AP CHEM REVIEW Atomic Structure and the Periodic Table The Periodic Table:

6 is the atomic number of the element, also number of protons and electrons around nucleus at neutral state. 12.01 is the molar mass, also called the atomic weight. The nucleus contains protons and neutrons. The mass number of an atom is the sum of its neutrons and protons. Different numbers of neutrons are called isotopes. Molar mass is the average of the mass numbers of all known isotopes. Horizontal rows are periods, vertical columns are groups.

Electrons: The position of electrons in relation to the nucleus is described as the quantum number. Each electron has four quantum numbers that apply to shell, subshell, orbital, and spin. Shells n= 1, 2, 3- In hydrogen, the shell of an electron determines its average distance from the nucleus as well as its energy. Shells with higher values are farther, have more energy and are less stale than shells with lower values. Subshells l= 0, 1, 2- describes the shape of an electrons orbital. The first shell (n=1) has one subshell, s or l=0. The second (n=2) has 2 subshells: s (l=0), and p (l= 1). The third shell (n=3) has 3 subshells: s (l=0), p (l=1), and d (l=2). S subshells are spherical, while the orbitals of p subshells are shaped like dumbbells. Orbitals m1=-1, 0, 1 - Describes the orientation of the orbital in space. S subshell has one orbital m1=0. P subshell has three orbitals, m1=-1 through +1. The D subshell has five orbitals, m1= -2 through 2. Spin m2= , -1/2, each orbital can contain two electrons one with positive spin, and one with negative. The Aufbau principle states that when building up the electron configuration of an atom, electrons are placed in orbitals, subshells, and shells in order of increasing energy. The Pauli Exclusion Principle states that within an atom, no two electrons can have the same set of quantum numbers.

Hunds rule states that when an electron is added to a subshell, it will occupy an empty orbital of one is available. Diamagnetic elements have all of their electrons sins paired ( all subshells completed)

Paramagnetic elements do not have all of their electrons spin paired. They are strongly affected by magnetic fields. The electrons have potential energy that increases with distance from the nucleus. Energy of the electron is quantized that means electrons can only exist at specific energy levels, separated by specific intervals. When atoms absorb energy in the form of electromagnetic radiation, electrons jump to higher energy levels. When electrons drop from higher to lower energy levels, atoms give off energy in the form of electromagnetic radiation. Daltons Elements: There are many different kinds of atoms, called elements. These elements combine to form compounds that always contain the same ratios of elements. He also said atom are never created or destroyed in chemical reactions. Mendeleev and Meyer independently arranged the elements into early versions of the periodic table. Thompsons Experiment- He watched the deflection of charges in a cathode ray tube and put forth the idea that atoms are composed of positive and negative charges. Millikans Experiment: He was able to calculate the charge of an electron by examining the behavior of charged oil drops in an electric field. Rutherfords experiment: He fired alpha particles at gold foil and observed how they were scattered. Showed that the positive parts of an atom are concentrated at the center and the atom in mostly empty space. This led to the idea of the positive nucleus. Electromagnetic energy is quantized. Which means, for a given frequency of radiation or light, all possible energies are multiples of a certain unit of energy, called a quantum. Bohr Model: It tried to predict that electrons orbit the nucleus at specific fixed radii, however this only works for atoms and ions with one electron i.e. H. Heisenberg Uncertainty principle states it is impossible to know both the position and momentum of an electron at a particular instant. This means, electron orbitals do not represent specific orbits. An electron orbital is a probability function describing the possibility that an electron will be found in a region of space. De Broglie said that all matter has wave characteristics. The closer an electron is to the nucleus; the more strongly it is attracted. The more protons, the stronger the attraction. If other electrons are between a valence electron and the nucleus, the less attraction from the valence electron; this is called shielding. Completed shells are stable; Atoms prefer to add or subtract valence electrons to complete shells if possible. Atomic radius is the distance from the nucleus to the valence electron. From left to right across the periodic table, protons are added to the nucleus, so the valence electrons are more strongly attracted to the nucleus; this decreases the atomic radii. Moving down a group, shells of electrons are added to the nucleus. When electrons are removed from an atom, a cation is formed; the outer shell is removed, making the cation smaller than the atom.

