Vapor-pressure curve: generally as pressure increases,

    temperature increases.

    Critical point: critical temperature and pressure for the gas.

    Melting point curve: as pressure increases, the solid phase isfavored if the solid is more dense than the liquid.

    Normal melting point: melting point at 1 atm.

    Phase Diagrams

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    Critical Temperature and Pressure

    Every substance has a:

    Critical temperature, Tc:

    Above it gas phase cannot be made to liquefy nomatter how great the applied pressure

    Highest T at which a substance can exist as a liquid

    Above Tc, there is no fundamental distinction betweenliquid and gas

    Critical pressure, Pc: minimum pressure required for

    liquefaction at Tc

    Phase Diagrams

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    Phase Diagrams

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    The Phase Diagrams of H2O and CO2

    Phase Diagrams

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    The Phase Diagrams of H2O and CO2

    Water:

    The melting point curve slopes to the left because ice is less

    dense than water. Triple point occurs at 0.0098C and 4.58 mmHg.

    Normal melting (freezing) point is 0C.

    Normal boiling point is 100C.

    Critical point is 374C and 218 atm.

    Phase Diagrams

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    The Phase Diagrams of H2O and CO2

    Carbon Dioxide:

    Triple point occurs at -56.4C and 5.11 atm.

    Normal sublimation point is -78.5C. (At 1 atm CO2sublimesit does not melt.)

    Critical point occurs at 31.1C and 73 atm.

    Phase Diagrams

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    Chapter 4_4Properties of Solutions

    David P. White

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    Prentice Hall 2003 Chapter 13

    A solution is a homogeneous mixture of solute (present in

    smallest amount) and solvent (present in largest amount).

    Solutes and solvent are components of the solution.

    In the process of making solutions with condensed

    phases, intermolecular forces become rearranged.

    The Solution Process

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    The Solution Process

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    Energy Changes and Solution

    Formation

    There are three energy steps in forming a solution:

    separation of solute molecules (H1),

    separation of solvent molecules (H2), formation of solute-solvent interactions (H3).

    We define the enthalpy change in the solution process as

    Hsoln= H1+ H2+ H3. Hsolncan either be positive or negative depending on the

    intermolecular forces.

    The Solution Process

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    Energy Changes and Solution

    Formation

    Breaking attractive intermolecular forces is always

    endothermic.

    Forming attractive intermolecular forces is alwaysexothermic.

    The Solution Process

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    Energy Changes and Solution

    Formation

    To determine whether Hsolnis positive or negative, we

    consider the strengths of all solute-solute and solute-

    solvent interactions: H1and H2are both positive.

    H3is always negative.

    It is possible to have either H3> (H1+ H2) or H3< (H1+

    H2).

    The Solution Process

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    Energy Changes and Solution

    Formation

    Examples:

    NaOH added to water has Hsoln= -44.48 kJ/mol.

    NH4NO3added to water has Hsoln= + 26.4 kJ/mol.

    Rule: polar solvents dissolve polar solutes. Non-polar

    solvents dissolve non-polar solutes

    If Hsolnis too endothermic a solution will not form.

    NaCl in gasoline: the ion-dipole forces are weak because

    gasoline is non-polar. Therefore, the ion-dipole forces do not

    compensate for the separation of ions.

    The Solution Process

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    Energy Changes and Solution

    Formation

    Water in octane: water has strong H-bonds. There are no

    attractive forces between water and octane to compensate for

    the H-bonds.

    The Solution Process

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    Why solute dissolves in a solvent if attraction for its own

    molecules are stronger than the solute-solvent attraction

    Solution process governed by energy(exothermic/endothermic) and entropy (tendency

    towards disorder)

    In pure state, the solvent and solute possess a fair degree

    of order (regular arrangement of molecules/ions/atoms)

    Order is destroyed when the solute dissolves in the

    solvent

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    The Solution Process

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    Solution Formation, Spontaneity, and

    Disorder

    A spontaneous process occurs without outside

    intervention.

    When free energy of the system decreases (e.g. droppinga book and allowing it to fall to a lower potential energy),

    the process is spontaneous.

    The Solution Process

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    Solution Formation, Spontaneity, and

    Disorder

    If the process leads to a greater state of disorder, then the

    process is spontaneous.

    Example: a mixture of CCl4and C6H14is less orderedthan the two separate liquids. Therefore, they

    spontaneously mix even though Hsolnis very close to

    zero.

