Chem 2 Text

● Solubility equilibria
○ In water, molecular compounds dissolve into individual covalent molecules

■ Ionic solids dissociate into positive and negative ions
○ Nonelectrolytes: solutes that don’t break up into ions when they dissolve ex. sucrose
■ Weak electrolytes: solutes that partially break up into ions (“partially soluble”)
■ Strong electrolytes: solutes that break up almost completely into ions when
they dissolve ex. NaCl
○ As the concentration of ions (from the ionic compound solute) increases, conductivity of
the solution increases proportionately...
■ Until solution reaches a certain concentration: equilibrium
● Rate at which AgCl dissolves to form Ag+ and Cl- ions is equal to rate at
which the ions recombine to form AgCl
○ Precipitation: “reverse” reaction in which soluble species form an insoluble product
○ Saturated solution: contains the maximum concentration of ions that can exist in
equilibrium with the solid ionic compound at a given temperature
■ Solubility: amount of substance that must be added to a given volume of solvent
to form a saturated solution
● Solubility rules
○ Soluble: dissolves in water to give a solution with a concentration of at least 0.1mol/L at
room temperature
■ Insoluble: concentration of a saturated aqueous solution is less than 0.001M at
room temperature
■ Slightly soluble: compounds between the extremes
○ Soluble ionic compounds in water
■ Na+, K+, NH4+, NO3-
■ Cl-, Br-, I- except compounds of Pb2+, Hg22+, Ag+, Cu+ ions
■ SO42- except BaSO4, SrSO4, PbSO4 are insoluble and Ag2SO4, CaSO4, Hg2SO4
are slightly soluble
○ Insoluble
■ S2- except Na2S, K2S, (NH4)2S, MgS, CaS, SrS, BaS
■ O2- except Na2O, K2O, SrO, BaO are soluble and CaO is slightly soluble
■ OH- except NaOH, KOH, Sr(OH)2, Ba(OH)2 are soluble and Ca(OH)2 is slightly
soluble
■ CrO42-, PO43-,CO32 except compounds of Na+, K+, NH4+ ions
● Net ionic equations
○ Condensed equations: reactants and products are written as electrically neutral
molecules
○ Ionic equations: strong electrolytes dissociate in aqueous solution into their ions
■ Spectator ions: appear on both sides of equation because they are unchanged
by reaction → cancel them out to get net ionic equation
● Colligative properties
○ Physical properties of solutions that depend on the number of solute particles in a
solution but not on their identity
■ 2 solutions with the same concentration of different solutes dissolved in the same
solvent have the same colligative properties
○ Mole fraction (𝟀): number of moles of compound of a solution divided by the total
number of moles of solute and solvent
■ 𝟀solvent + 𝟀solute = 1
○ Equations only work for ideal solutions: forces that hold solute particles together are
similar to those that hold solvent particles together
● Depression of the partial pressure of a solvent
○ Vapor pressure: pressure of the gas in equilibrium with the given liquid; pressure
exerted by the vapor of the solvent above the solution
○ Rauolt’s law: t he addition of a nonvolatile solute to a pure solvent lowers the vapor
pressure of a solvent
■ Psolution = 𝟀solvent POsolvent
■ Po: vapor pressure of the pure solvent
■ P: observed vapor pressure of the solution
■ P < PO
○ P = PO when the solvent is pure and the mole fraction of the solvent is 1
○ As mole fraction of the solvent decreases,
■ Partial pressure of the solvent escaping from the solution decreases
■ Difference between vapor pressure of the pure solvent and partial pressure over
the solution increases
○ When solute is added to pure solvent, the change in partial pressure of the solvent is
ΔP = PO - P
■ ΔP increases as more solute is dissolved in solvent
■ ????? So another form of Raoult’s law is ΔPsolvent = 𝟀solute solvent