When electrons are added to an atom, an anion is formed, electron-electron repulsions increase, and the valence electrons move farther out, increasing the radius. It takes energy to remove an electron; this energy is called ionization energy. Once an electron has been removed, the atoms become positively charged. Left to right across a period, protons are added, so the negatively charged valence electrons are more strongly attracted to the nucleus; this means ionization energy increases. Moving down a group, shells of electrons are added, so the pull of the nucleus on thee valence electrons is reduced, and the ionization energy is decreased. The second ionization id greater than the first ionization energy- the energy required to remove the first electron. When the valence shell is empty, the next electron must come from a shell that is much closer to the nucleus, making the ionization energy larger. For Na the second ionization energy is much larger than the first. For Mg the first and second ionization are comparable. For Al, the first three ionization energies are comparable. Electron Affinity is a measure of the change in energy of an atom when an electron is added to it. The atom becomes more stable when an electron is added, and energy is given off. When the addition of an electron makes the atoms less stable, energy must be put in. Electronegativity refers to how strongly the nucleus of an atom attracts the electrons of other atoms. They are estimated based on ionization energies.

Bonding Coulombs Law: Atoms stick together to form molecules, and atoms and molecules stick together to form liquids or solids because the electrons of one atom are attracted to the nucleus of another atom. From coulombs law- bigger charges mean stronger bonds; smaller charges mean weaker bonds. Charges close together mean strong bonds; charges far apart mean weak bonds.

Bonds: Atoms form molecules because they like to have a full shell of valence electrons- 8. When an atoms gives up electrons to another atom an ionic bond forms. When electrons are shared a covalent bond is formed. Ionic solids are held together by the electrostatic attractions between ions that are next to one another in a lattice structure. Often between metals and nonmetals. One atom gives up electrons and becomes a positively charged ion while the other atom accepts electrons and become a negatively charged ion. The two are then held together by the attraction. Substances held together by ionic bonds have high melting and boiling points.

In an Ionic solid each electron is localized around a particular atom, so electrons do not move around the lattice- this makes ionic solids poor conductors of electricity. Ionic liquids conduct electricity because the ions themselves are free to move about in the liquid phase. In a covalent bond, two atoms share electrons to complete their valence shell. The first covalent bond to form is a sigma bond. The second bond in a double bond and the second and third in a triple bond is a pi bond. Double and triple bonds are stronger and shorter than single bonds.

Bond type Designation Order Length Energy Double Triple One sigma One sigma One pi Two pi One Two Three Longest Intermediate Shortest Least Intermediate Greatest Usually, the more electronegative atom in a bond will have a stronger pull on the electronsenough to keep the electrons on one side longer- called polarity. This gives the molecule a dipole- where the side with electrons is negative, and the other positive. The diploe moment measures polarity. The larger, the more polar, the greater the charge at the ends, and the greater the distance, the greater the value of the dipole. To make a Lewis structure, count the valence electrons, take into count the charge, put the least electronegative atom in the center, and balance the valence shell. When double bonds are used, they can be placed anywhere- called resonance structures. They exist simultaneously, and have the same strength and length. Atoms can complete the outer shell without 8 valence electrons- called incomplete octets. These include hydrogen, born and beryllium. Atoms in the d subshell, the central atom can have more than 8 valence electrons- called expanded octets. They include: PCl5, SF4, and SF6. Molecules can have odd electrons, usually nitrogen, like NO and NO2. Single One sigma

Molecular Geometry: Molecules try to keep their electrons as far apart as possible. When we try to predict their positions, we use valence shell electron-pair repulsion (VSPER) model. The molecule is determined by the number of electron domains on the central atom. The central atom forms hybrid orbitals, each of which has a standard shape. If there are 2 electron domains, there is an sp hybridization, and a linear shape. If there are 3 electron domains, there is an sp2 hybridization, and a trigonal planar shape with 120 bond angles. With no lone pairs, the geometry is trigonal planar; with 1 electron pair, it is bent 120. If there are 4 electron pairs, there is an sp3 hybridization, with a tetrahedral shape and 109.5 angles. With no lone pairs, the geometry is tetrahedral. With 1 lone pair, it is trigonal pyramidal; with 2 lone localized pairs, it is bent 109.5.

