1.

1 Moles & Molar Mass

Mole – connect mass of substances reacting & number of particles
Avogadro’s number: 6.022 X 1023 / mol

Formula Mass
1. Count atoms in chemical formula
2. Find atomic mass of each element
3. Multiply atoms by atomic mass to find mass per element
4. Sum results to find total formula mass

Molar Mass – used to convert quantities btw mass units (grams) & count units (moles)
1 mole = molar mass, g (depends on identity of substance)

Conversion Factor
-ratio/fraction that represents relationship btw same quantity in 2 diff units
-used to convert an amount from 1 unit to another

1.2 Mass Spectroscopy of Elements

Mass Spectroscopy
-technique used to identify isotopes of element & relative abundance in nature
-determine elemental composition, mass of particle/molecule, isotopic composition

Each bar = diff isotope

X-axis = mass/charge, m/z, atomic mass
Height of bars = relative abundance

3 MAIN Q’s
1. Estimate atomic mass from mass spectrum
2. Identify element from mass spec
3. Identify isotope from mass spec

1.3 Elemental Composition of Pure Substances

Pure Substances – have fixed proportion (constant mass ratio of elements)
-elements present & ratio are same for every sample of compound
-cannot be separated by physical means (only chemical reaction)
Ex) every water sample has 2:1 ratio of hydrogen atoms and oxygen atoms

1. Multiply # of atoms by atomic mass  find mass per element

2. Sum results to find total formula mass
3. Divide mass of each element by total mass and multiply by 100  percent of each element

Chemical formula: identify substances by their unique combination of atoms

Empirical Formula – simplest whole number ratio of atoms of each element in compound
-determined from mass data generated from lab analysis
Molecular Formula – actual number of atoms of each element in compound
*Formulas for ionic compounds are ALWAYS empirical
*Formulas for molecular compounds MIGHT be empirical
Structural formula: shows arrangement of atoms & bonds within a molecule
1.4 Composition of Mixtures
Compound: can be broken down into elements by chemical process
Law of Definite Proportion: element mass ratio in compound is ALWAYS same
Element: cannot be decomposed into simpler substances by chemical means
Mixture – not chemically combined (can be separated physically)
-each part retains physical property
-variable compositions depending on identity & pure substances
Homogeneous: solution (salt water)
Heterogeneous: visually apparent diff substance (salad)

1.5 Atomic Structure & Electron Configuration

Structure of atom
-positively charged nucleus surrounded by electron
Proton: located in nucleus (+) 1 amu
Neutron: located in nucleus ( ) 1 amu
Electron: located in electron cloud (-) 0.0005 amu  0

Atomic Number = # of proton = # of electron

Atomic mass = # of proton + neutron
Cation: positively charged proton > electron
Anion: negatively charged proton < electron

Isotope: atoms of same element w/ diff # of neutrons  diff mass

Relative abundance: % of atoms within specific atomic mass in naturally occurring sample
Average atomic mass: weighted average – multiply relative abundance & atomic mass  SUM
-chemical properties are basically the same
-physical properties (melting/boiling point) differ

Coulomb’s law
-used to calculate force btw 2 charged particles
-force of attraction is proportional to magnitude of particle charges
-inversely proportional to distance btw them q1 = electrical charge on particle 1
q2 = electrical charge on particle 2
Ionization Energy r = distance btw them
-min E needed to remove an e- from atom/ion
-Coulomb’s law predict amount of E required to remove e- from atom
-further from nucleus = less E to remove
-closer to nucleus = more E to remove
-successive ionization energies are larger than previous ones (attractive force remains the same BUT
there’s less e-/e- repulsion)
1.6 Photoelectron Spectroscopy (PES)
Electron Configuration
-shorthand way to note location of electrons in atom
-electrons exist in “shell” (energy level) & “subshell” (sublevels)
-inner electrons = core electron outer electron = VE (s + p)
-subshells prefer to be either completely OR half filled
-orbital: 3D regions of space where e- may be found
Coefficient: # of energy level
Superscript: # of e- in the orbital

Group 1 & 2: VE in s orbital

Group 13-18: VE in p orbital
Group 3 – 12: inner/core electrons in d orbital
Lanthanide & actinide element: inner/core electron in f orbital

Octet rule: tendency for atoms to want 8 e- in Valence Shell

Effective nuclear charge: # of proton – shielding effect
EXCEPTION
Cr: 1s22s22p63s23p64s13d5
Cu: 1s22s22p63s23p64s13d10
*Transition element lose “s” before “d” when form ion