○ In a sealed container, 1 beaker with a pure solvent and 1 beaker with a solution with a
nonvolatile solute
■ Solvents evaporate to establish equilibrium between the liquid and vapor phases
■ Vapor pressure associated with pure solvent is larger
■ So solvent evaporates from beaker with pure solvent and condenses in beaker
containing solution
○ Vapor that accumulates above a solution containing a volatile solute is composed of
solvent and solute: its total pressure is sum of the partial pressures of both solute and
solvent
■ When solvent is only component volatile (evaporates) enough to have a vapor
pressure, partial pressure of the solution equals pressure produced by solvent
escaping from solution
● Boiling point elevation
○ Boiling point of a solution is higher than the boiling point of a pure solvent
■ Boil a pure liquid by heating it until the vapor pressure equals the pressure
pushing down on the surface of the liquid
■ If a nonvolatile solute is added to the liquid, the vapor pressure of the solvent
escaping from the solution decreases
○ Boiling point elevation: change in boiling point of a solvent when a solute dissolves in it
■ ΔTBP = kb * m * i
■ Kb: molal boiling point elevation constant for the solvent
■ m: molality of solution (moles of solute / kilogram of solvent)
■ I: van hoff factor
○ Molality (m) of a solution doesn’t change with temperature because its defined by mass
not volume of solvent
■ Molarity changes with temp. because the density of water changes with temp.
● Freezing point depression: change in freezing point of a solvent when a solute is added to it
○ ΔTFP = -kf * m * i
■ Kf: molal freezing point depression constant for the solvent
■ I: van hoff factor
■ m: molality of solution (moles of solute / kilogram of solvent)
○ Adding solute to a solvent lowers freezing/melting point of a solution
● Types of solids
○ Crystalline: regular structure, particles pack in a repeating pattern of rows
○ Amorphous (“without form”): random structure, no long range order
○ Polycrystalline: aggregates of many small crystals that are arranged randomly, but
within the grains the structure is regular
○ 3 types of bonds between adjacent atoms…
■ Nonmetals: covalent bonds
■ Metals and nonmetals form salts with ionic bonds
■ Metals: metallic bonds
● Molecular solids
○ Soft; low melting points
○ Strong intramolecular covalent bonds
○ Weak intermolecular forces
○ When substance is cooled, average KE (motion of molecules) decreases, so force of
attraction between molecules increases and holds them together, causing a phase
change
○ Cl2: no dipole moment, so weak intermolecular forces result in induced
dipole-induced dipole or nondirectional dispersion forces
■ Molecules pack as tight together as possible
○ HCl: dipole moment, so has directional dipole-dipole interactions
■ Molecules pack so (-) end of 1 dipole is oriented toward (+) end of the other
○ To estimate strength of intermolecular forces (1) Melting point (2) Enthalpy of fusion: heat
required to melt substance in KJ/mol
○ For the halogens, only intermolecular force is dispersion forces
■ Which depend on number of electrons in atom
■ As size of halogen atom increases, dispersion forces increase
■ So MP and Hfus increase (molecular weight also increases)
○ H2O: has dispersion, dipole forces and hydrogen bonding
■ Highest enthalpy of fusion (Hfus)
■ MP increases as number of hydrogen bonds increases
● Network covalent solids
○ Hard; difficult to melt
○ Covalent bonds in molecules that make up crystals
○ Ex. diamond: each C atom bonded to 4 others
○ Ex. quartz: made of SiO2
● Physical properties of molecular and network covalent solids
○ Illustrated by 2 crystalline allotropes (element forms) of carbon
○ Diamond: 1 giant molecule, hardest known substance, insulator
○ Graphite: less dense, very soft, conductor
■ Extended planes of carbon atoms in which each C forms strong covalent bonds
to 3 others in its plane → high MP and BP
■ Planes of atoms are held together by weak Van der Waals forces → easy to
deform solid by moving the planes relatively
○ Graphite (ΔHac: -716KJ/mol) is more stable than diamond (ΔHac: -714KJ/mol)
● Metallic solids
○ Metallic cations are immersed in sea of delocalized electrons
■ Molecular, ionic, and network covalent compounds have localized electrons:
reside on an atom or are shared by pair of atoms
○ To fill valence shell, metal atoms are surrounded by as many neighboring atoms as
possible and share electrons loosely among many atoms
■ Good conductors of heat and electricity: net flow of e- through metal
○ Metallic bonds: small ΔEN and small average EN
■ Each atom is surrounded by as many neighboring atoms as possible
○ Covalent bonds are stronger than metallic bonds, but metals have more bonds per atom
■ So enthalpy of atomization (s → g) is higher for metal
○ Elements become more metallic toward bottom left of table
■ Because size of atoms increases as you go down a column, so its easier to
remove valence electrons
○ Difference between the energies of the subshells within a given shell becomes smaller as
you go down a column
■ Subshells are even closer in energy when atom is bonded to another, which is
why e- move easily between valence shells of different atoms in a metal
○ Non-directional bonding with atoms as close together as possible
● Physical properties resulting from structure of metals
○ Luster
○ Solids at room temperature
○ Malleable and ductile
○ Conduct heat and electricity
● 3 properties are related to bond type…
○ 1. Metals are conductors: conduct electricity in (s) and (l)
○ 2. Ionic compounds are electrolytes: ions released when they dissolve in water can
conduct electricity
○ 3. Covalent compounds are insulators: localized electrons held tightly between nuclei
● Semimetals/metalloids
○ Small region on bond type triangle; semiconductors
○ Between delocalized (metallic) and localized (covalent/ionic) bonding
○ Elements that form metallic bonds- small AVEEs, small energy gaps in valence subshells
○ Elements that form covalent bonds- large AVEEs, large energy separation of valence
subshells
● Ionic solids
○ 3-D network of ions held together by strong force of attraction between opposite charges
○ F = ( q1q2 ) / r2
○ Force of attraction depends inversely on distance between positive & negative charges
○ Strength of ionic bond depends inversely on size of ions that form solid: large ions =
weak bond
○ Brittle; high MP and BP
○ Lattice energy: energy required to break an ionic compound into isolated ions in the gas
phase… tells you strength of bond in ionic compound
○ Lattice energy decreases as size of ions increase because distance between center of
charges increases
■ Takes less energy to break solid apart into ions/form solid from ions
■ Lattice energy is also higher if the charges are greater
● Equilibrium constant expressions
○ Equilibrium is dynamic: concentrations of reactants & products is constant and rate of
forward & reverse reactions are equal
○ Equilibrium constant (KC) = Kf / Kr
■ Numerator is the product of the concentrations of the products at equilibirum
raised to the power of that species’ coefficient in the equation
● Denominator is same but for reactants
■ Has no units, but concentrations are in molarity (moles/L)
○ Reaction is at equilibrium when KC is equal to equilibrium constant expression for
reaction at a given temperature
○ CINO2 + NO ⇄ NO2 + CINO
■ KC = Kf / Kr = [NO2][CINO] / [CINO2][NO]
■ Rateforward = kf (CINO
2)(NO)
■ Ratereverse = kr (NO2)(CINO)
● Reactant quotient
○ Reaction quotient (Qc) is compared to KC to decide whether a reaction is at equilibrium
& what direction reaction has to shift to reach equilibrium
○ If concentration of reactants is too large, rate of forward reaction will be faster than
reverse until equilibrium is achieved
2
○ H2 + I2 ⇄ 2 HI…. Qc = (HI) / (H2)(I2) Kc = [HI]2 / [H2][I2]
○ Brackets indicate reaction is at equilibrium whereas parentheses indicate QC can be
calculated at any moment in time
○ Only 1 possible value for Kc, whereas Qc can be any positive number
○ Large Qc if system has a lot of product and little reactant; small Qc if system has a lot of
reactant and little product
○ 1. If Qc < Kc, some reactants must be converted into products to reach equilibrium
○ 2. If Qc = Kc, reaction is at equilibrium
○ 3. If Qc > Kc, some products must be converted into reactants to reach equilibrium
● Changes in concentration that occur as a reaction comes to equilibrium
○ To predict how far the reaction has to go to reach equilibrium
○ See paper….
○ Finding final (at equilibrium) concentrations of reactants/products
● Hidden assumption that makes equilibrium calculations easier
○ See paper….
● What to do when the assumption fails
○ See paper….
● Effect of temperature on an equilibrium constant
○ Kc for a reaction changes with temperature
○ 2NO2 ⇄ N2O4 is exothermic so as temperature increases, KC decreases
○ Decrease in KC implies a shift toward the reactants of reaction at equilibrium
○ At high temperatures, equilibrium favors reactant
○ Remember KC = [N2O4] / [NO2]
● Le Chatelier’s principle
○ Change in one of the variables that describe a system at equilibrium will shift position of
the equilibrium
○ RULE A) increase in temperature shifts equilibrium in the direction in which the system
absorbs heat from its surroundings
■ In endothermic reactions, equilibrium shifts to the right as temperature increases
■ In exothermic reaction, equilibrium shifts to the left as temperature increases
○ RULE B) increase in pressure shifts equilibrium in the direction in which the volume of the
system decreases
○ Le Chatelier’s Principle describes what happens to a system at equilibrium when
something momentarily takes it away from equilibrium
○ 1) Change concentration of a component
■ Adding more of a species shifts the equilibrium away from that side to reduce it
■ Removing a species shifts the equilibrium toward that side to produce more of it
○ 2) Change pressure or volume of system
■ Changing volume has no effect on reactions in which the sum of the coefficients
of the gaseous products is equal to sum of coefficients for gaseous reactants
■ If pressure increases, equilibrium shifts in the direction of fewer moles of gas
■ If pressure decreases, equilibrium shifts in the direction of more moles of gas
○ 3) Change temperature
■ Changes in concentration and pressure shift the position of the equilibrium
■ Changes in temperature change the equilibrium constant
● Le Chatelier’s principle and Haber process
○ Haber process: increases pressure at which reaction is run to favor the products of the
reaction, because of net reduction in the number of molecules in system
○ N2 + 3H2 ⇄ 2NH3
○ Reaction is exothermic, so KC increases as temperature decreases
○ Yield of ammonia is maximized at low temperature and high pressure
● What happens when a solid dissolves in water
○ As the concentration of the ions increases, the reverse reaction competes with the
forward reaction until the rate of precipitation (formation of a solid from ions) and
dissolution are balanced
○ At equilibrium, no additional solid will dissolve and ion concentrations are constant
■ Saturated solution: contains maximum concentration of ions that can exist in
equilibrium with the solid salt
■ Solubility of a salt: maximum amount that must be added to a given volume of
solvent to form a saturated solution
● Solubility product expression
○ 1) Concentration of solids are never included in an equilibrium constant expression
because concentration of a solid does not change
○ 2) Concentration of liquids is included only when it changes during the reaction
○ Solubility product equilibrium constant (KSP) for a salt: product of the concentrations
of the ions in the solution at equilibrium