    There are solutions that form by physical processes and

    those by chemical processes.

    The Solution Process

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    Solution Formation, Spontaneity, and

    Disorder

    The Solution Process

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    Solution Formation and Chemical

    Reactions

    Example: a mixture of CCl4and C6H14is less ordered

    Consider:

    Ni(s) + 2HCl(aq) NiCl2(aq) + H2(g).

    Note the chemical form of the substance being dissolved

    has changed (Ni NiCl2).

    When all the water is removed from the solution, no Ni isfound only NiCl26H2O. Therefore, Ni dissolution in

    HCl is a chemical process.

    The Solution Process

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    Solution Formation and Chemical

    Reactions

    Example:

    NaCl(s) + H2O (l) Na+(aq) + Cl-(aq).

    When the water is removed from the solution, NaCl isfound. Therefore, NaCl dissolution is a physical

    process.

    The Solution Process

    S t t d S l ti d

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    Solutions can be characterized:

    Saturated solution: contains maximum amount of a solute that

    will dissolve in a given solvent at a specific temperature Unsaturated solution: contains less solute than it has the

    capacity to dissolve

    Supersaturated solution: a solution formed when more solute is

    dissolved than in a saturated solution. Not stable and solute willcome out from supersaturated solution as crystals

    Crystallization: process in which dissolved solute comes out of

    solution and forms crystals.

    Saturated Solutions and

    Solubility

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    F t Aff ti

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    Solute-Solvent Interaction

    Solubility is a measure of how much solute will dissolve in a

    solvent at a specific temperature.

    like dissolve like helpful in predicting solubility of substance in agiven solvent

    Miscible liquids: mix in any proportions.

    Immiscible liquids: do not mix.

    Polar liquids tend to dissolve in polar solvents. Intermolecular forces are important: water and ethanol are miscible

    because the broken hydrogen bonds in both pure liquids are re-

    established in the mixture.

    Factors Affecting

    Solubility

    F t Aff ti

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    Solute-Solvent Interaction

    The number of carbon atoms in a chain affect solubility:

    the more C atoms the less soluble in water.

    The number of -OH groups within a molecule increasessolubility in water.

    The more polar bonds in the molecule, the better it

    dissolves in a polar solvent.

    The less polar the molecule the less it dissolves in a polar

    solvent and the better is dissolves in a non-polar solvent.

    Factors Affecting

    Solubility

    F t Aff ti

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    Solute-Solvent Interaction

    Factors Affecting

    Solubility

    Factors Affecting

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    Solute-Solvent Interaction

    Factors Affecting

    Solubility

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    Example 3

    Predict the relative solubilities in the following cases

    Bromine (Br2) in benzene (= 0 D) and in water (= 1.87 D)

    KCl in carbon tetrachloride (= 0 D) and in liquid ammonia(= 1.46 D)

    Formaldehyde (H2C=O) in carbon disulfide (= 0 D) and in

    water

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    Factors Affecting

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    Solute-Solvent Interaction

    Network solids do not dissolve because the strong

    intermolecular forces in the solid are not re-established in

    any solution. Example: SiO2

    Factors Affecting

    Solubility

    Factors Affecting

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    Pressure Effects

    Solubility of a gas in a liquid is a function of the pressure

    of the gas.

    The higher the pressure, the more molecules of gas areclose to the solvent and the greater the chance of a gas

    molecule striking the surface and entering the solution.

    Therefore, the higher the pressure, the greater the solubility.

    The lower the pressure, the fewer molecules of gas are close to

    the solvent and the lower the solubility.

    Factors Affecting

    Solubility

    Factors Affecting

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    Pressure Effects

    Factors Affecting

    Solubility

    F t Aff ti

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    Henrys law states that the solubility of a gas in a liquid

    is proportional to the pressure of the gas over the

    solution

    Where c is the molar concentration (mol/L) of dissolved

    gas, k is a constant with the units mol/L .atm, andPis

    the pressure of the gas over the solution at equilibrium

    Prentice Hall 2003 Chapter 13

    Factors Affecting

    Solubility

    kPc

    Factors Affecting

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    Prentice Hall 2003 Chapter 13

    Pressure Effects

    Carbonated beverages are bottled with a partial pressure

    of CO2> 1 atm.

    As the bottle is opened, the partial pressure of CO2decreases and the solubility of CO2decreases.

    Therefore, bubbles of CO2escape from solution.