If there are 5 electron pairs, there is an dsp3 hybridization, with a trigonal bipyramidal shape. With no lone pairs, the geometry is trigonal bipyramidal; with 1 lone pair, it is seesaw; with 2 lone pairs, it is T-shaped; with 3 lone pairs, it is linear. If there are 6 electron pairs, there is a d2sp3 hybridization, with an octahedral shape. With no lone pairs, the geometry is octahedral; with 1 pair it is square pyramidal; with 2 pairs it is square planar.

Bonds between Molecules: Intermolecular forces only exist with covalently bonded molecules. Network solids have their atoms held together in a lattice of covalent bonds. They are hard, have very high melting and boiling points. Electrons are not free to move around because they are localized in covalent bonds between particular atoms. This makes them poor conductors. Carbon diamonds and silicon quartz are common examples. Diamonds are hard because of the tetrahedral network structure of carbon. Metallic Bonds can be compared to a group of nuclei surrounded by a sea of mobile electrons. Most metals are very hard; however they are malleable and ductile because their electrons are free to move around. Except for mercury, all metals are solid at room temp, and most have high boiling and melting points. Those with atoms of smaller nuclei tend to make stronger bonds than those with larger nuclei. The freedom of electrons makes them good conductors. Van der Waals forces: Dipole dipole occurs between neutral, polar molecules: the positive end of one polar molecule is attracted to the negative end of another. The greater the polarity, the greater the dipole-dipole attraction. Bigger dipole moments mean higher boiling and melting points. In general, the attraction is weak so there is low MP and BP. Most are gases and liquids at room temp. London dispersion forces occur between neutral, nonpolar molecules. They are very weak because the movement of the electrons is random. Molecules with more electrons have greater LD forces. They are even weaker than Dipole dipole. They have low MP and BP and are gases at room temp. In hydrogen bonds, the positive hydrogen end of a molecule is attracted to the negative end of another molecule (F, O, N). They are stronger than dipole-dipole forces because when hydrogen gives up its electron, its nucleus is unshielded. They have high MP and BP. Waters hydrogen bonds force ice molecules to form a crystal structure, which keeps them farther apart, and more dense than in the water state.

Stoichiometry and Chemical Equations Math: Nonzero numbers are sandwich zeros are significant. Zeros to the left of the first nonzero are not significant. Zeros at the end of a number to the right of the decimal are significant.

Zeros at the end of a number greater than 1 are not significant unless there is a decimal point. When multiplying/ dividing, the result should have the same number of sig-figs. When adding/subtracting, the result should have the same number of places. If 10x=y, then log y = x. If ex=y, then ln y = x. E= 2.7183; ln y= 2.303 log y. Log (ab) = log a +log b. Log (a/b) = log a log b. 1 mol = 6.0222 x 1023 Moles = liters/ (22.4 L/mol) STP= 1 atm at 273 K. At STP, one mole of gas occupies 22.4 L. moles= Molarity x liters Moles= molality x kg of solvent. The empirical formula is the simplest ratio of elements in a compound. The molecular formula is the actual formula.

Gases STP: Pressure= 1 atm=760 mmHg; Temp= 0 C = 273 K. 1 mol gas occupies 22.4 L.

Kinetic Molecular Theory: Gases are considered to behave in an ideal manner, thus you can assume- the kinetic energy of a gas is directly proportional to its temperature. The higher the temperature, the higher the KE. The total KE of a gas sample: KE= 3/2 nRT; R= 8.31 Joules/mol-k The average KE of a single gas molecule: KE= mv2 ; mass in kg. The average KE of a gas is based on the temperature, not on the specific gas. The volume of the gas container is more important than the volume of the gas. There are no forces of attractions between gas molecules Gas molecules are always in motion, and colliding with each other.

The Ideal Gas Equation: PV=nRT; (atm)(L)=mol(.0821 L-atm/mol-k)(K) P1V1/ T1 =P2V2/T2 When volume is constant: pressure and temperature are directly related. If the temperature is constant: pressure and volume are inversely related according to Boyles Law.

If the pressure is constant: Temperature and volume are directly related according to Charless Law.

Daltons Law The total pressure of a mixture of gases is the sum of all partial pressures of the individual gases in the mixture. Ptotal= P1+P2 The partial pressure of a gas is directly proportional to the number of moles of that gas present in the mixture. P1=(Ptotal)(Xa); Xa= moles of gas A/ total moles of gas.