■ Each concentration raised to a power equal to the coefficient of that ion in the
balanced equation for the solubility equilibrium
■ Constant KSP is proportional to the solubility of the salt
○ KSP = [Ag+][Cl-] AgCl (s) ⇆ Ag+ (aq) + Cl- (aq)
+ -
■ [Ag ] and [Cl ] are in moles per liter (M)
■ Derived from KC = [Ag+][Cl-] / [AgCl].... [AgCl] is omitted because its a solid
● Relationship between KSP and the solubility of a salt
○ Solubility product of a salt can be estimated from its solubility or vice versa
○ See paper
● Role of the ion product QSP in solubility calculations
○ AgCl is a 1:1 salt, so [Ag+] = [Cl-] in a saturated solution
○ Ion product Qsp = (Ag+)(Cl-)
○ If AgNO3 (s)
is added to saturated AgCl solution
■ AgNO3 dissolves, so [Ag+] > [Cl-]
■ Solution is no longer at equilibrium because the product of the concentrations of
the Ag+ and Cl- ions is too large
■ Ion product (QSP) is larger than solubility product (KSP)
○ When QSP > KSP, the reaction has to shift toward the solid to come to equilibrium
■ Excess ions will precipitate from the solution as solid AgCl until the reaction
reaches a new equilibrium
+ -
■ At equilibrium, QSP = KSP but [Ag ] and [Cl ] are different
○ Any point on a saturation curve corresponds to a system at equilibrium
■ Points below the curve are solutions for which QSP < KSP
■ Points above the curve are solutions for which QSP > KSP
● Come to equilibrium through the precipitation of AgCl (s)
● Common-ion effect
○ When AgNO3 is added to a saturated solution of AgCl, it is a source of a common ion
○ Common ion: ion that enters the solution from 2 different sources
○ Common ions affect solubility product equilibrium
○ A compound is less soluble in a solution containing one of its ions than it is in
pure water
○ See paper
● Properties of acids and bases
○ Acids: behave like vinegar- sharp odor, sour taste
■ Characteristic property is ability to dissolve most metals
● Zn(s) + 2HCl(aq) ⇄ ZnCl2(aq) + H2(g)
■ Change litmus blue → red
○ Bases (alkalies): behave like wood ash- bitter, slippery
○ Bases become less alkaline when they react with acids and vice versa
● Arrhenius definition of acids and bases
○ Acids dissociate in water to give H+ ions and a corresponding negative ion
■ HCl (g) ⇄ H+(aq) + Cl-(aq)
○ Bases dissociate in water to give OH- ions and a positive ion
■ NaOH (s) ⇄ Na+(aq) + OH-(aq)
○ Arrhenius acid: substance that ionizes when it dissolves in water to give H+ ex. HCN,
H2SO4
○ Arrhenius base: substance that ionizes when it dissolves in water to give OH- ex. KOH,
Ca(OH)2
● Bronsted-lowry definition of acids and bases
○ Assumes that acids donate H+ ions to another ion or molecule, which acts as a base
○ Instead of HCl dissociating, Bronsted Lowry states its hydronium ion (H+) is transferred
to the electronegative O of a water molecule to form H3O+
■ HCl (aq) + H2O (l) ⇄ H3O+ (aq) + Cl- (aq)
■ HCl is H+ donor and H2O is H+ acceptor
○ Bronsted acid: substance that can donate an H+ (proton) to a base
○ Bronsted base: substance that can accept an H+ (proton) from an acid
○ Acids we discuss are monoprotic: have a single H+ they can donate
○ Acids can be uncharged molecules, positive ions, or negative ions
○ Any molecule with 1 or more pairs of nonbonding electrons that can accept a proton is a
Bronsted base ex. CO32-, NH3, H2O
● Conjugate acid-base pairs
○ Acids and bases are coupled to form conjugate acid-base pairs: formulas are related by
the gain or loss of a hydrogen ion
○ HA (generic acid) + H2O (base) ⇄ H3O+ + A- (conjugate base)
○ A- (generic base) + H2O (acid) ⇄ HA (conjugate acid) + OH-
○ Some compounds can act as acids or bases
○ HNO3 (acid) + NH3 (base) ⇄ NH4+ (conjugate acid) + NO3- (conjugate base)
○ Products can be combined and written as an aqueous solution... NH4NO3
○ Neutralization reaction: products are neither as acidic or as basic as the reactants
■ Water is a product, because it is conjugate acid of a OH-
● Role of water in the Bronsted model
○ Water acts as an intermediate: dissociates to form ions by transferring an H+ from the
acid to the base
○ Acids react with water by donating an H+ to a water molecule acting as a base to form
H3O+
○ Bases react with water by accepting an H+ from a water molecule aciting a as an acid to
form OH-
● To what extent does water dissociate to form ions?
○ At 25℃, density of water is 0.9971g/mL so the concentration of water is 55.35M
■ Concentration of the H3O+ and OH- ions formed by the dissociation of pure
H2O at 25℃ is 1 x 10-7 mol/L
○ H3O+ + OH-
Reaction is at equilibrium: 2H2O ⇌
■ KC = [H3O+][OH-] / [H2O]2
■ KC * [H2O]2 = [H3O+][OH-] … left side is constants (H2O is liquid)
○ Water dissociation equilibrium constant KW = [H3O+][OH-]
○ At 25℃, KW = [1 x 10-7]2 = 1 x 10-14
○ What happens to OH- and H3O concentrations when you add acid to water?
■ Now there are two sources of H3O (acid and dissociation of water)
■ Common ion effect: drives equilibrium to the left & decreases extent to which
water dissociates into ions
■ Makes [H3O+] and [OH-] decrease from 10-7 it is in pure water
■ Total H3O+ concentration = [H3O+] from dissociation of the acid (0.01M) + [H3O+]
from dissociation of water (<1 x 10-7M)
● [H3O+] from water is so relatively small that it is negligible
● Thus at equilibrium, we assume [H3O+] ≈ 0.01M
● At equilibrium, [H3O+][OH-] = 1 x 10-14 so [OH-]=1 x 10-12M
■ Although there are 2 sources of H3O+, only source of OH- is water
● In acid solution, OH- concentration is much smaller than its concentration
when it dissociates in pure water
■ Adding an acid to water increases [H3O+] and decreases [OH-]
■ Adding a base to water increases [OH-] and decreases [H3O+]
● Because at equilibrium, product of 2 concentrations again must equal Kw
● pH as a measure of the concentration of the H3O+ ion
○ log (10-7) = -7
○ pH = -log [H3O+] [H3O+] = 10-pH
○ pOH = -log [OH-] [OH-] = 10-pOH
+
○ As concentration of H3O decreases from 1M to 10-14M, the pH of the solution increases
from 0 to 14
○ Acidic solution: concentration of H3O+ > 1 x 10-7 M
○ Basic solution: concentration of H3O+ > 1 x 10-7 m
○ Acid base indicators: weak acids or weak bases that change color when they gain or
lose an H+ ion, ex. Litmus
○ Ph meter: electrode emerged in solution produces electric potential related to [H3O+]
○ Product of concentrations of the ions at equilibrium at 25°C is 1 x 10-14
○ For an aqueous solution at 25°C, pH + pOH = 14
● Relative strengths of acids and bases
○ Conductivity apparatus: brighter the lightbulb glows, the larger the number of positive
and negative ions in the solution (greater ability to conduct a current)
■ Glows brightly in HCl: strong acid- all of the HCl molecules react with H2O to
form H3O and Cl-, ions so few HCl molecules are left
■ Acetic acid: weak acid- most of the Ac molecules remain undissociated
○ Acid-dissociation equilibrium constant Ka: describes extent to which an acid
dissociates in water to produce the H3O+ ion
■ General equation HA (aq) + H2O (l) ⇄ H3O+ (aq) + A-(aq)
■ Kc = [H3O+][A-] / [HA][H2O]
■ Concentration of H2O is a constant so it is eliminated… Kc * [H2O]
■ Ka = [H3O+] [A-] / [HA]
■ Ka > 1 for strong acids
● When strong acid dissolves in water, it all dissociates into ions-- good at
transferring H+ to water
■ Ka < 1 for weak acids
● When weak acid dissolves in water, it barely reacts-- bad at transferring
H+ to water
○ Base ionization equilibrium constant Kb: describe strength of bases
■ Strong bases: ionize almost completely in water to produce OH- ion
■ Examples of strong bases
● Group IA metal hydroxides (LiOH, NaOH, KOH, RbOH, CsOH)
● Group IIA metal hydroxides that are soluble or slightly soluble (Ca(OH)2,
Sr(OH)2, Ba(OH)2)
● Soluble metal oxides (Li2O, Na2O, K2O, CaO)
■ pKa = - log (Ka) and pKb = - log (Kb)
● Relationship of structure to relative strengths of acids and bases
○ Stronger a base is, the weaker its conjugate acid
○ Stronger an acid is, the weaker its conjugate base
■ HCl is a strong acid (good proton donor) so its conjugate base Cl- is a weak base
(poor proton acceptor)
■ HCl + H2O ⇆ H3O+ + Cl-
■ HCl dissolves completely so there is little tendency for reaction to go in reverse
reaction
● Relative strengths of different acids and bases
○ Look at table….
■ Higher the Ka, the stronger the Bronsted Acid (reactant side)
■ Lower the Ka, the stronger the Bronsted Base (product side)
○ Every acid-base reaction converts an acid into its conjugate base and a base into its
conjugate acid (2 pairs)
■ Stronger acid has the weaker of the conjugate bases
■ Stronger of a pair of acids reacts with stronger of a pair of bases to form a
weaker acid and a weaker base
+
○ Acids with Ka > 55 (that of H3O ) dissociate completely in water
○ HCl (stronger acid) + H2O (stronger base) ⇆ H3O+ (weaker acid) + Cl- (weaker base)
■ Stronger acid is on left side of equation, suggests reaction proceed to the right
○ CH3CO2H (weak acid) + H2O (weak base) ⇆ H3O+ (strong acid) + CH3CO2- (strong base)
■ Only small number of the CH3CO2H molecules donate an H+ to water to form the
H3O+ and CH3CO2- ions
○ At equilibrium, an acid-base reaction should lie on the side of a equation that contains the
weaker acid and base
○ The table is used to predict whether acid-base reactions should occur
■ Each base is strong enough to deprotonate the acid in any line above it
○ Levelling effect of water: t endency of water to limit the strengths of strong acids and
bases
■ All strong acids dissociate to produce the same H3O+ ion, they appear to have the
same strength when dissolved in water, regardless of their Ka value
■ HClO4 (Ka = 1 x 108) is a stronger acid than HCl (Ka = 1 x 106)
■ But when they react with water, 0.1M of HCl and 0.1M of HClO4 both produce
0.1M H3O+, so they have the same acidity
■ Strength of a strong acid or base is limited by the strength of the acid H3O or
base OH- formed when water molecules accept or lose an H+ ion
● Relationship of structure to relative strengths of acids and bases
○ 3 factors affect the acidity of the X-H bond in an acid
○ Ka indicates
the strength of an acid: higher the Ka, the stronger the acid
○ 1. Polarity of the X-H bond
■ As bond gets more polar, acids become stronger
■ So acids get stronger as ΔEN between X and H increases and the partial charge
(δH)on the hydrogen atom increases
■ More polar the bond, the easier it is to break and form ions H+ and X-, and the
larger the Ka value
○ 2. Size of the X atom
■ Acids get stronger as you go down the column of periodic table
■ Acids get stronger as X-H bond gets weaker, and bonds become weaker as the
atoms get larger
■ As atom gets larger, enthalpy of atom combination (ΔH°ac) decreases
○ 3. Charge on the ion/molecule (acid/base)
■ As negative charge increases, compounds become less acidic
■ In order of acidity: H3PO4 > H2PO4- > HPO42-
■ Because its easier to remove a positive H+ ion from a neutral than a negatively
charged molecule
■ Similarly for bases, there is a strong force off attraction between negative
molecule and H+
○ Relative strength of oxyacids
■ For O-H bonds in oxyacids of the same element
● H2SO4 is stronger acid than H2SO3 and HNO3 is stronger acid than HNO2
■ Acidity increases as number of O atoms attached to the central atom
increases
■ Oxygen is highly electronegative so it draws electron density toward itself and
away from the other atom in the bond, so H gets more positive partial charge
○ Relative strength of Bronsted bases
■ Predicted from relative strength of their conjugate acids
■ Rule that stronger of a pair of acids always has the weaker conjugate base
● Strong acid pH calculations
○ Calculate pH of solution formed by adding 5 x 10-5 mL of 2M HCl to 100mL of water...
HCl (aq) + H2 O (l) → H3 O (aq) + Cl (aq)
+ -
○ HCl is a strong acid (Ka = 106), so it dissociates completely in water

