CHEM. 2AP UNIT 8 CH.

10

Liquids and Solids

CHEM. 2AP UNIT 8 CH. 10 LIQUIDS AND SOLIDS; CH. 11 PROPERTIES OF SOLUTIONS CH. 10 LIQUIDS AND SOLIDS READ P.451-502 ASSIGNMENTS: #1 P.503-504 #13-17, 36-42 even #2 P.505-506 #47-50, 57-59, 63, 64, 71, 72 #3 WS Calorimetry #1-9 NOTES #4 P.508 #81-87 odd, 90, 91 #5 WS Liquids and Solids Review #1-15 NOTES #6 WS Review: Concepts L & S #1-23 NOTES CH. 11 PROPERTIES OF SOLUTIONS READ ASSIGNMENTS: #1 P.552-553 #9-13 odd, 14, 27-33 odd #2 P.554 #39-43 #3 P.554-555 #47-57 #4 P.555-556 #59-67 odd, 68, 71, 72 #5 WS Colloids #1-12 NOTES P.513-552

LIQUIDS AND SOLIDS Gas Low density High compressibility Completely fills its container Indefinite shape, indefinite volume

Solid High density Only slightly compressible Rigid Maintains its shape Definite shape, definite volume Liquid Properties lie between those of solids and gases

H2O(l) H2O(s) H2O(g) H2O(l)

H fusion = 6.02 kJ/mol H vaporization = 40.7 kJ/mol

The large value of H vaporization suggests a much greater change in structure in going from a liquid to a gas than from a solid to a liquid Suggests that there are extensive attractive forces among the molecules in liquid water, similar but not as strong as those in the solid state.

Similar densities of the solid and liquid state indicate similarities in the structure of liquids and solids: Densities of the three states of water: D = 3.26 x 10-4 g/cm3 (400C) H2O(g) H2O(l) D = 0.9971 g/cm3 (25C) D = 0.9168 g/cm3 (0C) H2O(s)

12/24/2002

CHEM. 2AP UNIT 8 CH. 10

Liquids and Solids

PHASES OF MATTER AND THE KINETIC MOLECULAR THEORY Solids and liquids are grouped together separate from gases because they have some common properties that can be examined. The densities, compressibilities and heats of phase change all indicate that the forces that hold solids and liquids together are similar. Gases have no such forces. 1. 2. 3. 4. The kinetic molecular theory of gases assumes that Gas molecules or atoms are widely separated No forces of attraction exist between them The molecules are in continual, random and rapid motion Their kinetic energy is determined only by the gas temperature.

The first two points only are the ones that distinguish gases from liquids and solids. Because gases have no forces attracting molecules to one another, gases can expand infinitely to fill their containers uniformly and completely. In contrast, stronger forces exist in liquids and solids, and these attractive forces in a liquid or solid prevent a significant expansion of a liquid or solid. The properties of liquids and solids are determined by the forces that hold the components of the liquid or solid together. They may be: Covalent bonds Ionic bonds Weaker intermolecular forces between molecules Intermolecular Forces (IMFs) Intramolecular forces are covalent bonds between atoms to form molecules. These are forces within a molecule. (Water the intramolecular forces are covalent bonds that hold the O and H atoms to each other within the water molecule. Intermolecular forces mean forces between molecules. These are forces that hold the components of the liquid or solid together. (Forces holding one water molecule to another water molecule.) Intermolecular forces are weaker than covalent and ionic bonds. That is why it is easy to separate water molecules from one another but very difficult to separate a water molecule into H and O atoms. It is important to realize that when a substance such as water changes from solid to liquid to gas, the molecules remain intact. The changes in states are due to changes in the forces among the molecules rather than in those within the molecules. ****IN THIS SECTION, WHEN CONSIDERING THE TYPES OF FORCES BETWEEN PARTICLES (INTERPARTICLE FORCES), YOU MUST ALWAYS AND FOREMOST ASK WHAT KIND OF PARTICLES ARE BEING ATTRACTED TO EACH OTHER. THE POSSIBLE TYPES OF PARTICLES ARE: IONS ATOMS BY THEMSELVES: o GROUP 8A ATOMS (INERT GASES) o METAL ATOMS o SPECIFICALLY CARBON ATOMS AND SILICON ATOMS (WITH OXYGEN) MOLECULES TYPES OF INTERPARTICLE FORCES In order to understand the forces between solid and liquid particles (interparticle forces), we will first determine the types of forces that can exist between particles and then move to a description of the liquid and solid phases. There are different forces of attraction involved in solids and liquids. From strongest to weakest they are: 1. Network Covalent Bonds bonds between single carbon atoms; bonds with silicon atoms (explained later). 2. Ionic Bonds bonds between ions 3. Metallic Bonds bonds between metal atoms 4. Intermolecular forces bonds between molecules (and Group 8A atoms). Three types: (a) Dipole-dipole IMFs (b) Hydrogen bonds (c) London dispersion forces (aka Van der Waals Forces) Without these forces, all substances would be in the gas state EVEN YOU!!!

