Chapter 11 & 13

Intermolecular Forces, Liquids, and Solids Properties of Solutions

Intermolecular Forces
Intermolecular Forces are attractive forces between neighboring molecules. Intermolecular Forces are responsible for: The nonideal behavior of gases. The strength of boiling and melting points. At the boiling or melting point. Enough energy must be supplied to overcome the attractive forces among molecules before they can enter the vapor or liquid phase. Stronger intermolecular forces create higher boiling or melting points.

van der Waals Intermolecular Forces

Dipole-Dipole Forces: are attractive forces between polar molecules. The larger the dipole moment, the greater the force.

van der Waals Intermolecular Forces

Ion-Dipole Forces: are attractive forces between an ion and a polar molecule.
Hydration is an example of ion-dipole forces, where the ionic solid dissolves in water, which is polar, and separates the solid into its cations and anions surrounded by water.

van der Waals Intermolecular Forces

Induced Dipole: when an atom comes into contact with an ion or a polar molecule. The charge creates an induced dipole on the atom. The larger the atom, the more polarizable it will be.
Two types are: (b) Ion-induced dipole (c) Dipole-induced dipole

This figure shows an example with a helium atom in (a) then an induced dipole is created from a cation in (b) and finally an induced dipole is created from a polar molecule in (c).

van der Waals Intermolecular Forces

Every atom has an Instantaneous Dipole due to the location of the electrons in the diffuse cloud of the orbital. These instantaneous dipoles all cancel each other out because they are very short lived. But, within a collection of atoms, an instantaneous dipole from one atom can create an temporary dipole in a neighboring atom. These interactions produce:

London Dispersion Forces: are attractive forces that arise as a result of temporary induced dipoles in atoms or molecules. These can occur in nonpolar molecules. The heavier the molecule, the higher the b.p. due to these forces and their polarizability.

The Hydrogen Bond

The hydrogen bond is a special type of dipole-dipole interaction between the hydrogen atom in a polar bond and an electronegative O, N, or F atom. An example is: N-H, O-H, or F-H. When hydrogen is attached to O, N or F atom, a dipole is produced in which the Hydrogen is made + and the more electronegative O, N or F atom is made -. If neighboring molecules have the same type of bond created, the two will be attracted to one another and a hydrogen bond (which is still intermolecular) is created. A dashed line represents the intermolecular force of the hydrogen bond. Because hydrogen bonding is very strong, boiling points of compounds that have hydrogen bonds are very high!

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Strengths of intermolecular bonding

London Dispersion Forces are the weakest intermolecular Forces. Dipole-Dipole Forces are stronger than london dispersion Forces but weaker than Hbonding. Hydrogen Bonds are the strongest intermolecular force. Intramolecular forces within a molecule are stronger than all the intermolecular forces (some exceptions, but not to worry about).

Intramolecular Forces
Intramolecular forces holds the atom together in a molecule. Chemical bonding, from previous chapters, involves intramolecular forces. Generally, intramolecular forces are much stronger than intermolecular forces. For these reasons, you can boil something and pull apart its intermolecular forces before you can break apart and create a chemical change in a molecule.

Properties of Liquids
Molecules within a liquid are pulled in all directions by intermolecular forces. Surface Tension: molecules at the surface are pulled downward and sideways by other molecules, but not upward away from the surface. These intermolecular attractions tend to pull the molecules into the liquid and cause the surface to tighten like an elastic film.

Surface Tension is a measure of the elastic force in the surface of a liquid. It is the amount of energy required to stretch or increase the surface of a liquid by a unit area (example: by 1 cm3).
Liquids that have strong intermolecular forces also have high surface tensions.
Capillary action is also surface tension. Adhesion is an attraction between unlike molecules, such as the water and the glass in (a). Cohesion is the intermolecular attraction between like molecules, such as the mercury in (b). If adhesion is stronger than cohesion, (a) occurs. If cohesion is stronger than adhesion (b) occurs. Notice each meniscus.

Using Spheres in Liquids to Minimizing Surface Area

Because there is little or no attraction between polar water molecules and the nonpolar wax molecules on an apple; a drop of water assumes the shape of a small round bead. The sphere shape minimizes the surface area of the polar water liquid being in contact with the nonpolar wax molecules on the apple.

Viscosity
Viscosity is a measure of a fluids resistance to flow. The greater the viscosity, the more slowly the liquid flows. The viscosity of a liquid usually decreases as temperature increases; thus hot molasses flows much faster than cold molasses. Liquids that have strong intermolecular forces have higher viscosities than those with weak intermolecular forces. If molecules are irregularly shaped, they may also slow down when they try and slip past one another, creating a higher viscosity.