○ Assume [H3O+] at equilibrium is the same as initial concentration of the acid
○ Calculate number of moles of HCl added
■ ( 2 mol / 1 L )( 5 x 10-5 L ) = 1 x 10-4 mol HCl
○ Calculate concentration of initial solution prepared
■ ( 1 x 10-4 mol HCl )( 0.1L ) = 1 x 10-3 M HCl
○ So H3O+ concentration at equilibrium is 1 x 10-3 M
○ Calculate pH using pH = - log [H3O+]
■ pH = - log [1 x 10-3) = -(-3) = 3
● Weak acid pH calculations
○ Weak acids dissociate slightly in water meaning only some of its molecules combine to
form H3O
○ So the undissociated form (HA) remains along with the dissociated (H3O+ + A-) form of
the acid
○ Concentration of H3O+ in solution of a weak acid depends on
■ 1) strength of acid, given by acid dissociation equilibrium concentration Ka
■ 2) concentration of acid, in moles per liter
● For solutions of the same concentration, as Ka increases, the amount of
H3O+ ion
at equilibrium increases
○ Assumption 1) amount of acid that dissociates is small compared with initial
concentration of acid
■ If acid is strong, must solve with quadratic equation (can’t assume)
○ Assumption 2) enough acid dissociates so that we can ignore the contribution to the total
H3O+ concentration from the dissociation of water
■ If acid is weak/dilute (can’t assume)
● Base pH calculations
○ Base ionization equilibrium constant (Kb)
○ Kb values for some bases are found in table, but others must be determined using the
value of Ka for its conjugate acid using K a Kb = Kw
■ HOAc + H2O ⇆ H3O+ + OAc-
■ Know conjugate acid HOAc has Ka of 1.8 x 10-5
■ Ka = [H3O+][OAc-] / [HOAc] Kb = [HOAc][OH-] / [OAc-]
■ Plug in Kw = 1 x 10-14
■ Kb = Kw / Ka = 1 x 10-14 / 1.8 x 10-5 = 5.6 x 10-10
■ Relationship between KA and Kb for a conjugate acid-base pair is why
● The stronger the acid, the weaker its conjugate base
● The stronger the base, the weaker its conjugate acid
■ Product of Ka for a Bronsted Acid and Kb for its conjugate base is equal to Kw for
water, KaKb =
K w = 1 x 10-14
● A large Ka indicates a strong acid
● A large Kb indicates a strong base
○ Acid-base properties of a salt
■ Reaction of an acid with a base produces an ionic compound
■ Soluble salts ionize completely in water, so acid-base properties of the
compounds are determined by acid-base properties of their ions in solution
■ Group I and II cations have no significant acid or base properties
■ Conjugate bases of strong acids are weak/have no basic properties
■ KF is basic salt: F+ ion is the conjugate base of a weak acid HF, so it has basic
properties in water
■ NH4NO3: NH4+ is conjugate acid of weak base NH3 so behaves as acid in water
■ NaCl is neutral salt: Cl- is conjugate base of a strong acid so is too weak to have
base properties & Na+ is not a Bronsted acid or base
● Mixtures of acids and bases: buffers
○ Buffer: a mixture of a weak acid and its conjugate base
○ So far we’ve examined 0.1M solutions of acetic acid ([H3O+] = 1.3 x 10-3M and pH 2.9)
and sodium acetate ([H3O+] = 7.5 x 10-6M and pH 8.9)
○ Prepare a buffer from enough of both solutions so solution is 0.1M in both HOAc and
NaOAc
○ See paper
● Buffers and buffer capacity
○ Buffers lessen the drastic change in pH that occurs when small amounts of acids/bases
are added to water
○ Buffer is made by mixing a weak acid and its conjugate base so significant amounts of
both are present in solution
○ HOAC (weak acid) + H2O (l) ⇆ H3O+ + OAc- (conjugate base)
○ At equilibrium, Ka = [H3O+][OAc-] / [HOAc]
○ Rearrange [H3O+] = Ka x [HOAc]/[OAc-]
○ If strong acid H3O+ is added to buffer...
■ OAc- + H3O+ ⇆ HOAc + H2O
■ Equilibrium constant for this reaction is inverse of Ka value
for acetic acid
because its the opposite of the equation for dissociation of acetic acid
● K’ = 1/Ka = 1/1.8 x 10-5 = 5.6 x 104
■ Calculate H3O+ concentration after acid is added to buffer solution…
● [H3O+] = 1.8 x 10-5 [HOAc]/[OAc-]
● [H3O+] = 1.8 x 10-5 [0.1 + ΔC]/[0.1 - ΔC]
■ Net result is slight increase in undissociated [HOAc] and decrease in [OAc-]
● Ratio of the concentrations is roughly the same, so [H3O] and pH of
buffer stay the same
● H3O gets converted to equivalent amount of HOAC
■ Unaffected because amounts of [HOAc] and [OAc-] in buffer are larger than that
of acid or base added to solution
○ Buffer capacity: amount of strong acid or base that can be added before the pH of buffer
solution changes significantly
○ pH = pKa + log ( [OAc-]/[HOAc] )
○ Henderson hasselbach: pH = pKa + log ([conjugate base]/[conjugate acid])
■ If concentrations of conjugate base and conjugate acid used to prepare a buffer
are the same, log term is 0 so pH of solution = pKa of acid
○ Adjust ratio of conjugate acid and base to prepare a buffer with a pH slightly above or
below pKa
■ Acidic buffer: formed by mixtures of HOAc and OAc- ion (pKa = 4.76)
■ Basic buffer: formed by mixtures of NH3 and NH4+ (pKa = 9.25)
-7
■ Mixture of a conjugate acid base pair is acidic if Ka > Kb so Ka >
10
■ Mixture of a conjugate acid base pair is basic if Kb > Ka so Kb > 10-7
● Acid-base reactions
○ Strong acid-strong base: Kc = 1/Kw = 1014
■ pH is 7: resultant solution has equal concentrations of H3O+ and OH-
■ Can produce a salt and water
■ HCl + NaOH → H2O + NaCl
■ Equilibrium for this reaction lies to the right
○ Weak acid-strong base: Kc = Ka x 1/Kw
■ Reaction goes almost to completion and proceeds to the right
■ HNO2 + OH- → H2O + NO2-
○ Strong acid-weak base: Kc = Kb x 1/Kw
■ CH3NH2 + HI → CH3NH3 + I-+
■ Assuming HI dissociates completely in water, we can write the equation as