12/24/2002

CHEM. 2AP UNIT 8 CH. 10

Liquids and Solids

STRENGTH OF INTERPARTICLE FORCES STRONG BONDS (strongest to weakest) 1. Network Covalent Bonds 2. Ionic Bonds 3. Metallic Bonds WEAK BONDS (strongest to weakest) (Intermolecular Forces) 1. Ion-Dipole Forces 2. Hydrogen Bonding (a very strong dipole-dipole force) 3. Dipole-Dipole Forces (about 1% as strong as covalent or ionic bonds) 4. Dipole-Induced Dipole forces 5. Induced Dipole-Induced Dipole Forces **London Dispersion Forces occur when any induced dipoles exists (4 and 5 above) All these forces will be explained first briefly. More explanation with regard to the three strong bonds will be coming later when we discuss specific solids and liquids. THE STRONG FORCES 1. NETWORK COVALENT BONDS Strongest strong bond. Occur only in solids In a network solid, atoms are covalently bonded in a lattice structure (crystals) Network solids are very hard and their strong bonds result in very high melting and boiling point temperatures. Network solids have localized electrons that are in fixed positions in the covalent bonds. The electrons stay localized with their atoms. This makes network solids poor conductors of electricity. Examples of network solids include o Diamond a form of carbon in which its electrons have an sp3 hybridization and the atoms are arranged in a tetrahedral network. o Quartz (rock) SiO2 IONIC BONDS (Between ions) Medium strong bond. In an ionic solid, adjacent ions have electrostatic attractions and are arranged in a lattice structure. Ionic solids have strong bonds resulting in high melting and boiling point temperatures. Ionic solids have localized electrons which are in fixed positions around the atoms. This makes ionic solids poor conductors of electricity. Ionic liquids however (ex. molten NaCl) do conduct electricity because the electrons are free to move about. Coulombs Law states that the force of attraction between two objects is equal to the product of their charges (q1 and q2) divided by the square of the distance between them (r). F= o o

2.

q1q2 r2

Therefore, the charges on the ions in an ionic solid are directly proportional to the strength of the ionic bonds, that is the higher the charge on the ion, the stronger the ionic bond. The sizes of the ions in an ionic solid are inversely proportional to the strength of the ionic bonds, that is the larger the ion, the weaker the ionic bond. Ex: The ionic bonds in MgO (charges +2 and 2) are stronger than those in NaF (charges +1 and 1). Ex: The ionic bonds in LiF are stronger than those in KBr (because LiF is much smaller than KBr).

3.

METALLIC BONDS (bonds between metal atoms) Weakest strong bond Metallic solids are often described as a group of nuclei surrounded by a sea of mobile electrons. In other words, the electrons in metallic solids are delocalized and are free to move about, making metals good conductors of electricity. Metallic bonds are still relatively strong forces of attraction and most metals have high melting and boiling point temperatures. Mercury is the only metal that is not solid at room temperature. Though most metals are very hard, the unrigid structure of the electrons makes them malleable and ductile. Like in ionic solids, Coulombs Law can be used to describe the relative strengths of metallic solids:

F=

q1.q2 r2
12/24/2002

CHEM. 2AP UNIT 8 CH. 10

Liquids and Solids

When considering the interparticle force between metal atoms, the first determining factor is the size of the ionic charge. The larger the ionic charge of the cation, the more strongly held they are and the higher the melting point. Melting point Pb4+ > melting point Na+ even though Na+ has a smaller ionic radius. The size of the metal atoms is inversely proportional to the strength of the metallic bonds. In other words, the smaller the atoms, the stronger the force. Smaller size allows for the positively charge nucleus of one metal atom to be closer to the negatively charged electrons of another, increasing the strength of the attraction between them. Forces of Na+ > forces of K+ because Na+ has a smaller radius. Therefore, Na metal has a higher melting point than K metal.