Aufbau Principle
-“To build up”
-electrons fill lower E levels first
EXCEPTION: electrons enter 4s block prior to 3d block

Pauli Exclusion Principle

-orbital can hold a max of 2 electrons
-to occupy in same orbital, 2 electrons must spin in opposite directions

Hund’s Rule
-“empty bus seat rule” – place 1 electron per orbital before pairing
-electrons occupy equal-E orbitals
-max # of unpaired electrons results

Photoelectron Spectroscopy
-experimental technique to determine relative E of electrons in atoms/ions
-use radiation to remove electrons from atom
-valence electrons  less attraction to nucleus  easier to remove
-core electrons  more attraction to nucleus  harder to remove
Position of peak: related to E required to remove an electron from corresponding subshell
Height of peak: proportional to # of electrons in that subshell
1.7 Periodic Trends
Periodic Table
-arrangement based on reoccurring element properties
-periodicity: repeating pattern  predictions of atomic properties

Periodicity: trends in properties of elements as we move across OR up & down

Period: horizontal row - 7
Group: vertical column (aka family) – 18  same VE & property
Metal: left side of table  form cations
-lustrous, ductile, malleable, good conductors
-often oxidized in reactions due to low ionization energies
-metallic character increases as go down-and-to-the-left

Nonmetal: right side of table  form anions

-good insulators, gases/brittle solids

Metalloid: semimetals – stair btw metals & nonmetals

-semiconductors (B, Si, Ge, As, Sb, Te, Po)

Hydrogen Nonmetal (no family) React w/ other nonmetals to form molecular compound
Alkali metal Group 1 (except H) 1+ charge Very reactive (unstable)
Alkaline earth Group 2 2+ charge Less reactive than alkalis
metal
Transition element Group 3-12 Variable charges
Chalcogen Group 16 2- charge Reactive
Halogen Group 17 1- charge Very reactive
Noble Gas Group 18 0 charge Unreactive (completely filled s & p orbital)
Lanthanide Element 58-71 F block
Actinide Element 90-103 F block
Main block element Groups 1, 2, 13-18 s & p blocks

Shielding effect: kernel e- “shield” valence e- from attractive force of nucleus

-caused by core & valence e- repelling each other

Properties
Atomic Radius
-size of a neutral atom (distance from nucleus to outermost electron)
-decrease ACROSS period (larger nuclear charge  greater attraction 
-move down periodic table  new E level is added  radii increase
-move across table  larger effective nuclear charge  greater attraction  smaller radius

Ionization Energy
-Energy required to remove electron from atom  inversely related to atomic radius
-ALWAYS positive (E is required for removal of electron)
Smaller radius  nuclear charge increases  increase ionization E (difficult to remove closer
electron)
Larger radius  nuclear charge decreases  decrease ionization E (easier to remove farther
electron)

Remove 1 electron when 2 electrons are in the orbital  due to repulsion btw electrons, ionization energy is
slightly lower than removing 1 electron when there’s only 1 electron

Electronegativity
-ability of an atom in a molecule to attract shared electrons to itself (F > O > N)
 -increase UP (fewer E levels  less shielding  attract electrons better)
-increase RIGHT (more protons  E levels are same  better attraction)

Electron Affinity
-E change when an atom becomes negatively charged
-atom wants extra electron if electron affinity values are negative
-can be endothermic (gain E - positive) OR exothermic (lose E - negative)
-for most atoms, adding e- causes E to be released
-ACROSS  values get more negative (some exceptions)
-DOWN  more electron shell  electron added to outer shell is farther to nucleus & more shielded
EXCEPTION: noble gasses (added e- must of into new higher E level, higher-energy p orbital, first one
to double-up a p orbital)

Metals
-easier to lose electrons
-nucleus doesn’t have strong attraction valence electron
-add electron = endothermic/slightly exothermic
-electron affinity – positive OR negative

Nonmetals
-easier to gain electrons
-nucleus has stronger attraction to valence electron
-add electron = exothermic
-electron affinity - negative

Ionic Radius
Cations are smaller than neutral atoms from which they are derived (lose e-)
-lose electrons but same # of protons  effective nuclear charge is greater  radius decreases
-increases as moving from top to bottom in a group
Anions are larger than neutral atoms from which they are derived (gain e-)
-gain electrons but same # of protons  effective nuclear charge is smaller  radius increases
-increases as moving from top to bottom in a group