CH3NH2 + H3O+ → CH3NH3+ + H2O
■ Find equilibrium constant by combining appropriate reactions for which
equilibrium constants are known
● CH3NH2 + H2O → CH3NH3+ + OH-... Kb = 4.8 x 10-4
+ -
● H3O + OH → 2H2O…
■ Kc = Kb x 1/Kw = 4.8 x 1010
■ In general, a strong acid reacts completely with a weak base
○ Weak base-weak acid: Kc = Ka x Kb x 1/Kw
■ CH3NH2 + HNO2 → CH3NH3 + NO2-
+
■ Combining 3 equations
○ Reaction proceeds to an extent that depends on magnitude of equilibrium constant
■ Small Kc indicates the reaction hardly proceeds and large KC means reaction
proceeds near completion
● pH titration curves
○ Measure the concentration of a solution by titration
■ Slowly adding a solution of known concentration to a known quantity of a reagent
with which it reacts until we observe something that tells us equivalent numbers
of moles of reagents are present
■ Acid base titrations: acid of unknown concentration tated with a base with
known concentration
○ Indicators: weak acids or bases whose conjugate acid-base pairs have different colors in
aqueous solution
■ Ex. phenolphthalein is pink in base & colorless in acid
■ HIn(aq) + H2O (aq) ⇆ H3O+ (aq)+ In- (aq)
■ HIn represents acid form of indicator and In- represents base form of indicator
■ Color of indicator solution depends on hydronium concentration
■ When [H3O+] is large, [HIn] > [In-] and color is of acid form
○ Endpoint: when the indicator turns color
■ Try to use indicators for which the end point is as close as possible to the point of
equivalence
○ Equivalence point: when exactly enough base has been added to neutralize the acid
■ For titrations between a strong acid and a strong base, the pH is neutral at the
equivalence point
■ For solutions of a weak acid and strong base, pH is basic at equivalence point
○ See paper
○ Titration curve: plot of solution pH vs. amount of titrant added
■ HOAc(aq) + H2O (l) ⇆ OAc- (aq) + H3O+ (aq)
■ Point A- pH at the start of titration
● pH of a 0.1M HOAc solution, calculated from…
● Ka = 1.8x10-5 = [OAc-][H3O+] / [HOAc] = ΔC / 0.1M
● ΔC = 1.3x10-3 = [H3O+]
● pH=2.9
■ As NaOH is added to HOAc solution, some of the acid is converted to its
conjugate base
● Equilibrium constant for reaction between a weak acid and strong base is
large, so equilibrium is to the right: dominated by forward reaction
● As titration proceeds, a buffer of HOAc and OAc- forms
● pH changes slowly as buffer capacity is exceeded
■ Point B- half of HOAc molecules have been converted to OAc-
● [H3O+] is controlled by equilibrium between HOAc and OAc- described
by Ka = [H3O+][OAc-] / [HOAc]
● At this point [HOAc] = [OAc-]
● Because ratio is 1:1, Ka = [H3O+] and pH = 4.7
● Can find Ka for an acid in this way
■ Point C- equivalence point
● What remains in solution is Na+ and OAc- ions
● Na+ has no effect on pH
● OAc- react with water to produce basic solution
○ OAc-(aq) + H2O(l) ⇆ HOAc(aq) + OH-(aq)
● Calculate moles of OAc- from initial moles of HOAc…
○ 0.025L * 0.1mol/L HOAc = 2.5x10-3 mol HOAc
○ So 2.5x10-3 mol of OAc- formed
○ No HOAc left
● Total volume = initial 25mL HOAc + 25mL NaOH required to reach
equivalence point
● Calculate concentration of OAc-...
○ [OAc-] = 2.5x10-3mol OAc- / 0.05L = 5x10-2 M OAc-
● Calculate pH of solution from equilibrium constant Kb for above
reaction…
○ Kb = [HOAc][OH-] / [OAc-]
○ 5.6 x 10-10 ≈ (ΔC)2 / 5 x 10-2 M
○ ΔC = [OH-] = 5.3 x 10-6 M
○ pOH ≈ 5.3, so pH = 8.7
● Want endpoint to be close to equivalence point so choose an indicator
whose color changes around pH 8.7
■ Point E
● 50mL of NaOH have been added, which 25mL in excess of amount
required to react with acetic acid
● 0.1mol/L * 0.025L = 0.0025 excess mol NaOH
● [OH-] = 0.0025mol/0.075L = 0.033M
● pOH is 1.5, so pH is 12.5
○ Shape of titration curve
■ pH rises rapidly at first because adding strong base to a weak acid and base
neutralizes it
■ pH is constant because some of the HOAc present initially is converted into OAc-
ions to form a buffer
■ Once most of acid has converted to its conjugate base, pH rises rapidly because
HOAc became OAc- and buffer is exahusted
■ pH levels off to look like a 0.1M NaOH solution
○ Titration curve for a weak base titrated with a strong acid is analogous, except pH is high
at first and decreases as acid is added
12
● Common oxidation-reduction “redox” reactions
○ Corrosion ex. rusting of iron in presence of oxygen and water
■ “Rust” refers to series of iron(III) oxides
○ Reactions used as sources of heat or work are always redox
○ Electrons are transferred: same number is gained & lost
■ Element/compound that gains electrons is reduced
■ Element/compound that loses electrons is oxidated
■ Half reactions: seperate oxidation & reduction reactions
■ 1 half reaction can’t occur without other
○ Oxidation half reaction: 2 Na ⇆ 2 Na + + 2e-
■ Reduction half reaction: Cl2 + 2e- ⇆ 2 Cl-
○ Atom transfer reactions: redox reactions that transfer atoms (instead of electrons)
■ Oxygen: CINO2 + NO ⇆ CINO + NO2
■ Hydrogen: C2H4 + H2 ⇆ C2H6
○ Any reaction that results in a change in oxidation number/state for 1 or more atoms is a
redox reaction
● Determining oxidation numbers
○ Assign oxidation numbers to atoms by treating the compound as if it is ionic
○ OXa = Va - Na
■ Na: #
of electrons in the atom after the shared electrons in each bond have been
assigned to the more electronegative element
● Evenly divide electrons in bonds between same element
■ Va: # of valence electrons on atom of that element
■ Useful method for organic compounds where carbons have different oxidation
numbers
■ OX# on a carbon decreases as its number of hydrogens increases
○ Sum of oxidation numbers of individual atoms must be equal to overall charge on
molecule on ion
■ For NO3- ion, OXN + 3(OXO) = -1
■ OXO is -2 so OXN is -5
● Recognizing oxidation-reduction reactions
○ Oxidation occurs when oxidation number of an atom gets more positive
○ Reduction occurs when oxidation number of an atom gets more negative
○ Organic compounds are oxidized by removing H or adding O atoms
■ Some redox reactions with organic compounds are shown as structures initial
reactant and product, instead of a reactant
● Ethanol → acetic acid
● K2Cr2O7 above
arrow is the reagent that produces the reaction (can also
have other conditions)
● Number of O and H atoms are both sides are not balanced
● Voltaic cells
○ Some metals react with acids
○ Zn (s) + 2H+ (aq) ⇆ Zn2+ (aq) + H2 (g)
■ Exothermic and large Kc (all reactants converted into products)
■ Oxidation: Zn ⇆ Zn2+ + 2e-, reduction: 2H+ + 2e- ⇆ H2
■ By separating the half reactions so the electrons must pass through an external
circuit, energy given off
○ Voltaic/galvanic cells: electrochemical cells in which an oxidation reduction reaction
produces an electric current that can be used to do work
■ Immerse strip of zinc into Zn(NO3)2 solution
■ Bubble H2 gas over surface of platinum wire immersed in H+ solution
■ Connect zinc and platinum wire with electrical conductor
■ Salt bridge: U tube filled with saturated solution of a soluble salt
○ Oxidation takes place at zinc anode
■ As reaction proceeds, zinc electrode dissolves as zinc is oxidized to aqueous
Zn2+; electrons given off collect on zinc electrode, so it becomes negatively
charged
○ Reduction takes place at platinum cathode
■ H+ ions in solution around platinum electrode are reduced to form H2 gas which
bubbles out of solution; platinum electrode provides electrons so it becomes
positively charged
○ Electrons on zinc electrode move through wire toward platinum electrode
■ This produces electric current
■ If voltmeter is connected between 2 electrodes, can measure cell potential:
potential of cell to do work on its surroundings
■ Potential of 1 volt is produced when 1 joule of energy is used to transport 1
coulomb, C, of electrical charge… 1 V = 1 J / 1 C
○ Larger the cell potential, the larger the driving force pushing the reaction towards
the products
○ Salt bridge maintains electric neutrality
■ Negative NO3- diffuse into zinc solution, which balances positive Zn2+ ions
produced at electrode when zinc metal is oxidized
■ K+ diffuse into acid solution, which balances negative charge from H+ ions being
reduced to form H2
○ Cations flow toward cathode and anions flow toward anode
■ Anode: electrode at which oxidation occurs in electrochemical cell
■ Cathode: electrode at which reduction occurs
○ Balancing oxidation-reduction equations
■ Cu ⇆ Cu2+ + 2e-; Ag+ (aq) + e- ⇆ Ag (s)
■ Law of conservation: MASS AND CHARGE must be balanced
■ For every Cu oxidized, 2 electrons are released; only 1 electron needed to
reduce Ag+ to Ag
■ Double the 2nd half reaction
■ Electrons are not created or destroyed,
■ Cu + 2Ag+ ⇆ Cu2+ + 2Ag
● Standard cell potentials
○ Standard state conditions
■ Each solute has a concentration of 1M
■ All gases have a partial pressure of 1 bar
■ Usually 25 degrees C
o
○ E : standard cell potential
■ Measures relative reducing power of Zn metal compared to H2 gas
■ Get absolute reducing power by defining the Eo for the reduction of H+ ions to H2
gas as 0 V
○ Eocell: Eoox + o
E red, meaning sum of half reduction and oxidation cell potentials is the overall
potential for the voltaic cell
■ Units are volts
■ When combing half reactions, just add (do not have to multiply to balance the
number of electrons)
○ Magnitude of cell potential is a measure of the driving force behind a reaction
■ Larger the Eocell, the farther the reaction is from equalium
■ Sign of Eocell tells you direction in which reaction must shift to reach equilibrium (+
means shift right and - means shifts left)
■ Spontaneous reactions: have positive Eocell which means reaction favors the
formation of products and occur naturally
● Oxidizing and reducing agents
○ Zn (s) + 2H+ (aq) ⇆ Zn2+ (aq) + H2 (g)
■ Zn metal is reducing agent: when immersed in acidic solution, it donates
electrons to and reduces H+ ions to H2 gas
■ H+ ion is oxidizing agent: it accepts electrons and oxidizes zinc
○ oxidizing agent: undergoes a decrease in oxidation number and causes the oxidation of
another species
○ Reducing agent: undergoes an increase in oxidation number and causes the reduction
of another species
○ When Zn metal loses electrons, it forms a conjugate oxidizing agent that could gain
electrons if the reaction were reversed: Zn ⇆ Zn2+ + 2e-
○ When H+ gains electrons, it forms a conjugate reducing agent that could lose electrons if
the reaction were reversed: 2H+ + 2e- ⇆ H2
■ If species is a good reducing agent, its conjugate oxidizing agent is weak
■ If species is a strong oxidizing agent, its conjugate reducing agent is weak
○ Many atoms have multiple possible oxidation numbers…
■ When an element is in an intermediate oxidation state, it can act as either an
oxidizing agent or reducing agent
■ If an element is in its lowest oxidation state, it can only act as a reducing agent
(can’t be reduced farther)
■ If an element is in its highest oxidation state, it can only act as an oxidizing
accent (can’t be oxidized further)
● Relative strengths of oxidizing and reducing agents
○ Redox reactions should occur when they convert the stronger of a pair of oxidizing
agents & the stronger of a pair of reducing agents into a weaker oxidizing agent &
a weaker reducing agent
○ Zn (stronger reducing agent) + 2H+ (stronger oxidizing agent) ⇆ Zn2+ (weaker oxidizing
agent) + H2 (weaker reducing agent)
○ Standard reduction potentials
■ All of half reactions are written as reduction half reactions!
■ Gives reduction potential: measure of the driving force behind a reduction half
reaction in units of volts (V)
■ Half cell potential for strongest reducing agent… Eo = -2.924 V
■ Half cell potential for strongest oxidizing agent… Eo = +3.03 V
o
○ E red values are used to predict the direction in which an oxidation reduction reaction is
spontaneous
■ More positive Eored value means that forward reaction is more likely to occur
○ Zn + 2e- ⇆ Zn (Eored= - 0.7628V); Ag+ + e- ⇆ Ag (Eored= 0.7996 V)
2+
■ Zn is a stronger reducing agent than Ag