INTERMOLECULAR FORCES (the weak forces)

1. ION-DIPOLE FORCES (strongest weak bond) A dipole consists of separated positive and negative charges, so an ion can be attracted to one end of the dipole and be repelled by the other. Polar molecules are dipoles; they have a positive end and a negative end. Ion-dipole forces are especially important in solutions of ionic substances in polar liquids. An ion-dipole interaction that is of particular interest to chemists involves the interaction of ions with water molecules, because these interactions are involved in the dissolving of ionic solids such as salt NaCl in water. The strength of an ion-dipole attraction depends on: 1. The distance between the ion and the dipole: the closer the ion and the dipole the stronger the attraction. 2. The charge on the ion: the higher the ionic charge, the stronger the attraction. 3. The magnitude (size) of the dipole: the greater the magnitude of the dipole, the stronger the attraction. (The more positive or negatively charged the ends of the molecule are). DIPOLE-DIPOLE FORCES (medium weak bond) A dipole-dipole force exists between neutral polar molecules. Polar molecules attract each other when the positive end of one molecule is attracted to the negative end of another molecule. Dipole-dipole forces are about 1% as strong as covalent or ionic bonds. They become weaker with distance. The greater the polarity (difference in electronegativity of the atoms in the molecule), the stronger the dipole-dipole attraction. Dipole-dipole attractions are very weak and substances held together by these forces have low melting and boiling point temperatures. Generally, substances held together by dipole-dipole attractions are gases at room temperature. In general, the melting point and boiling point for a polar compound are higher than those for a nonpolar compound of approximately equal molar mass. Substance Molar mass (g/mole) Boiling point (K) Propane (non polar) 44 231 Acetaldehyde (polar) 44 294 The presence of permanent dipoles influences how soluble a substance is. Polar molecules dissolve in polar solvents and nonpolar molecules dissolve in nonpolar solvents giving rise to the saying LIKE DISSOLVES LIKE. Water (polar) dissolves alcohol (polar). Water and oil (non-polar) do not mix but oil and gasoline mix because both are nonpolar.

2.

12/24/2002

CHEM. 2AP UNIT 8 CH. 10

Liquids and Solids

3.

LONDON DISPERSION FORCES (involve induced dipoles - weakest weak bond) London dispersion forces (LDF) occur between neutral, nonpolar molecules. LDF occur due to the random motion of electrons. Non-polar molecules must exert some kind of force or they would never solidify. They are the most common of all IMFs and are found in all molecular substances. They are electrostatic in nature and arise from attractions involving induced dipoles. The fact that non-polar gases can be liquefied tells us that there must be some kind of attractive interactions between the particles. Dispersion forces are attractive forces that arise as a result of temporary dipoles induced in atoms or molecules. O2 is nonpolar and isnt expected to be very soluble in water which is highly polar. The very fact that it dissolves in water at all is due to the ability of polar molecules to induce (to make happen) a dipole in a nonpolar molecule. The approach of the polar molecule causes a shift in the electron density of the nonpolar molecule thus inducing a temporary or instantaneous dipole in the otherwise nonpolar substance. All the electrons will shift to one side of the molecule. The process of inducing a dipole is called polarization and the degree to which the electron cloud of an atom or molecule can be distorted is called its polarizability. The more electrons there are in atom or molecule, the more easily the electrons can be polarized, because they are further from the restraining forces of atomic nuclei. Polarizability therefore increases with increasing size, and increasing size is usually accompanied by increasing molar mass. Polarizability is thought of to be the measure of the squashiness of its electron cloud. DISPERSION FORCES EXIST BETWEEN ALL MOLECULES (whether polar or non-polar) AND ATOMS. THE ONLY ATTRACTIVE IMFS THAT EXIST BETWEEN NONPOLAR MOLECULES ARE DISPERSION FORCES. DISPERSION FORCES INCREASE IN STRENGTH WITH INCREASING MOLECULAR WEIGHT. (See chart below). This table shows the increased boiling point as the molar mass (and number of electrons increases. MELTING POINTS OF SIMILAR NONPOLAR COMPOUNDS COMPOUND MELTING POINT (C) CH4 -182.5 CF4 -150.0 CCl4 - 23.0 CBr4 90.0 CI4 171.0