    Factors Affecting

    Solubility

    http://d/Media_Portfolio/HenrysLaw/HenrysLawMovie.html
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    Example 4

    The solubility of nitrogen gas at 25oC and 1 atm is

    6.8x10-4mol/L. What is the concentration in molarity of

    nitrogen dissolved in water under atmospheric

    conditions? The partial pressure of nitrogen gas in the

    atmosphere is 0.78 atm

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    Factors Affecting

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    Temperature Effects

    Experience tells us that sugar dissolves better in warm

    water than cold.

    As temperature increases, solubility of solids generallyincreases.

    Sometimes, solubility decreases as temperature increases

    (e.g. Ce2

    (SO4

    )3

    ).

    Factors Affecting

    Solubility

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    F t Aff ti

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    Fractional crystallization: separation of a mixture of substances

    into pure components on the basis of their different solubilities

    Example: 90 g of KNO3is contaminated with 10g of NaCl.

    To purify KNO3, dissolve mixture in 100ml of water at 60oC then

    cool to 0oC.

    Solubility KNO3and NaCl are 12.1g/100g H2O and 34.2g/100g

    H2O

    Therefore, 78 g of KNO3will crystallize out of the solution

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    Factors Affecting

    Solubility

    Factors Affecting

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    Temperature Effects

    Experience tells us that carbonated beverages go flat as

    they get warm.

    Therefore, gases get less soluble as temperatureincreases.

    Thermal pollution: if lakes get too warm, CO2and O2

    become less soluble and are not available for plants or

    animals.

    Factors Affecting

    Solubility

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    Ways of Expressing

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    Mass Percentage, ppm, and ppb

    All methods involve quantifying amount of solute per

    amount of solvent (or solution).

    Generally amounts or measures are masses, moles orliters.

    Qualitatively solutions are dilute or concentrated.

    Definitions:

    Ways of Expressing

    Concentration

    100solutionofmasstotal

    solutionincomponentofmasscomponentof%mass

    Ways of Expressing

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    Mass Percentage, ppm, and ppb

    Parts per million (ppm) can be expressed as 1 mg ofsolute per kilogram of solution.

    If the density of the solution is 1g/mL, then 1 ppm = 1 mg

    solute per liter of solution.

    Parts per billion (ppb) are 1 g of solute per kilogram of

    solution.

    Ways of Expressing

    Concentration

    610solutionofmasstotal

    solutionincomponentofmasscomponentofppm

    Ways of Expressing

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    Mass Percentage, ppm, and ppb

    Mole Fraction, Molarity, and Molality

    Recall mass can be converted to moles using the molar

    mass.

    Ways of Expressing

    Concentration

    910solutionofmasstotal

    solutionincomponentofmasscomponentofppb

    solutionofmolestotal

    solutionincomponentofmolescomponentoffractionMole

    solutionofliters

    solutemolesMolarity

    Ways of Expressing

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    Mole Fraction, Molarity, and Molality

    We define

    Converting between molarity (M) and molality (m)

    requires density.

    Ways of Expressing

    Concentration

    solventofkg

    solutemolesMolality, m

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    Example 5

    The density of a 2.45M aqueous solution of methanol

    (CH3OH) is 0.976 g/ml. What is the molality of the

    solution? Molar mass of methanol is 32.04g/mol

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    Ways of Expressing

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    The choice of concentration unit is based on the purpose

    of the experiment

    Advantage of molarity is easier to measure the volume ofsolution than to weigh the solvent. Thus molrity is

    usually preferred.

    However, molality is independent of temperature.

    Volume of solution increases with increasing T so that asolution that is 1.0M at 25oC may become 0.97M at 45oC

    Can affect accuracy of experiment

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    Ways of Expressing

    Concentration

    C lli ti P ti

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    Colligative properties are properties that depend only on

    the number of solute particles in solution and not on the

    nature of the solute particles. depend on number of solute particles present.

    Vapor-pressure lowering, boiling point elevation, freezing

    point depression and osmotic pressure

    Colligative Properties

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    Lowering Vapor Pressure

    If a solute is nonvolatile the vapour pressure of its solution is

    always less than that of the pure solvent.

    Thus the relationship between solution and solvent vapor pressure

    depends on the concentration of the solute in the solution

    Non-volatile solvents reduce the ability of the surface solvent

    molecules to escape the liquid.

    Therefore, vapor pressure is lowered.

    The amount of vapor pressure lowering depends on the amount of

    solute.