■ Ag+ is a stronger oxidizing agent Zn2+
■ Ag+ is more likely to undergo the reduction half reaction
○ To make a reduction half reaction into an oxidation reaction, reverse it and reverse the
sign of its potential value
■ Zn ⇆ Zn2+ + 2e- (Eoox= 0.7628V)
■ This oxidation reaction is more likely to occur than its reverse
■ Therefore, in the voltaic cell, the zinc metal undergoes oxidation!
○ Determine standard potential of the cell using Eo cell = Eoox + Eored
■ Add Eoox for Zn and Eored for Ag+
■ Eocell is positive, meaning the reaction is spontaneous
○ Reducing agents become stronger toward upper right of tabe and strength of oxidizing
agents increases toward bottom left of table
■ Strongest reducing agent is K metal (right side: top half reaction is K+ + e- ⇆ K
● So when using this reaction, must reverse its direction to make it
oxidation
■ Strongest oxidizing agent is F2 (left side): bottom half reaction in table is F2 +
2H+ + 2e- ⇆ 2HF
● Electrochemical cells at nonstandard conditions: Nerst Equation

○ Daniell voltaic cell used as a battery dies after some time
■ Zn (s) + Cu2+ (aq) ⇆ Zn2+ (aq) + Cu (s)
■ As reaction goes forward, cell potential gets smaller until voltaic cell dies
■ Cell potential is magnitude of driving force behind a reaction
■ E°cell = 0 at equilibrium
● No net change in ion concentrations, so no net flow of electrons,
meaning potential to do work is 0
○ Nerst equation: E = E° - (RT/nF) ln Qc
■ E: cell potential for reaction at some point in time
■ E°: cell potential when reaction is at standard conditions
■ R: ideal gas constant 8.314 in units of J/mol*K
■ F: charge on a mole of electrons, 96,485.31 C/mol e-
■ T: temperature in Kelvin, usually 25°C
■ Qc: reaction quotient at that moment in time
■ N: number of electrons transferred in the balanced reaction equation
○ E = 1.10V - ( 8.314*273.15 / 2*96,485.31) ln [Zn2+ / Cu2+]
■ When Qc is small (ln Qc <0), cell potential is positive and large
● Reaction is far from equiibirum
■ When Qc is large ( lnQc), cell potential is small
● When cell potential becomes negative, reaction must shift back towards
reactants to reach equilibrium
○ Nerst equation also used to determine equilibrium constant for a reaction
■ No driving force at equilibrium so E = 0 and Qc = Kc
■ At equilibrium, Nerst equation is nFE° = RT ln Kc so Kc = enFE° / RT
● Electrolysis and Faraday’s law
○ Cells we’ve discussed use a spontaneous reaction to produce an electrical current in an
external circuit
■ Electrolytic cells: use electrolysis to drive a redox reaction in the direction in
which it doesn’t occur spontaneously
○ Electrolytic cells can plate 1 metal onto another
■ Cathode half reaction: Ag(CN)2- (aq) + e- ⇆ Ag (s) + 2CN- (aq)
■ Oxidation at Ag anode produces Ag+ ions in solution which react with CN- ions in
solution to form Ag(CN)2-, which is reduced at the cathode to form layer of silver
on fork
○ Faraday’s law: the amount of a substance consumed or produced at one of the
electrodes is directly proportional to the amount of electricity that passes through the
electrolytic cell
■ 1 C (colomb of charge) = 1 A (ampere current) * 1 s
○ Calculate amount of time that a 10-amp current has to be driven through a molten
ion
solution of Al 3+
to produce 15g of Al.
■ 15g Al / 27 g/mol = 0.556 mol Al
■ Cathode reduction reaction: Al 3+ + 3e- → Al
■ 0.556mol Al * 3 mol electrons/1 mol Al = 1.67 mol electrons
■ Use faraday’s constant… (1.67mol e-)(96,485 C/1 mol e-) = 1.61x105 C
■ 1C = 1A * 1s so… 1.61x105 C / 10 amp = 1.61x104 s
● Electrolysis of molten NaCl
○ Electrolysis: using an electric current to split a compound into its elements
○ 2 NaCl (l) → 2 Na (l) + Cl2 (g)
■ Na+ cations flow toward the cathode (negative electrode) and Cl- anions flow
toward the anode (positive electrode)
■ Reduction (at cathode): Na+ + e- → Na
■ Oxidation (at anode): 2Cl- ⇆ Cl2 + 2e-
○ Electrolytic cells use electrical work as a source of energy to drive the reaction in the
opposite direction VS. voltaic cells use energy given off in a spontaneous reaction to do
work
○ 2 electrodes are separated so products of the reaction don’t react with each other
______
● Spontaneous chemical and physical processes
○ Many processes proceed in the direction in which they are spontaneous
○ Spontaneous reactions can be exothermic or endothermic
○ Exothermic: give off heat to their surroundings
■ Ex. Oxidation of Fe to Fe (III) oxide
○ Endothermic: absorb energy from their surroundings
■ Ex. Below 0°C, water freezes spontaneously
○ Above 0°C, process is spontaneous in opposite direction: H2O (s) → H2O (l)
○ 2 driving forces that determine direction in which a process is spontaneous are
temperature and entropy
● Entropy and disorder
○ Entropy: measure of the randomness or disorder of a system
○ Water molecules in ice have high degree order: H bonds restrict their motion so its a rigid
structure
■ Increase in energy when water melts and boils
■ Water molecules in liquid water are more disordered: able to move through
space
○ Relationship between microscopic disorder and entropy given by S = k ln W
■ S: state function for entropy of system
■ K: proportionality constant
■ Ln: logarithm to the base e
■ W: measure of disorder on atomic scale
○ W: number of energetically equivalent ways you can put together a given macroscopic
state
■ W is higher for gases than liquids, which have higher W than solids
■ As W increases, entropy of system increases
■ W is small for a perfect crystal at 0K (only 1 way it can be formed)
■ W increases as crystal is warmed (motion of particles increases which increases
# of ways the particles can exist)
○ Particles of an ideal gas have certain distribution of kinetic energies (some have more KE
than average and some have less)
■ If T of gas increases and volume V same, average kinetic energy of the particles
increases
■ At higher temperature, energy distribution changes so more particles have a
higher KE
● Higher entropy means more random energy distribution
○ Entropy (S) is a state function so ΔS = Sfinal - Sinitial
○ Suniv is positive when a process produces an increase in the disorder of the universe
● Entropy and 2nd law of thermodynamics
○ 2nd law of thermodynamics: for a natural process to occur, the entropy of the universe
must increase… ΔSuniv ≥ 0
■ Processes for which ΔSuniv < 0 will probably never occur
■ If ΔSuniv = 0, process can occur in either direction
○ Universe consists of a system and its surroundings
■ ΔSuniv = ΔSsys + ΔSsurr
○ If ΔSsys > 0, system becomes more disordered during the reaction
○ If ΔSsys < 0, system becomes less disordered during the reaction
○ Solids have a smaller entropy than their corresponding liquids because they have a more
regular structure
○ Gases have a larger entropy than their corresponding liquis because their particles are
distributed over a larger volume
○ A process that increases the number of particles increases the entropy
○ Endothermic reactions (ΔH<0) are often but not always spontaneous
○ Reactions that increase the disorder of the system (ΔS>0) are often but not always
spontaneous
● Standard state entropies of reaction
○ Standard state entropy of reaction (ΔS°): change in entropy of a system due to a
reaction, measured under standard state conditions
○ Standard state conditions: all solutes have a 1 M concentration and all gases have a 1
bar (~1atm) partial pressure
○ Standard state entropies are often measured at 25°C
■ Table B.13 has standard state entropies of atom combination at 25°C
● 3rd law of thermodynamics
○ 3rd law of thermodynamics: the entropy of a perfect crystal is 0 when the temperature
of the crystal is absolute 0 (0 Kelvin)
○ As temperature increases, particles move more vigorously (average KE increases) so
disorder and thus entropy increases
○ Even at absolute 0, matter is never at rest
○ Abrupt increase in entropy (S°, with units J/mol*K) as a substance transitions from solid
to liquid and liquid to gas phases
○ Thermal entropies are a measure of the increase in disorder over that at 0K that are
produced by warming
● Calculating entropy changes for chemical reactions
○ Entropy change for a reaction measures changes in constraints to the motion of
atoms/molecules
■ So the more negative the enthalpy of atom combination, the more freedom of
motion the atoms have lost
○ 3 types of motion associated with a molecule
■ Translationional: motion of molecule as a whole; larger the mass of the
molecule, the larger its contribution to entropy
■ Rotation: turning/twisting atoms around a bond; amount depends on molecular
weight and shape... symmetrical molecules have less
■ Vibrational: within molecule because bonds stretch/compress
○ When atoms form molecules, the magnitude of decrease in entropy depends on number
of atoms in molecule, symmetry of molecule, and nature of bonds between atoms
○ Overall ΔS°>0 means reaction had an increase in entropy (more freedom of motion
and disorder for products)
■ ΔS° is always positive when bonds are broken to produce isolated atoms in gas
phase
■ Gaseous atoms can then combine to reform the starting materials or rearrange to
form the products… which process does entropy favor?
○ 2nd law of thermodynamics: natural processes tend toward maximum disorder
■ So entropy favors process with smallest decrease in entropy
■ For 2NO2 ⇆ N2O4, entropy favors recombining into starting materials (ΔS°=-470)
not the rearranging into products (ΔS°=-647)
● Gibbs Free Energy
○ Some reactions are spontaneous because they give off heat (ΔH<0) and some reactions
are spontaneous because they increase the disorder of the system (ΔS>0)
■ Both values used to determine driving force behind a reaction; balance between
them reflected by the state function Gibbs free energy (G)
○ G = H - TS
○ ΔG = ΔH - TΔS
○ Value of ΔG (change in free energy of system during a reaction) determines if reaction is
spontaneous
○ Favorable: ΔH < 0, ΔS > 0
○ Unfavorable: ΔH > 0, ΔS < 0
○ ΔG is negative for favorable/spontaneous reactions
■ When ΔG < 0, ΔH<0 and ΔS > 0 meaning reaction is favored by both enthalpy
and entropy terms
○ ΔG is positive for unfavorable/nonspotnaeous reactions
○ Reactions are either exothermic (negative ΔH) or endothermic (positive ΔH) depending
on whether they give off or absorb heat
○ Reactions are either exergonic (negative ΔG) or endergonic (positive ΔG) depending
on whether the free energy of the system decreases or increases during the reaction
○ Free energy calculations are necessary when reaction is favored by only 1 of the factors
■ If reaction is favored by both enthalpy and entropy (ΔH < 0, ΔS > 0), it will
proceed as written
■ If reaction is not favored by both enthalpy and entropy (ΔH > 0, ΔS < 0), it will not
proceed as written
○ Standard state free energy of reaction (ΔG°): change in free energy of a system that
occurs during a reaction under standard state conditions
■ ΔG° = ΔH° - TΔS°
● Effect of temperature on free energy of a reaction
○ Balance between contributions of enthalpy and entropy terms to the free energy of a
reaction depends on the temperature
○ At high temperatures, entropy term is more important than enthalpy
○ ΔG° = ΔH° - TΔS°
● Beware of oversimplifications
● Standard state free energies of reaction
○ Standard state free energy of atom combination (ΔG°ac): Gibbs free energy change
for the formation of 1 mole of a substance from its isolated atoms in the gas phase
○ See paper
● Equilibria expressed in partial pressures
○ N2 (g) + 3 H2 (g) ⇆ 2 NH3 (g)
○ Equilibrium constant KC: “c” indicates it was calculated from concentrations of
reactants and products in units of moles/liter
■ KC = [NH3]2 / [N2][H2]3
○ Equilibrium constant expressions are also written in terms of partial pressures of
components of reaction
■ By rearranging the ideal gas equation PV = nRT
■ P = [n/v] RT
■ KP = PNH32 / PN2PH23
■ KP requires partial pressures to be in units of atm
○ KP = KC * (RT)Δn
■ Δn: number of moles of gaseous products minus number of moles of gaseous
reactants in balanced equation
○ Compare reaction quotient QP to KP to predict how a gas phase reaction will shift position
of equilibrium in response to changes in temperature, pressure, or concentrations
■ QC = Qn/VΔn
■ QP = QC * (RT)Δn
■ QP = Qn * (Ptotal/ntotal)Δn
● Interpreting standard state free energy of reaction data
○ ΔG° is difference between the free energies of the reactants and products in a reaction
when all components are present at standard state conditions
○ Sign of ΔG° tells you direction that ration has to shift from standard state conditions to
come to equilibrium
■ ΔG° < 0… shift right (convert some reactants to products)
○ Magnitude of ΔG° tells you how far the standard state is from equilibrium
■ Larger ΔG° means its farther from equilibrium
● Relationship between free energy and equilibrium constants
○ Only one value of ΔG° for a reaction at given temperature, but infinite possible values of
ΔG
■ Non-standard state free energy of reaction (ΔG) used when reaction leaves
standard state because of change in pressure or concentration
○ ΔG = ΔG° + RT ln Q
■ RT and ΔG° are constants
■ Q is reaction quotient in pressure or concentration units
■ Equation can be put in straight line form y=mx+b
○ Small QP value: more reactant than product; ΔG is large and negative
■ So system far from equilibrium and must shift right
○ Large QP value: more product than reactant; ΔG is large and positive
○ When QP=1, ΔG = ΔG°
○ When QP=KP, ΔG = 1
■ For point at which line crosses horizontal axis: no driving force ( ΔG = 0 ) behind
reaction so its at equilibrium ( Q = K )
■ At equilibrium, ΔG° = - RT ln K
■ K: equilibrium constant
○ Can also get equilibrium constant from electrode potential using Nernst Equation
■ E = E° - RT/nF ln QC
■ At equilibrium, nFE° = RT ln KC
■ ln KC = nFE° / RT where E°: standard electrode potential
○ Relationship between standard state Gibbs free energy and standard electrode potential:
ΔG° = -nFE°
■ Half reactions whose standard reduction potentials have a E° > 0 will have a ΔG°
< 0: so half reactions (table 12.1) with most positive E° values have greatest
tendency to occur
○ ΔG is positive if equilibrium constant < 1 and ΔG is negative if equilibrium
constant > 1
■ Equilibrium constant is KP if reaction involves gases
■ Equilibrium constant is KC if reaction involves only aqueous solutions, pure
liquids, and solids
● Temperature dependence of equilibrium constants
○ Decreasing the temperature of an exothermic reaction increases the equilibrium
constant, making the reaction shift toward product
○ If ΔH° is positive, the equilibrium constant increases as temperature increases
○ ln K = - (ΔH°/RT) + ΔS°/R
○ ΔG° = ΔH° - TΔS°
● Gibbs free energy of formation and absolute entropies
○ Free energy of formation: difference in free energy between compound and elements that
compose it in their stable states
○ ΔG° can be found from standard state free energies of formation (ΔG°f)
■ aA + bB → cC + dD
■ ΔG° = [ c ( ΔG°f)C + d (ΔG°f)D ] - [ a (ΔG°f)A +
b (ΔG°f)B ]
■ ° for standard state means 1 atm for gases, liquids, solids and 1 M concentration
of solutes, usually 298 K
○ Tables have absolute entropies (S°) which are absolute values
■ Entropy change for a reaction can be calculated from S° values (table B.16) by
ΔS = [ cS°C + dS°D ] - [ aS°A + bS°B ]
____________________
● Reactions that don’t go to completion