Grahams Law: Used to find the average speed of a gas molecule. See pg 86 for equation. At a given temperature, lighter molecules move faster than heavier ones.

Van Der Waals Equation: At low temperatures and/or high pressures, gases are no longer ideal; the assumptions made in kinetic molecular theory are no longer true because molecules are packed too tightly together. At these conditions, the volume of the gas becomes significant, and gas molecules attract one another and stick together. (P + n2a/V2)(V-nb)=nRT; a and b are constants.

Density:

Density is always measured the same; mass/volume.

Phase Change The Phase Diagram: High pressure and low temperature is solid phase. Low pressure and high temperature is gas phase. Liquid phase is in between. Lines on the phase diagram show where the substance can be both phases at equilibrium. Freezing point is where the solid-liquid line crosses the 1 atm pressure line. Boiling point is where the liquid- gas line crosses the 1 atm line. Triple point is the temperature and pressure where the substance can be all three phases in equilibrium. Critical point is the temperature beyond which the molecules of a substance have too much KE to stick together and form a liquid.

Phase Change: Solid to liquid- Melting Liquid to solid- Freezing Liquid to gas- Vaporization Gas to liquid- Condensation Solid to gas- Sublimation Gas to solid- Deposition Phase changes occur because of changes in temperature and/or pressure. Some particles in a liquid or solid will have enough energy to break away from the surface and become gaseous. The pressure they exert is called vapor pressure. When the l/s phase is in equilibrium with the gas phase the gas pressure will equal the vapor pressure. Temperature and vapor pressure are directly proportional. When the vapor pressure is equal to the atmospheric pressure, the liquid boils. The heat of fusion is the energy needed to melt a substance, by overcoming the forces holding the solid together. It is also the heat released during freezing. The heat of vaporization is the energy needed to turn a liquid into a gas, by overcoming the forces holding the liquid together. It is also the heat given off during condensation. A substance can either change phase or increase temperature when heat is added.

The Phase diagram for water: The solid-liquid equilibrium line slopes downward. So when pressure is increased, a normal substance would change from liquid to solid, but water will change from liquid to solid. This is because the H-bonds form a lattice structure in water when it freezes, keeping the molecules farther apart in ice than in water. This makes the solid phase less dense than the liquid.

The Heating Curve: This shows how the temperature of a substance changes as it is heated. As heat is added, KE and temperature increase. The flat lines are phase changes; all the heat goes to overcoming intermolecular forces, so there is no increase in KE or temperature. The length of the line is proportional to the heat of fusion/ vaporization.

Thermodynamics The first and second laws: First law- the energy of the universe is constant; energy can neither be created or destroys, only converted.

Second law- If a process is spontaneous in one direction, it is not spontaneous in the reverse. Entropy of the universe increases during reversible reactions. Enthalpy change (H), entropy change (S), and free-energy change (G) are state functionsthey all depend only on the change between the initial and final states of a system, not the process.

Standard State Conditions: Enthalpy: When bonds are formed, energy is released; when broken energy is released. Enthalpy change is Hproducts- Hreactants If products have stronger bonds than reactants, the products have low enthalpy and are stable; energy is released by the reaction so it is exothermic. If products have weaker bonds than reactants, then the products have high enthalpy and lower stability; energy is absorbed in the reaction so it is endothermic. The lower the energy state, the more stable a substance is. Exothermic process are more spontaneous than endothermic. Heat of formation is the energy that takes place when one mole of a compound is formed from its component pure elements under standard state conditions. If H.o.F is negative energy is released, and the product is more stable than the elements; the process is exothermic. If H.o.F is positive, energy is absorbed, and the product is less stable than the elements; the process is endothermic. H=Hf products reactants. Bond energy is the energy needed to break a bond. H= Bonds broken bond formed; Hesss law- if a reaction can be described in a series of steps, then H for the overall reaction is the sum. Heat capacity is how much the temperature of an object is raised when it absorbs heat. h/t. Large heat capacity means an object can absorb a lot of heat without much temperature change. A small heat capacity means a large increase in temperature but only a small amount of absorbed heat. Specific heat is the amount of heat needed to raise the temperature of one gram by one degree C. All gases are at 1 atm All liquids and solids are pure All solutions are 1M The energy of formation of an element is 0 Is at room temperature, 25 C.