Solids
Solids can be divided into 2 categories:
1. Crystalline Solids possesses rigid and long-range order in its atoms, molecules or ions. The 4 types are: Ionic, Covalent, Molecular, and Metallic Crystals. 2. Amorphous Solids lack a well-defined arrangement and have no long-range order. Solids are most stable in crystalline form. However, if a solid is formed rapidly (ex: when a liquid is cooled quickly), its atoms or molecules dont have the time to align themselves properly. The result is an amorphous solid such as glass SiO2. The color in glass comes from added transition metal oxides.

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Crystalline Solid (SiO2 quartz)

Amorphous Solid (glass SiO2 quartz)

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SiO2 Crystal

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Types of Crystals:
Ionic Crystals the lattice points are composed of charged species and anions and cations are generally quite different in size. Most have high melting points (strong electrostatic forces holding them together). To measure the stability of an ionic crystal you look at the lattice energy (the higher it is the more stable the crystal). They do not conduct electricity unless melted (molten) or dissolved in water. They are hard and brittle. Covalent Crystals (AKA Network Crystals) atoms are held together in an extensive 3-D network entirely by covalent bonds. An example is carbon. Both the allotropes diamond and graphite are covalent crystals but have different 3-D networks. In a covalent crystal, the lattice points that hold the crystal together are occupied by separate and different atoms. The atoms can collectively be the same as in the carbon crystals or they may each be altering different atoms an example is SiO2, where one silicon takes up a lattice point and one oxygen bonds covalently on each side of the silicon with each oxygen in their own specific lattice point. They are hard, have high melting points and are poor conductors of electricity. Molecular Crystals the lattice points are occupied by molecules instead of atoms or ions. The attraction between the molecules that hold the crystal together is van der Waals forces and/or H-Bonding. The molecules can be created from one type of atom (such as I2, P4 or S8) or they can have more than one type of atom (such as H2O). They are soft, have low melting points and are poor conductors of electricity.

Ionic

The cations and anions surround one another to minimize repulsions

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Covalent
(a)

(b) Structure of Graphite

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In Molecular Crystals the above lattice points are occupied by molecules, and the attractive forces between them are Intermolecular Forces.

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Molecular Crystal

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S8 at each lattice pt

Molecular Crystal

Metallic Crystals
Metals are good electrical conductors, shiny and malleable. This is all dependant upon their bonding. Metals have a very small number of outer electrons available for bonding. For this reason, the metal atoms become ions with positive charges and the outer electrons are considered delocalized electrons because they float all over the solid in order to stabilize the positive metal cations. In a metal, the bonding electrons are delocalized over the entire crystal. In fact, metal atoms in a crystal can be imagined as an array of positive ions immersed in a sea of delocalized valence electrons. The great cohesive force resulting from delocalization is responsible for a metals strength. The mobility of the delocalized electrons makes metals good conductors of heat and electricity. The group 1A metals have only one outer electron per atom and therefore they have less electrons in their sea of electrons for this reason, they are softer metals. Group 2A have two outer electrons and are therefore harder than the 1A metals. The transition metals are the hardest metals because their outer electrons include d orbitals and can take place in the sea of delocalized electron bonding.

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The positive charges represent the metal cations and the grey areas surrounding them represent the mobile sea of electrons that make the metals stable solids.

Phase Changes
Phase changes are the transformations from one phase to another. They occur when energy is added or removed. Liquid-Vapor Equilibrium When molecules in a liquid have sufficient energy to escape from the surface of a liquid, a phase change occurs. Evaporation, or vaporization, is the process in which a liquid is transformed into a gas. Vapor Pressure increases as temperature increases! When a liquid evaporates, its gaseous molecules exert a vapor pressure. As soon as molecules overcome the intermolecular forces of a liquid they become gases and a vapor pressure is established. This is measurable only after a fair amount of vapor is present. This process does not continue indefinitely. Eventually a maximum equilibrium vapor pressure holds as a constant and the number of molecules that leave the liquid = the number of molecules that enter the liquid (condensation = change from gas to liquid). Therefore the vapor pressure of the liquid stays the same. Condensation occurs because a gas molecule strikes the top of the liquid and is trapped by the intermolecular forces of the liquid. Equilibrium is when the rate of the forward process is equal to the rate of the reverse process.

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h = the vapor pressure of the liquid

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Equilibrium Vapor Pressure is independent of the amount of liquid as long as there is some liquid present, the vapor pressure will be the same for a substance.

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Vapor Pressure increases as temperature increases!

Heat of Vaporization and Boiling Point

A measure of the strength of intermolecular forces in a liquid is the molar heat of vaporization DHvap, which is the energy (usually in kilojoules) required to vaporize 1 mole of a liquid. This is directly related to the intermolecular forces of the liquid. If the intermolecular attraction is strong, it takes a lot of energy to free the molecules from the liquid phase. Therefore, the liquid would have a low vapor pressure and a high molar heat of vaporization.

