Chemistry Notes

Steven W. Walker February 8, 2012

Basic Thermodynamics of Chemistry

The change in heat of a substance can be dened as: q = mCs T Where CS is the specic heat of the substance. When objects are in thermal equilibrium, qsubstance qsubstance b .
a

Enthalpies of Vaporization and Fusion When a substance freezes or vaporizes, it takes an energy of nH or mH depending on the units H is given in. When a substance is undergoing a phase change, there should be no change in temperature. Phase Diagrams There are several key features on a standard pressure vs. temperature phase diagram.

Triple Point The triple point is where all 3 phases of a substance can coexist. Critical Point The critical point is the last point where a liquid can exist. Beyond this point there is only gas and a special phase known as the supercritical uid. Deposition The change from gas to solid. Sublimation The change from solid to gas. Condensation The change from gas to liquid. Evaporation The change from liquid to gas.

Melting The change from solid to liquid. Freezing The change from liquid to solid.

Vapour Pressure
Vapour pressure is dened as the pressure of vapours above a condensed liquid in a closed system. IMPORTANT: The vapour pressure at the boiling point og a substance is 1 atm. Note that vapour pressure reaches a dynamic equilibrium, meaning it never stays completely stable but rather relies on the constant exchange of particles. It can be described using the Clausius-Clapeyron relation. One Point Clasius-Clapeyron ln(P ) = Hvap + ln() RT

Two Point Clasius-Clapeyron ln( P2 Hvap 1 1 )= ) ( P1 R T2 T1

Crystal Structures
Crystalline units are known as Unit Cells. An arrangement of unit cells within a solid is known as a crystalline lattice. Much like a polymer, unit cells repeat. Cubic Unit Cells Cubic unit cells possess equal edge lengths and 90 angles at each corner. There are 3 types (Simple, BodyCentred, and Face Centred). Atoms are shared between neighbouring units. Corners share 8 units while faces share 4. The coordination number refers to the number of atoms with which each atom is in direct contact. Edge length is dened as the radius of an atom. The packing eciency refers to the percentage of volume occupied by atoms. Simple Cubic Unit Cells Simple Cubics possess a coordination number of 6 1 atom per unit cell and an edge length of 2r. Body Centred Cubic Unit Cells These unit cells have a coordination number of 8, 2 atoms per unit 4r cell, and an edge length of 3 . Face Centred Cubic Unit Cells These cells have a coordination number of 12,4 atoms per unit, and an edge length of 8r.
g Example Platinum crystallises in a face-centred cubic lattice. It has a density of 21.45 cm3 and an g atomic mass of 195.08 mol . What is the unit cell edge length? First nd the volume of a single cell

Now take the cubic root.

1 mol 4 atoms cm3 195.08 g cm3 = 6.04 1023 23 atoms 21.45 g mol 6.022 10 cell cell 3 6.04 1023 = 3.9235 108 cm

Closest-Packing of Atoms Layers of atoms that orient relative to each other can maintain two possible closest packing forms, hexagonal (hcp) and cubic (ccp). The CCP corresponds to face-centred cubic unit cells.

Important Relations
Mole Fraction xi = Molarity Mi = Molality mi = ni ntotal ni Vtotal ni mtotal

Solutions
A solution is composed of a solvent and the solutes that are dissolved in it. Solutions can be in any phase, not just liquids. The mixing of two like liquids is spontaneous.

Properties Relating to Solubility:

Solubility The amount of a substance that will dissolve in a given amount of solvent is the solubility. This varies with the substance, solvent, and temperature. Entropy Entropy is a measure of disorder. The combination of two substances results in spontaneous mixing. Species above 0 K have energy. Mixing allows energy to spread. Intermolecular Forces Dierent IMFs can either help or hinder the formation of a solution. Solution interactions include solute-solute, solvent-solvent, and solvent-solute. Solvent-Solute Solvent-Solute Solvent-Solute > = < Solvent-Solvent and Solute-Solute Solvent-Solvent and Solute-Solute Solvent-Solvent and Solute-Solute Miscible Miscible Solution may or may not form

In any solution Hsolute > 0 and Hsolvent > 0. Hmixed > 0 However can be less than 0 for an endothermic reaction or greater than 0 for an exothermic reaction. At the equilibrium of a solution, the ration of dissolution should equal the rate of recrystallization. Solubility and Environmental Conditions Solubility is generally lower at higher temperatures and is much higher in high pressure environments as solubility and pressure are directly proportional. Henrys Law Henrys Law quanties the solubility of gases. Sgas = kH Pgas Molarity vs. Molality Molarity is
molsolute Lsolution

while Molality is

molsolute kgsolvent

Colligative Properties
Colligative properties are found in solutions. They depend on the number of particles dissolved and NOT on identity. Vant Ho Factor, i The number of moles of particles per unit. N aCl i = 2 AlCl3 i = 4 KN O3 i = 2 C6 H12 O6 i = 1 Vapour Pressure Depression Vapour pressure of a solution will be lower in a solution than in the pure solvent. Raoults Law
o Psoln = solvent Psolvent

Where P is the vapour pressure, is the mole fraction, and P o is the vapour pressure of the pure solvent. Freezing Point Depression Solutions generally have lower freezing points than a pure solvent. This can be be calculated using: T = imKf Where FP is the change in temperature, i is the Vant Ho factor, m is the molality, and Kf is the freezing point depression constant. 3

Boiling Point Elevation Boiling point is raised by the addition of a solute. T = imKb Where FP is the change in temperature, i is the Vant Ho factor, m is the molality, and Kb is the boiling point elevation constant. Osmotic Pressure Osmosis is the ow of a solvent from a lower concentration to a higher concentration through a semipermeable membrane.Osmotic pressure is the amount of pressure needed to stop osmotic ow. = iM RT In this case, is the osmotic pressure, i is the Vant Ho factor, M is the molarity, and R is the ideal gas constant. T must be in Kelvin. A solution will share colligative properties with an isotonic (isosmotic) solution where the number of particles is the same. When there is a higher solute concentration outside of a membrane than inside, the solution is known as hypertonic. When the concentration of solute is higher inside a membrane than outside, the solution is hypotonic. Solvent always ows from low concentration to high concentration. Volatile Solute in a Volatile Solvent Both contribute to vapour pressure.
o PA = A PA o PB = B PB

Ptotal = PA + PB Colloids Colloids are similar to a solution, but dierent. These substances are a mixture in which a dispersed substance is divided in a dispersant. The particles dispersed are generally rather large (comparatively speaking). Types of colloids: Classication Aerosol Solid Aerosol Foam Emulsion Solid Emulsion Dispersing Substance liquid solid gas liquid liquid Dispersing Medium gas gas liquid liquid solid Example fog smoke whipped cream milk opal