Entropy: Entropy is the randomness or disorder if a system. There is always entropy. Liquids have higher entropy than solids; gases have higher values than liquids; particles in a solution have higher values than solids; two moles have a higher value than one. S- S products - Sreactants

Gibbs Free Energy: The measure of the spontaneity of a reaction. If negative, then spontaneous. If positive than not. If 0, then at equilibrium. G= Gf products- Gf reactants

G, H, and S: G and G: Standard gives the spontaneity of a reaction when all concentrations of reactants and products are in their standard state concentrations (1 M). G= G+ RT lnQ; R= 8.31 J/mol-k At equilibrium, G=0 and Q=k. If G is negative, K must be greater than 1, and products will be favored at equilibrium. If G is positive, K must be less than 1, and reactants will be favored. Nature likes to move towards low entropy and high disorder, so spontaneous processed must result in decreasing enthalpy or increasing entropy or both. G= H- Ts See pg 118

Energy Diagrams: During an exothermic reaction, reactants start out with some energy, and need more to start the reaction called the activation energy. At this point, all reactant bonds have been broken, but no product bonds have been formed- highest energy but lowest stability. After the activation complex is passed, products are formed . H is negative. During an endothermic reaction, the energy of the products is greater than the reactants, so H is positive. A catalyst speeds up a reaction by lowering the activation energy.

Solutions

Concentration Measurements: Molarity expresses the concentration of a solution in terms of volume. Moles/liter.

Molality expresses the concentration in terms of the mass of a solvent. Moles of solute/ kilograms of solvent. It tells you moles of solute per mass of the solvent. Mole fraction gives the fraction of moles of a given substance out of the total moles present in a sample. Moles of substance/ total number of moles in a solution.

Solutes and Solvents: Solutes divide in solvents Like dissolves like: polar or ionic solutes will dissolve in polar solvents. When an ionic substance dissolves, it breaks up into ions- called dissociation. Those ions are called electrolytes because they can conduct electricity. Vant Hoff factor tells how many ions one unit will dissociate into in solution, if no dissociation, i=1.

Colligative Properties: Colligative properties are properties of a solution that depend on the number of solute particles in the solutions. The identity of the particles is not important. When a solute is added to a solution, the boiling point of the solution increases. When a solute is added to a solution, the freezing point of the solution decreases. When a solute is added to a solution, the vapor pressure of the solution will decrease. When a pure solvent and a solution are separated by a membrane that only allows solvent to pass through, the solvent will try to pass through the membrane to dilute the solution. The pressure that must be applied to this process is osmotic pressure. A salt if soluble if more than 1 gram of the salt can be dissolved in 100 mL of water. Most solids become more soluble in a liquid as the temperature is increased. Salts that are slightly insoluble/ insoluble still dissociate to some extent. Ksp measures salt dissociation in solution. The greater the ksp, the more soluble the salt. It is the concentrations of the products, raised to the coefficients. The ksp tells us the concentrations of the products at equilibrium. Common ion effect says that when ions common to two chemicals like AgCl and NaCl are added to a solution, it will affect equilibrium. This is because they share a common ion Cl-. The more soluble salt can cause the less soluble salt to precipitate; generally the salt with the lower value of ksp will precipitate first.

Solubility Rules:

Cations: All salts of the Alkali metals are soluble. Li, Na, K, Rb, Cs. All ammonium salts are soluble. NH4. The solubility of the earth metal depends on the anion. Anions: all nitrate salts are soluble No3.

All chlorate salts are soluble. ClO3. All perchlorate salts are soluble. ClO4. All acetate salts are soluble. C2H3O2. Salts containing Chloride, Bromide, and Iodide are soluble. Cl-, Br-, and I- . EXCEPT with Ag, Pb, and Hg. Sulfate salts are soluble. SO4. EXCEPT with Ag, Pb, Hg, Ca, Sr, and Ba. Hydroxide salts are insoluble. OH. EXCEPT with alkilai metals and Ca, Sr, Ba. Carbonate salts are insoluble. CO3. EXCEPT with alkali metals and ammonium. Phosphate salts are insoluble. Po4. EXCEPT with alkali metals and ammonium. Sulfite salts are insoluble. SO3. EXCEPT with alkali metals and ammonium. Chromate salts are insoluble.CrO4. EXCEPT with alkali metals, alkaline earth metals, and ammonium. Sulfide salts are insoluble. S2-. EXCEPT with alkali metals, alkaline earth metals, and ammonium. The lower the temperature and the higher the pressure of gas, the more soluble the gas will e.