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    Colligative Properties

    C lli ti P ti

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    Lowering Vapor Pressure

    Colligative Properties

    C lli ti P ti

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    Lowering Vapor Pressure

    Raoults Law: vapor pressure of a solvent over a solution,

    PAis given by the vapor pressure of the pure solvent, Po

    A,

    times the mole fraction of the solvent in the solution, XA

    In a solution containing only one solute, X1= 1-X2, where

    X2 is the mole fraction of the solute.

    Colligative Properties

    AAA PP

    ABAAA PPPP ?

    C lli ti P ti

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    Lowering Vapor Pressure

    Ideal solution: one that obeys Raoults law.

    Raoults law breaks down when the solvent-solvent and

    solute-solute intermolecular forces are greater thansolute-solvent intermolecular forces.

    If both components of a solution are volatile(measureable

    vapor pressure) the vapor pressure of the solution is the

    sum of the individual partial pressures

    PT= PA+ PB

    Colligative Properties

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    Example 6

    Calculate the vapor pressure of a solution made by

    dissolving 218 g of glucose (molar mass = 180.2 g/mol)

    in 460ml of water at 30oC. What is the vapor pressure

    lowering? The vapor pressure of pure water at 30oC is

    31.82 mmHg.Assume the density of the solution is

    1.00g/ml

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    Boiling-Point Elevation

    Boiling point is the T at which its vapor pressure equals

    the external atmospheric pressure Non-volatile solute lowers the vapor pressure. Therefore,

    boiling point of the solution must be affected.

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    Boiling-Point Elevation

    At 1 atm (normal boiling point of pure liquid) there is a

    lower vapor pressure of the solution. Therefore, a higher

    temperature is required to teach a vapor pressure of 1 atmfor the solution (Tb).

    Molal boiling-point-elevation constant,Kb, (oC/m)

    expresses how much Tbchanges with molality, m:

    Colligative Properties

    mKT bb

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    Freezing Point Depression

    When a solution freezes, almost pure solvent is formed

    first.

    Therefore, the sublimation curve for the pure solvent is thesame as for the solution.

    Therefore, the triple point occurs at a lower temperature

    because of the lower vapor pressure for the solution.

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    Freezing Point Depression

    The melting-point (freezing-point) curve is a vertical line

    from the triple point.

    The solution freezes at a lower temperature (Tf) than thepure solvent.

    Decrease in freezing point (Tf) is directly proportional

    to molality (Kfis the molal freezing-point-depression

    constant):

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    mKT ff

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    Freezing involves transition from disordered to ordered

    state

    Therefore energy must be removed from system Solution has greater disorder than pure solvent, more

    energy needs to be removed from it to create order than

    pure solvent

    Therefore the solution has a lower freezing point than itssolvent

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    Example 7

    Ethylene glycol is a common automobile antifreeze. It is

    water soluble and fairly nonvolatile (b.p 197 oC). Calculate

    the freezing point of a solution containing 651 g of this

    substance in 2505 g of water. Would you keep this

    substance in your car radiator during the summer? The

    molar mass of ethylene glycol is 62.01 g/mol.

    Kf = 1.86o

    C/m and Kb = 0.52o

    C/m

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    Osmosis

    Semipermeable membrane: permits passage of some

    components of a solution. Example: cell membranes and

    cellophane. Osmosis: the movement of a solvent from low solute

    concentration to high solute concentration.

    There is movement in both directions across a

    semipermeable membrane.

    As solvent moves across the membrane, the fluid levels

    in the arms becomes uneven.

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    Osmosis

    Eventually thepressure difference between the arms

    stops osmosis.

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    Osmosis

    Osmotic pressure, , is the pressure required to stop

    osmosis:

    Isotonic solutions: two solutions with the same

    separated by a semipermeable membrane.

    Colligative Properties

    MRT

    RTV

    n

    nRTV

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    Osmosis

    Hypotonic solutions: a solution of lower than a

    hypertonic solution.

    Osmosis is spontaneous. Red blood cells are surrounded by semipermeable

    membranes.

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    Osmosis

    Crenation:

    red blood cells placed in hypertonic solution (relative to

    intracellular solution);

    there is a lower solute concentration in the cell than the

    surrounding tissue;

    osmosis occurs and water passes through the membrane out of

    the cell. The cell shrivels up.

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    Osmosis

    Active transport is the movement of nutrients and waste

    material through a biological system.

    Active transport is not spontaneous.

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