Boiling Point of a Liquid

The boiling point is the temperature when the vapor pressure of a liquid equals the external pressure. When the liquid converts into the gas phase, at the boiling point temperature, the gas forms a bubble inside the liquid. It then rises to the surface and we see the boiling effect. The reason that the boiling point occurs when the vapor pressure of the liquid equals the external pressure is because the only pressure on the bubble is equal to the external pressure of the atmosphere. If the vapor pressure is equal to the external pressure, then the bubble will not pop and it will successfully make its way to the surface. If, however, the external pressure is higher than the vapor pressure inside the bubble, the bubble would collapse and the boiling action would not occur. The normal boiling point is when the external pressure is 1 atm.

Atmospheric Pressure & B.P.

As you get closer to the earth, gravity has more of an effect on things.

Therefore, as you get closer to the earth, the air becomes more dense due to the fact that the gravity pulls more of the molecules in the air towards the earth. As you therefore go further away from the ground, the pressure of the molecules in the air decreases. Meaning that the atmospheric pressure decreases as you get further and further away from the earth. If the Boiling Point is when the atm pressure = vapor pressure, then as you get further away from the earth, the boiling point of water will decrease due to the fact that the atmospheric pressure decreases.

Critical Temperature and Pressure

The opposite of evaporation is condensation turning a gas into a liquid. A gas can be made to liquefy by either: 1. Cooling the gas (decreasing kinectic energy) until the molecules clump together to form a liquid. 2. By applying pressure to the gas, which will decrease the distance between the gas and then they will clump together to form a liquid. Every substance has a critical temperature (Tc) the highest temperature at which the vapor and liquid states of a substance can exist in equilibrim. Above this temperature, gas will not form a liquid, no matter what applied pressure you add. Critical pressure (Pc) is the minimum pressure that must be applied to bring about liquefaction at the critical temperature.

Freezing Point / Melting Point

The freezing/melting point is when the vapor pressure of the solid = the vapor pressure of the liquid. The normal freezing/melting point is when atmospheric pressure = 1 atm.

The Molar Heat of Fusion DHfus is the energy (usually in kilojoules) required to melt 1 mole of a solid. DHfus is smaller than DHvap because there is more disorder in gas and vaporization needs more energy in order to overcome more intermolecular forces than simply going from a solid to a liquid, which still contains intermolecular forces.

Molar Heat of Fusion DHfus

Sublimation
Sublimation is when the solid molecules go directly into the vapor phase. The Molar Heat of Sublimation DHsub is the energy (usually in kilojoules) required to sublime 1 mole of a solid. It is equal to the sum of the molar heats of fusion and vaporization: DHsub = DHfus + DHvap

Phase Diagrams
The overall relationships among the solid, liquid and vapor phases are best represented in a single graph known as a phase diagram. The point at which all three phases meet is called the triple point, which is the only condition under which all three phases can be in equilibrium with one another.

Specific heat (s) of water for different phases: Solid H2O = 2.09 J/goC Liquid H2O = 4.184 J/goC Gas H2O = 2.01 J/goC
q5 = m (DT) s

q4 = DHvap (mol)

q3 = m (DT) s

q1 = m (DT) s

q2 = DHfus (mol)

qtotal = q1 + q2 +q3 + q4 + q5

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Types of Solutions
Remember that a solution is a homogeneous mixture of two or more substances. This means the substance can be anything, a gas, solid or a liquid. We will focus on solutions consisting at least one liquid: Gas-Liquid, Liquid-Liquid and Solid-Liquid solutions. Remember the capacity to dissolve a solute is as follows: 1. Saturated Solution : contains the maximum amount of a solute that will dissolve in a given solvent at a given temperature. 2. Unsaturated Solution: contains less solute than it has the capacity to dissolve.

3. Supersaturated Solution: contains more solute than is present in a saturated solution. These are not very stable. In time, some of the solute will come out of a supersaturated solution as crystals. To push the process, a seed crystal can be added in order to create a rapid growth of crystals. 4. Crystallization: is the process in which dissolved solute comes out of solution and forms crystals. Crystals differ from precipitates in that they are large and well formed. Precipitates are made up of small particles.