○ Reactions with ⇆ stop before the limiting reagent is fully consumed and reach
equilibrium
○ Reactions with → go to completion
○ [ ] around a species refers to its concentration in M when the reaction is at equilibrium
○ ( ) refers to its a concentration at any moment
● Gas phase reactions
○ Simplest reactions occur in gas phase in a single step
○ Initially there is no product present, but over time amount of reactant decreases as its
transformed
○ Total # of moles of product and reactant = initial # of moles of reactant
■ nproduct = x
■ nreactant =
1 - x, where initial # of moles of reactant was 1
○ At equilibrium, no more product is being produced
○ Equilibrium constant KC = [product]/[reactant]
■ C means its been calculated from concentrations in units of moles/liter
■ At a given temperature, the ratio of the equilibrium concentrations of the 2
components of the reaction is constant
● Rate of reaction
○ Rate of reaction: rate at which reactants are transferred into the products
■ Change in concentration of one of the components (M) over a given time
■ Δ(X) = (X)final - (X)initial
■ If X is a product, then ΔX is positive: rate = Δ[X] / Δt
■ If X is a reactant, then ΔX is negative: rate = - Δ[X] / Δt
○ Rate decreases as the starting materials are consumed
■ Minimize error by calculating rates for infinitely short periods of time
■ Instantaneous rate of reaction: rate = - d(X) / dt
■ Rate at any moment is equal to negative of the slope of a tangent drawn to the
curve
○ Rate is proportional to concentration of reactant (rate is not constant)
■ K: rate constant
■ Rate law: rate = k [reactant]
● Collision theory model of gas phase reactions
○ Plot has 2 lines showing change in the concentrations of reactants over time as the
product is formed
■ Kinetic region: period in which concentrations of the components is constantly
changing
■ Equilibrium region: period after the reaction “stops” where concentrations of
components stays the same
○ Collision theory: explains why some reactions come to equilibrium, i.e.stop before all
the reactants are consumed an
■ Rate of reaction is proportional to the concentrations of reactants because this
affects # of collisions/second
○ CINO2(g) + NO(g) ⇆ NO2(g) + CINO(g)
■ rate = k (CINO2)(NO)
■ Rateforward = kf (CINO2)(NO)
■ Ratereverse = kr (NO2)(CINO)
○ Initially: rateforward is
much greater than ratereverse
■ As reactants are consumed, reaction slows because fewer collisions/sec
■ As concentration of products increases, the reverse reaction speeds up
○ At equilibrium: rateforward is equal to ratereverse
■ No change in the concentration of products and reactants over time
● Forces that control a chemical reaction

○ Reactions under thermodynamic control behave as thermodynamics predicts
○ Reactions under kinetic control are predicted to occur by thermodynamics, but their
rates are negligibly slow
● Chemical kinetics: focuses on what factors influence rate of reaction
○ Rate = (X)final - (X)initial / tfinal - tinitial
○ (X) indicates concentration of a reactant or product at that moment in time, in moles per
liter
○ Rate = k (reactant)
○ Rate of reaction (rate at which reactant is consumed) at any moment is directly
proportional to the concentration of the reactant at that moment
○ Proportionality constant K: rate constant
○ Rate of reaction decreases with time because reactant concentration decrease as it is
consumed in reaction
● Is the rate of reaction constant?
○ Phenolphthalein: end point indicator used in acid-base titrations; colorless in presence of
acid but pink in base
■ Once endpoint has been reached, solution will gradually turn colorless again as
phenolphthalein reacts with excess base
○ Rate = - Δ(phenolphthalein) / Δt
○ Rate law: rate = k [phenolpthalein]
■ Rates of reaction must be positive, but Δ (phenolphthalein) is negative because
its consumed in reaction
● Instantaneous rates of reaction
○ Rate of reaction between phenolphthalein and OH- decreases with time
○ To minimize error, we measure rate of reaction over infinitely small periods of time
○ Instantaneous rate of reaction = - d(X) / dt
○ Rate of reaction at any moment equals negative of the slope of the tangent drawn to the
curve
○ Initial instantaneous rate of reaction: rate that reactions occurs only at the moment the
reactants are mixed
● Rate law vs. the stoichiometry of a reaction
○ Rate law for a reaction can’t be predicted from the stoichiometry, must be
determined experimentally
■ Rate of reaction can be proportional to the concentrations of both reactants or
the concentration of just 1 reactant
○ Value you get for rate of reaction depend on which reactant you chose
● Order and molecularity
○ Some reactions occur in a mechanism with multiple steps
○ Steps of a reaction are classified in terms of their molecularity: the number of molecules
consumed
■ Unimolecular: step where 1 molecule is consumed
■ Bimolecular: step where 2 molecules are consumed
○ Reactions are also classified by their order
○ Zero order reaction: rate of reaction depends on the concentration of reactant to the 0
order
■ Rate of reaction is constant and doesn’t depend on the concentration of any
reactants!
■ 2N2O → 2N2 + O2
■ Rate = k = k[N2O]0
○ First order reaction: rate of reaction depends on the concentration of reactant raised to
the 1st power
■ N2O5 → NO2 + O2
■ Rate = k[N2O5]
○ Second order reaction: rate of reaction depends on the concentration of reactant raised
to the 2nd power
■ 2HI → H2 + I2
■ Rate = k[HI]2
○ When the reaction has n more than 1 reactant, the reaction is classified in terms of the
order of each reactant
■ CH3Br + OH- → CH3OH + Br-
■ Rate = k(CH3Br)(OH-)
■ Reaction is first order in respect to both CH3Br and OH- so second order overall
○ For general reaction A + B → C + D
■ Rate = k(A)m(B)n
■ Overall order of the reaction is m+n
■ m is the order with respect to A, and n is order with respect to B
○ Order describes the macroscopic level... we determine it experimentally by watching the
products appear or reactants disappear
■ Molecularity describes the molecular level... we deduce it to explain experiment
results
● Collision theory model of chemical reactions
○ Collision theory: rate of a step in a reaction depends on the frequency of collisions
between the involved particles
■ Kinetic molecular theory: # of collisions per second in a gas depends on the # of
particles per unit volume
■ Rate at which products are formed is proportional to the concentrations of the
reactants consumed in that step
■ Particles must collide in the proper orientation to react
○ For reaction with 1 step: CH3Br + OH- → CH3OH + Br-
■ Rate = k(CH3Br)(OH-)
○ For reactions with multiple steps: (CH3)3CBr + OH- → (CH3)3COH + Br-
■ Overall rate of the reaction is close to rate of the rate limiting step
■ Rate limiting step (RLS): step that limits the rate at which the products can be
formed
■ Rate constant for RLS is smaller than rate constants for the other steps
● Rate constant for the 1st step (k1) is smaller than the rate constants for
the other two steps (k2, k3)
● RateRLS = rateoverall = k((CH3)3CBr)
● Only 1 reactant in first step
○ Rate limiting step is not necessarily the slowest step in sequence
■ Identify RLS with the relative magnitudes of rate constants and reactant
concentrations
■ Existence of rate limiting steps is why rate law differs from what we would predict
from stoichiometry
● Mechanisms of chemical reactions
○ 2 step reaction 2 NO + O2 → 2 NO2
■ Rate2nd = k2( N2O2 )( O2 )
■ 2nd step is the rate limiting step so rateoverall ≈ rate2nd
■ However, this rate law is unhelpful because N2O2 is an intermediate
■ We can’t measure the concentrations of intermediates, which are simultaneously
formed and consumed
○ Rate law for a reaction should use concentrations of initial reactants
○ Use step 1: 2 NO ⇄ N2O2
■ Step occurs rapidly so it reaches equilibrium
■ rateforward = ratereverse, so kf(NO)2 = kr(N2O2)
■ Solve for a term that appears in rate law for 2nd step
■ kf / kr (NO)2 = (N2O2)
■ Plug expression for (N2O2) into rate law for 2nd step
■ Rate2nd = k2( kf / kr )(
NO )2( O2 )
■ Since k’s are constants, we replace expression k2( kf / kr ) with the new constant
k’
■ Rateoverall = k’(NO)2(O2)
● Zero order reactions
○ Rate law is zero-order for a component if that component is not involved in the
rating limiting step
○ How are some reactions zero-order in ALL reactants?
■ If for the reaction to occur, the reactants must bind to a catalyst that has a limited
number of active sites
■ If both reactants must bind to catalyst and are present in excess, the rate of
reaction is zero-order for both
● Determining the order of a reaction from rates of reaction
○ We determine the rate law experimentally by noting what happens to the instantaneous
rate of reaction when we start with different initial concentrations of the reactants
○ 2 HI → H2 + I2
■ Doubling [HI] quadrupled the rate and increasing concentration of the reactant 3x
lead to 9x increase in rate
■ Rate is proportional to the square of the HI concentration
■ Reaction is second-order in HI: rate = k(HI)2
● Integrated form of zero, first, second order rate laws
○ Use integrated form of rate laws to calculate how much reactant remains or how much
product will be formed in a given time
○ (X) is concentration of X at any time, (X)0 is initial concentration of X, k is rate constant,
and t is time since reaction started
○ Integrated form of zero order rate law: (X) - (X)0 = - kt
■ Original rate law - d(X)/dt = k(X)0 = k
○ Integrated form of first-order rate law: ln [ (X)/(X)0 ] = - kt
■ Original rate law - d(X)/dt = k(X)
○ Integrated form of second-order rate law: 1/(X) - 1/(X)0 = kt
■ Original rate law - d(X)/dt = k(X)2
○ Difference between second order reactions with a rate law that is 2nd order in 1 reactant
and those with a rate law that is 1st order in 2 reactants
■ If 1st order in 2 reactants, rate = k(X)(Y)
■ Integrated form kt = ( 1/[X]0 - [Y]0 ) ln ( [Y]0[X] / [X]0[Y] )
○ Half life (t1/2): time it takes for half of a sample to decay
■ Only half lives of first-order reactions are constant
■ All radioactive decay processes are first order
■ Others depend on the initial concentration of X
○ Calculate half life of 14 C
given rate constant of 1.21 x 10-4 y -1
.
■ Rate = k(14C)
■ ln [ 14C ]t / [ 14
C
] = - kt
■ By nature [ C ] = 0.5 [ 14
14
C