Equilibrium The Equilibrium Constant, Keq: Most chemical reactions are reversible; reactants can form products, and products can form reactants. A reaction is at equilibrium when the rate of the forward reaction is equal to the rate of the reverse reaction. The equilibrium expression is the concentrations of the products raised to the coefficients over the concentrations of the reactants raised to the coefficients. This is only for aqueous solutions, not solids or liquids. Partial pressures may also be used. Kc is the constant for molar concentrations Kp is the constant for partial pressures. Ksp is the solubility product, which has no denominator because the reactants are solids. Ka is the acid dissociation constant for weak acids. Kb is the base dissociation constant for weak bases. Kw describes the ionization of water; = 1 x 10-14.

Keq and Gases: Kp= Kc(RT)n. R= .00821.

The Reaction Quotient: Instead of conditions in equilibrium, initial concentrations are used. If Q<K, it is a forward reaction and products are produced.

If Q>K, it is a backwards reaction and reactants are produced. If Q=K, it is in equilibrium.

Keq and Multistep Processes: If two reactions can be added together to make a third the Keq from both can be multiplied together to get Keq for the third.

Le Chatliers Law: Whenever a stress is placed on a situation at equilibrium, the equilibrium will shift to relive that stress. When concentration is increased, the reaction will proceed in the direction that will use up the added substance. When decreased, the reaction will produce in the direction that will produce more of the substance that was removed. When the volume is increased, the reaction will move in the direction where more moles of gas will be produced. When decreased, the reaction will move in the direction where fewer moles of gas will be made. If there is no gas, or the reactants and products have the same number of moles of gas, the volume change has no effect on the equilibrium. When temperature is increased, the reaction will proceed in the endothermic direction, or positive H. When decreased, it will go in the exothermic direction, or H. When pressure is increased, the reaction will go towards the side with less moles of gas. When decreased, it will go towards the side with more moles of gas.

Acids and Bases An Arrhenius acid is a substance that ionizes in water and produces hydrogen ions. An arrhenious base ionizes in water and produces hydroxide ions. Bronsted-Lowry defined an acid as a substance that is capable of donating a proton; a base is a substance that is capable of accepting a proton. The species with the H+ ion is the acid, and the same species without the H+ is the conjugate pair. Lewis defined a base as an electron pair donor, and an acid as an electron pair acceptor; P(anything)= -log pH= -log[H] pOH= -log[OH] pka=-logKa pkb=-log Kb when [H]=[OH], the solution is neutral with a pH of 7. When [H] is greater the solution is acidic with a pH of less than 7. When [H] is less the solution is basic with a pH of more than 7.

Weak Acids:

When a weak acid is placed in water, small fraction of its molecules will dissociate into H+ ions and conjugate base ions (B-). Most of the acid wont dissociate. Ka= [H+][A-]/[HA]. A- is conjugate base ions. HA is un-dissociated acid molecules. Kb= [HA+][OH-]/[B]; HA is protonated base ions, B un-protonated base molecule. The bigger Ka the more dissociation and the stronger the acid.

Weak Acids and Calculations: ICE chart. Solve for x in order to find []. Then find pH or pOH.

Strong Acids: Strong acids dissociate completely in water; the reaction goes to completion without reaching equilibrium, so there is no dissociation constant. Strong acids: HCl, HBr, HI,, HNO3, HClO4, H2SO4 Strong bases: LiOH, NaOH, KOH, Ba(OH)2, Sr(OH)2 Reverse reaction do not usually happen, so the Conjugate base of a strong acid is very weak. Oxoacids are acids that contain oxygen. The final concentration of [H+] is the same as the initial concentration, so pH is easy to calculate.