In fact, dispersion forces between polar molecules can contribute more to overall attractive forces than do dipole-dipole forces. For example, the B.P. of HBr is 206.2K. The B.P of HCl is 189.5K. The stronger attractive forces for HBr cannot be attributed to greater dipole-dipole forces because HCl is more polar so it should have a higher B.P. The higher B.P of HBr (a heavier molecule) is due to the stronger LDFs due to the increased molecular weight and size. In this case LDF the attractive forces contribute more to the attraction between molecules than does the dipole-dipole interaction. In general, dispersion forces are weaker forces than dipole-dipole IMFs. In many cases, dispersion forces are the same or even greater than dipole-dipole forces between polar molecules. This is because some nonpolar molecules contain many more electrons than the electrons in the molecule with a dipole. The electrons are held very loosely so a very strong induced dipole is created. Here is another example: (M.P. 141.8 C) IMFs: dipole-dipole, dispersion forces CH3F polar nonpolar (M.P. 23 C) IMFs: dispersion forces only. CCl4 The M.P. of CH3F should be higher because dipole-dipole forces are stronger. CCl4 has a higher M.P. because it contains more electrons (higher molar mass). As a result, the dispersion forces between CCl4 molecules are stronger than dispersion forces plus the dipole-dipole forces between CH3F molecules.

12/24/2002

CHEM. 2AP UNIT 8 CH. 10

Liquids and Solids

LDFs are very weak and short-lived. To form a solid when only LDFs exists requires very low temperatures. The molecules or atoms must be moving slowly enough for the LDFs to hold the molecules or atoms together in a solid unit. Notice that as the MM of the noble gas increases, the freezing point increases. This implies that the LDF between the atoms is stronger as the MM increases. Element Freezing Point (C) helium -269.7 neon -248.6 argon -189.4 krypton -157.3 xenon -111.9 HYDROGEN BONDING (strongest weak bond after ion-dipole force) A hydrogen bond is an especially strong dipole-dipole IMF. It exists between the hydrogen atom in a polar bond and is a bridge between hydrogen and highly electronegative atoms namely F, O, and N. (FON) Because H is very small and the other atoms are highly electronegative, a very strong dipole is produced. Ex. H2O, HF, NH3.

Example 1: Which of the following can form hydrogen bonds with water? (Hint: Draw the structures first and determine the shape. (a) CH3OCH3 (e) Na+ (c) F(b) CH4 (d) HCOOH

Example 2: Which of the following species are capable of hydrogen bonding among themselves? (Hint: Draw the structures first.) (a) H2S, (b) C6H6 (c) CH3OH

12/24/2002

CHEM. 2AP UNIT 8 CH. 10

Liquids and Solids

TRENDS IN THE PERIODIC TABLE Boiling points and melting points have a tendency to increase as molecular weight increases. As you go left to right across a period, the boiling points of similar substances containing elements in the same period should increase with increasing molecular mass. (See chart below for CH4, NH3, HF, H20.) Contrary to the trend, the lightest compound has the highest boiling point contrary to our expectations based on molar mass (should be higher molar mass = higher B.P.). Expected B.P.: HF > H2O > NH3 > CH4 Actual B.P.: H2O > HF > NH3> CH4 Why this exception? All are polar except CH4. (only dispersion forces) therefore CH4 has the lowest B.P. as expected. H2O has extensive H bonding due to 2 unshared pairs of electrons on O. HF and NH3 both have H bonding but HF is more polar due to the high electronegativity of F. Another exception: As you go down a family or group, the B.P. is expected to increase due to increased molecular mass. In group 4A the trend is followed. In groups 5A, 6A, and 7A the trend is not followed due to the effect of strong hydrogen bonding. (See figure below.)

LINEAR AND BRANCHED MOLECULES - FORCES IN MOLECULES WITH THE SAME MOLECULAR WEIGHT Two molecules have the same molecular formula C4H10 (M.W. 58.14 amu). but different structures: n-butane (B.P. 0.5C) methylpropane (B.P. 11.7C) Linear structures are held more strongly by IMFs because they can be stacked making more bonds. (See the diagrams below.)

12/23/2002

CHEM. 2AP UNIT 8 CH. 10

Liquids and Solids

PROBLEMS 1. Indicate the most important types of intermolecular forces that exist in each of the following substances (e) Cs (a) BaSO4 (i) P4 (f) Hg (b) H2S (j) H2O (c) Xe (g) P4 (d) C2H6 (h) Hg 2. 3. 4. 5. Which of the following substances should have the strongest intermolecular forces and why? N2, Ar, F2, Cl2 HCl has a higher dipole moment than HCN. Which one should have the highest boiling point and why? Put the following molecules in order of increasing polarizability: GeCl4, CH4, SiCl4, GeBr4. Predict which would have the greater interparticle force: (a) CO2 or OCS (b) PF3 or PF5 (c) SO2 or SO3 (d) SF2 or SF6

DO ASSIGNMENT #1 ON ASSIGNMENT SHEET P. 503-504 #13-17, 36-42 even

12/23/2002