]0
■ Plug into integrated form of rate law… -kt = ln ( 0.5 [14 C]

/ [14
0 C]

)
0
■ ln 0.5 = -kt
■ Solve for t… t = ln (2) / 1.21 x 10-4 = 5730 years
○ Zero order half life equation: t1/2 = (X)0 / 2k
○ First order half life equation: t1/2 = 0.6931 / k
○ Second order half life equation: t1/2 = 1 / k(X)0
● Determining the order of a reaction with the integrated form of rate laws
○ If reaction is zero order in X, plot of (X) vs. time will be a straight line with a slope of -k
■ y=mx+b form is (X) = -KT + (X)0
○ If reaction is first order in X, plot of ln (X) vs. time will be a straight line with a slope of -k
■ y=mx+b form is ln (X) = -kt + ln (X)0
○ If reaction is second order in X, plot of 1 / (X) vs. time will be a straight line with a slope of
k
■ y=mx+b form is 1/(X) = kt + 1/(X)0
○ If reaction is first order in two different reactants (second order overall), a plot of natural
log of the ratio of the concentrations of X and Y will be a straight line
● Reactions that are first order in 2 reactants
○ Reactions that are first order in two different reactants (second order overall) have rate =
k(X)(Y)
○ Make a pseudo-first-reaction by making the initial concentration of one of the reactants so
large that it is basically constant
■ So the reaction is zero-order for the excess reagent
○ If you have excess of reagent Y, rate = k’(X)
■ Reaction is first order in X
■ plot of ln (X) over time will give a straight line with a slope of -k’
○ If you have excess of reagent X, rate = k’’(Y)
■ Reaction is first order in Y
■ Plot of ln (Y) over time will be linear with a slope of -k’’
○ Value of rate constant obtained from those equations = (rate constant for the reaction)
TIMES (concentration of the reagent in excess)
● Activation energy of chemical reactions
○ Only a small fraction of the collisions between reactant molecules convert the reactants
into the products of the reactions
■ Atom must collide in specific orientation
■ Molecule must have sufficient kinetic energy
○ Not all of them molecules have the same KE
■ KE is energy source to get a reaction started by breaking bonds
■ Even if ΔG° is negative for a reaction, meaning it is favorable…
○ Reaction can’t start until the reactants overcomes the activation energy (Ea, forward) for
the forward reaction
○ Activation energy for the reverse reaction (Ea, reverse): difference between the energy of
the products and the top of the energy of activation curve
○ Enthalpy of reaction (ΔH°): difference between the energy of the reactants and
products
○ As the temperature of the system increase, the number of molecules that have enough
energy to react when they collide increase
■ Rate of reaction generally doubles for every 10°C increase in temperature of
system
● Catalysts and the rates of chemical reactions
○ 5 criteria for a substance to be a catalyst:
■ Increase the rate of reaction
■ Not consumed by the reaction
■ Small quantity of catalyst affects the rate of reaction for a large amount of
reactant
● Because catalysts aren’t consumed (like reactants), they can catalyze
reaction over and over again
■ Do not change ΔH or ΔS for a reaction
● ΔH or ΔS are state functions that don’t depend on the path of reaction
■ Don’t change the equilibrium constant: don’t affect reactants or products
● Catalysts speed up the rate of forward and reverse reactions equally so
equilibrium constant stays the same
○ Catalysts increase the rate of reaction by providing a new mechanism (pathway for the
reaction) that has a smaller activation energy, Ea
■ So a larger proportion of collisions between reactants have enough energy to
overcome Ea
● Determining the activation energy of a reaction
○ As temperature increases, average KE of particles increase, so they move faster and
collide more often, so more collisions overcome the activation energy, which increases
the rate of reaction
○ Rate constant depends on temperature: k = Ze-Ea/RT
■ Z: proportionality constant unique to a reaction
■ e: base of natural log
■ R: ideal gas constant in joules per mole Kelvin
○ Arrhenius equation: in y=mx+b form, ln k = -Ea/R (1/T) + ln Z
■ To determine the activation energy for a reaction
■ Plot of ln k over 1/T should give a straight line with a slope of -Ea/r
○ To predict the effect of a temperature change on the rate constant for a reaction: ln (k1/k2)
= Ea/R (1/T2 - 1/T1)
● Kinetics of enzyme-catalyzed reactions
○ Enzymes: proteins that catalyze reactions in living systems
○ Enzyme catalyzed hydrolysis of sucrose changes from first to zero order
■ At low concentrations, reaction is first order: as concentration of reactant
increases, rate gets faster
■ At high concentrations, reaction is zero order: rate doesn’t change as
concentration of reactant increases
■ There is a maximum initial rate of reaction: once it is reached, only way to
increase rate is to add more enzyme
○ Reaction has a 2 step mechanism
■ 1. Enzyme combines with sucrose to form ES complex in a reversible reaction
● Rate constant for the forward reaction: k1
● Rate constant for the reverse reaction: k-1
■ 2. ES complex decomposes to form product P and regenerate enzyme E
● This is rate limiting step, so rate of overall reaction is determined by
concentration of ES complex
● Rateoverall ≈ rate2nd = k2(ES)
● Limit to the rate at which the enzyme can consume sucrose: no matter
how much [sucrose] is increased, reaction can’t occur any faster so it is
zero-order
○ Rate = k(sucrose)0 = k
○ Enzyme catalyzed reactions are similar to metal catalyzed reactions
■ When there is enough reactant in the system so that all of the catalytic sites are
occupied at a time, the reaction acts zero-order

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● Solubility equilibria

○ In water, molecular compounds dissolve into individual covalent molecules

○ HCl is a strong acid (Ka = 106), so it dissociates completely in water

■ Assuming HI dissociates completely in water, we can write the equation as

■ Zn is a stronger reducing agent than Ag

● Electrochemical cells at nonstandard conditions: Nerst Equation

● Reactions that don’t go to completion

● Forces that control a chemical reaction

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Chem 2 Text

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Chem 2 Text

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● Solubility equilibria

○ In water, molecular compounds dissolve into individual covalent molecules

○ HCl is a strong acid (K​a​ = 10​6​), so it dissociates completely in water

■ Assuming HI dissociates completely in water, we can write the equation as

■ Zn is a stronger reducing agent than Ag

● Electrochemical cells at nonstandard conditions: Nerst Equation

● Reactions that don’t go to completion

● Forces that control a chemical reaction

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○ HCl is a strong acid (Ka = 106), so it dissociates completely in water