Kw: pH+pOH = 14. [H][OH] must equal 1 x 10-14 pKa + pKb= 14

Acid and Base Salts: If a salt is composed of the conjugates of a strong base and a strong acid, its solution will be neutral. If a slt is composed of the conjugates of a weak base and a strong acid, its solution will be acidic. If a salt is composed of the conjugates of a stong base and a wek acid, its solution will be basic. If a salt is composed of the conjugates of a weak base and a weak acid, the pH of its solution will depend on the relative strngths of the CA and ase of the specific ions in the salt.

Buffers: A buffer is solution with a very stable pH. Acid and base can be added without change. It is made of weak acid or base into a solution with its conjugate. They will not neutralize each other because of the common ion effect. Henderson Hasselbach: pH= pKa+log [A-]/[HA]; pOH= pKb+ Log [HB]/[B].

Polyprotic Acids and Amphoteric substances: Substances that acts as either acids or bases are called amphoteric. Acids that can give up more than one hydrogen are called polyprotic.

Anyhdrides: Titration: Kinetics The rate law using initial concentration: rate law describes the dependence of the initial rate of a reaction on the concentrations of its reactants. It has the Arrhenius constant k which takes into account activation energy. Law must be determined from experimental data. The rate of reaction if the rate of disappearance of a reactant or disappearance of a product. The bigger the reactants exponent, the more change in concentration will affect the rate. To find exponents you must examine the changes in individual reactants- to do that look at what happen when the concentration of one reactant doubles. To find the order, add the exponents of the concentrations. To find the rate constant, plug in one line of data from the chart and solve for k. The rate of appearance of the product is the same as the rate of disappearance for the reactants if they have the same coefficient in the balanced equation. When an acid and a base are mixed, a neutralization reaction occurs- these are performed by titrations, where a base of known concentration is added to an acid or vice versa. The equivalence point is when there is exactly the same amount of base and acid. Page 180 for specific titration curves. An acid anhydride is a substance that combines with water to form an acid. A basic anhydride is a substance that combines with water to form a base.

The Rate Law Using Concentration and Time: The rate of first-ordered reactions depends on the concentration of a single reactant raised to the first power. As the concentration of A is depleted over time, the rate of reaction will decrease with a characteristic half-life.

First order time vs [A]

The rate law for a first order reaction: ln[At]-ln[A0]= -kt; when natural logs are graphed, the rate law creates a linear graph comparing concentration and time, The slope is k and the y-

int is ln[A]0. Half-life= ln 2/k The rate of a second-order reaction depends on the concentration of a single reactant raised to the second power. The second order rate law is: 1/[A]t- 1/[A]0= kt The use of the inverse creates a linear graph comparing concentration and time. The line moves upwards as the concentration decreases. The slope is k and the y-int is 1/[A]0.

The rate of a zero order reaction does not depend on the concentration of reactant at all; the rate will always be the same. The graph is a straight line with a slope k.

Collision Theory: Chemical reactions occur because reactants are constantly moving around and colliding with one another. Effective collisions are when reactants collide with enough energy to create a reaction. Ineffective collisions do not produce chemical reactions. Reaction rate increases with increasing concentration of reactants because if there are more reactant molecules moving around a given volume, more collisions occur. Reaction rate increases with temperature because the molecules move faster and have more KE. Increasing temperature increases the fraction of reactant molecules above activation energy.

The Rate Constant and Temperature: The rate constant will increase with temperature. The Arrhenius equation in lnK= -E/R(1/T) + lnA.

When lnK is graphed vs 1/T, it makes a straight line with a slope of Ea/R.

Reaction Mechanism: Catalysts: A catalyst increases the rate of a chemical reaction without being consumed in the process; they do not appear in the balanced equation. Sometimes it is necessary to have a catalyst because without out it the reacting would be useless. A catalyst lowers the activation energy by providing an alternative reaction pathway. Most balanced equations are the sum of a series of simple steps. The steps that are omitted are called intermediates- they cancel out in the balanced equation. The speed of the entire mechanism is as fast as the determining step- the slowest step.