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A Molecular View of the Solution Process

The intermolecular attractions that hold molecules together in liquids and solids also play a central role in the formation of solutions. When the solute dissolves in the solvent, particles of the solute disperse throughout the solvent. The solute particles occupy positions that are normally taken by solvent molecules. The ease with which a solute particle replaces a solvent molecule depends on the relative strengths of three types of interactions: 1. Solvent-solvent intermolecular forces 2. Solute-solute intermolecular forces 3. Solvent-solute intermolecular force

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The heat of the solution is: DHsoln = DH1 + DH2 + DH3 If the solute-solvent intermolecular attraction is stronger than the solvent-solvent and the solute-solute intermolecular attractions, the solution process is favorable, or exothermic (DHsoln < 0). If the solute-solvent intermolecular attraction is weaker than the solvent-solvent and solute-solute intermolecular attractions, then the solution process is endothermic (DHsoln > 0). Sometimes, solutions form even if they are endothermic and take energy to create. You may wonder why? The reason is that the solution has more disorder than the order of the pure solvent or pure solution. Always remember that all physical and chemical processes are governed by both energy and the tendency towards disorder in nature!

Predicting Solubility
Always remember the term, like dissolves like! What this means is that two substances with intermolecular forces of similar type and magnitude are likely to be soluble in each other. If two liquids are soluble in each other, they are said to be miscible. For example, the following molecules are miscible in water because they H-bond with water.

Solvation / Hydration
Ionic solids should be miscible in polar solvent compounds due to the intermolecular ion-dipole interactions. Solvation is the process in which an ion or a molecule is surrounded by solvent molecules arranged in a specific manner. This is known as hydration when the solvent is water. Ionic solids are not miscible in nonpolar solvents due to the inability to solvate the ionic solid.

The Effects of Temperature on Solubility Most of the time, temperature increases solubility. But, the effects are best determined experimentally.

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Fractional Crystallization is the separation of a mixture of substances into pure components on the basis of their differing solubilities. For example, if we have a sample that contains 90 grams of KNO3 that is contaminated with 10 grams or NaCl, then we would dissolve the mixture in 100 mL of water at 60 oC and then gradually cool the solution to 0 oC. At this temperature, the solubilities of KNO3 are 12.1 g/100 g water and NaCl is 34.2 g/100 g water. Therefore, (90 12) g, or 78 g, of KNO3 will crystalize out of the solution, but all of the NaCl will remain dissolved. In this manner, we can obtain about 90 percent of the original amount of KNO3 in pure form. The KNO3 crystals can be separated from the solution by filtration.

Gas Solubility and Temperature

The solubility of gases in water usually decrease with increasing temperature. This should make sense from watching a pot of water heat up. As it heats, you can see bubbles of air forming on the sides of the pot before it boils.
On a hot summer day, a good fisherman knows to fish in a deep spot because it is colder further down with more oxygen gas in the water for the fish.

The Effect of Pressure on the Solubility of Gases

The quantitative relationship between gas solubility and pressure is given by Henrys Law, which states that the solubility of a gas in a liquid is proportional to the pressure of the gas over the solution: c = kP Where c is the molar concentration (mol/L) of the dissolved gas; P is the pressure of the gas over the solution (in atm); and for a given gas, k is a constant that depends only on temperature, with the units of (mol/L x atm). It should make sense that the concentration of the gas is directly proportional to the Pressure. Because, the more gas molecules there are, the more they will hit the surface of the liquid and be able to enter into the liquid and vice versa. The only exception to this rule is if the dissolved gas reacts with the solvent it is in.

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Osmotic Pressure
Osmosis is the selective passage of solvent molecules through a porous membrane from a dilute solution to a more concentrated one. This will occur until the concentrations are equal or there is enough pressure applied to stop the flow of the solvent (osmotic pressure). In the next slide you will see this example, where the left side of the apparatus contains pure solvent and the right contains a solution. The two sides are separated by a semipermeable membrane, which allows passage of solvent molecules but blocks the passage of solute molecules. In the beginning, the water levels are equal. After some time, the level in the right side will rise and continue to go up until the equilibrium is reached, when no further change occurs. The osmotic pressure (p) of a solution is the pressure that is required to stop osmosis. This pressure can be measured directly from the difference in the final fluid levels. osmotic pressure p = MRT M = molarity of the solution, R is the gas constant (o.0821 L x atm/K x mol), and temperature is in Kelvin.

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Colligative Properties of Electrolyte Solutions

Electrolyte solutions contains ionic solids which have dissociated into their ions and is surrounded by a polar solvent. For this reason, we have more than one unit per dissolved electrolyte to think of. For example: NaCl separates into Na+ and Cl-. Therefore, salt should have twice as great colligative properties than a nonelectrolyte solute would have. Another example is CaCl2 , which would produce 3 different ions effect the colligative properties three times as much. To account for this effect we define a quantity called the vant Hoff factor: i = actual # of particles in soln after dissociation number of formula units initially dissolved in solution Then, NaCl and KNO3 = 2 = i & Na2SO4 and CaCl2 = 3 = i. Therefore we know would use: DTbp = iKbm DTfp = iKfm p = iMRT