Kinetics and Equilibrium: Keq= kf/kr

Redox and Electrochemistry Oxidation States: The oxidation state of an atom indicates the number of electrons that it gains or loses when it forms a bond. Oxygen generally gains two electrons, which are negative, so the oxidation number is -2. Sodium loses one electron, so the oxidation number is +1. The oxidation state of an atom that is not bonded to an atom of another element is zero. Either an atom that is not bonded to any other atom or an atom that is bonded to another atom of the same element. The oxidation numbers for all the atoms in a molecule must add up to zero. The oxidation numbers for all the atoms in a polyatomic ion must add up to the charge on the ion. Element Oxidation number Alkali metals +1 Alkaline earths +2 Group 3A +3

Oxygen -2 Halogens -1 Transition metals can have several oxidation states, which are differentiated from one another by a Roman numeral in the name of the compound.

Oxidation-Reduction Reactions: In redox reactions, electrons are exchanged by the reactant, and the oxidation of some of the reactants are changed over the source of the reaction. When an atom gains electrons, its oxidation number decreases, and its reduced. When an atom loses electrons, its oxidation number increases, and its oxidized. If a reactant contains an atom that is being oxidized, it is a reducing agent, or reductant. If a reactant contains an atom that is being reduced, it is an oxidizing agent or oxidant. A redox reaction can be written as two half reactions- one for reduction, one for oxidation.

Reduction Potentials: Every half-reaction has a potential, or voltage associated with it These are given as reduction half reactions, but they can be reversed and the sign changed to get oxidation potentials. The larger the potential for a half-reaction, the more likely it is to occur. You can calculate the potential of a redox reaction if you know the potentials for the two half-reactions that make it up.

Voltage and Spontaneity: A redox reaction will be spontaneous if its potential has a positive value. It is also spontaneous if free energy is negative. G= -nFE If E is positive, G is negative and the reaction is spontaneous, if the other way around, it is not spontaneous.

Voltage and Equilibrium: The standard reaction potential is related to the equilibrium constant for a reaction by the equation: E=RT/nf (lnK0

Galvanic Cells: In a galvanic cell, a spontaneous redox reaction is used to generate a flow of current. The two half reactions happen in separate cells, and the electrons that are released by the oxidation reaction pass through a wire to the chamber where they are consumed in the reduction reaction. This creates current- the flow of positive charge, so current is always opposite the flow of electrons.

Oxidation is in the anode electrode; reduction is in the cathode. The salt bridge maintains neutrality in the system by providing enough negative ions to equal the positive ions being created at the anode and enough positive ions to replace whats being used up at the cathode. Under standard conditions, the voltage of the cell is the same as the voltage of the redox reaction. If not standard, use the Nernst equation: Ecell= Ecell- RT/nf lnQ. As the concentration of the products increase, the voltage decreased; as the concentrations of the reactants increase, the voltage increases.

Electrolytic Cells: An electrolytic cells uses an outside source of voltage is used to force a nonspontaneous redox reaction to take place. If you know the current and the time, you can calculate the charge by: I=q/t. From there you get coulombs; from coulombs you can get electrons and then mols of electrons and mols of metal.

Nuclear Decay Types of Nuclear Decay: Alpha decay- the nucleus emits helium molecule- 2 protons and 2 neutrons. 42 alpha= 42He; Subtract 4 from the mass number, and 2 from the atomic number. Beta particle is an electron. In beta decay the nucleus changes a neutron into a proton and an electron and emits the electron. The mass number is the same, add one to the atomic number. A positron is an electron with a positive charge. The nucleus changes a proton into a neutron and a positron and emits the positron. The mass number is the same, subtract 1 from the atomic number. In electron capture, the nucleus captures a low energy electron and combines it with a ptoton to form a neutron. The mass number is the same, subtract 1 from the atomic number. Gamma rays are the most penetrating of the nulear decay products. They have no mass or charge

Nuclear Stability: Nuclei undergo decay to become more stable. If an isotopes mass number is greater than its atomic weight the nucleus will try to gain protons and lose neutrons- beta decay. If an isotopes mass number is less than its atomic weight , the nucleus will try to lose protons and gain neutrons- positron emission or electron capture.

Half-Life: The half- life is the time it takes for half of the substance to decay.

Mass Defect and Binding Energy: The mass of the nucleus is less than the mass of the neutrons and protons that make it up- this difference is called the mass defect. To decompose the nucleus the same amount of binding energy is needed, given by E=mc2