Isoelectronic series: list of species having identical electron configuration

Ex) N3-, O2-, F-, Ne, Na+, Mg2+, Al3+
(big radius) (small radius)
MORE negative ion  larger size
1.8 Valence Electrons & Ionic Compounds
Valence Electron
-outer shell electrons
-likelihood that 2 elements will form chemical bond – determined by interaction btw VE
-elements in the same column of periodic table tend to form analogous compound (bc of same VE)

Ion Charges
-element in same column – form analogous compounds
-typical charges of atoms in ionic compounds – determined by location on periodic table & # of VE
MCQ
Q: 2 diff ionic compounds each contain only copper & chlorine. Both are powders, and elemental analysis is
performed on each powder. Which questions is most likely to be answered by the results of the analysis?
A: What is the formula unit of each compound? (moles of copper & chlorine can be calculated, then mole ratio
of copper to chlorine can be calculated. This ratio is the formula unit of ionic compound)

Q: P and S, whose 1s peak would be on the left on photoelectron spectrum?

A: Sulfur. 1s electron is in lower energy state and thus has larger binding energy because the nucleus of the S
has more protons than P, so the nuclear charge is greater. Electrons in the farthest right pea have smallest
binding energy bc they have weakest attraction to nucleus & are more easily removed from the atom.

Q: Which represent element that has largest jump btw second and third ionization energy?
A: ns2 (third ionization would involve removing electron closer to the nucleus than first two electrons 
require much more energy than removal of first two electrons)
-largest jump occurs btw removing one last electron & removing the next electron (in lower energy state)

Q: Why electronegativity of Cl is less than F?

A: Cl bonding electrons are more shielded from Cl nucleus than F bonding electrons are shielded from F
nucleus.

Q: Why electron affinity of Br has greater magnitude than I?

A: There is a greater attraction btw added electron and nucleus in Br than in I.

FRQ
Q: In terms of atomic structure, explain why atomic radius of K is larger than that of Na.
A: The valence electrons of K are in higher energy shell than Na.
The outer orbitals have higher principal quantum number in K than Na.
Valence electrons of K are less attracted to nucleus than those of Na.

Q: In terms of atomic structure, explain why first-ionization energy of K is less than Ca.
A: K has one fewer proton than Ca, so this results in lower attraction between the valence electron and
nucleus. Therefore, the electron is more easily removed from K nucleus.

Q: A chemist can determine mass of K. Can the chemist determine if it is pure K2O or K2O2?
A: Yes, the chemist can determine the identity of the compound. If the mass of K is determined, the percent
mass of K in the compound can be calculated and compound identified because the percent mass is different
for the two compounds.

Q: Why F- ions is smaller than O2- ion?

A: F- has larger nuclear charge than O2- has. (same electron #, but F has more proton)

Q: Elements in which of the following have most nearly same atomic radius? (Be, B, C, N) (Ne, Ar, Kr, Xe)
A: Cr, Mn, Fe, Co (ALL in d-subshell)

*Gravimetric: measures mass

*Mass Spectrometry: measure mass/charge ratio (specifically for isotopes)
*Absorbance spectroscopy: measure light absorbed by colored solutions
*Titration: acid/base and redox reactions
Q: The reactivity of alkali metals increases going down the group. Why?
A: Ionization energy decreases as you move down the group, thus it requires less energy to remove the E and
results in greater reactivity.

Q: Which represents first electron affinity of chlorine?

A: Cl(g) + e-  Cl–(g)

2.1 Types of Chemical Bonds

Electronegativity – ability of atom in a molecule to attract shared electrons to itself
Chemical bond – attraction btw nucleus of atom A & electron of atom B
-balance btw attraction (proton-electron) & repulsion (proton-proton and electron-electron)

Types of Bonds
Ionic Bond – transfer electrons (usually metal + nonmetal)
Covalent Bond – share electrons (usually 2 nonmetals)
Nonpolar – electrons shared equally
Polar – electrons shared unequally  dipole (opposite electric charges)
MORE bond  more electrons shared  stronger attraction  stronger bond
Metallic Bond – electrons not associated w/ single atom or molecule (delocalized electron)

Rule of 1.7
Electronegativity differences > 1.7  ionic bonds
Electronegativity differences < 1.7  polar covalent bonds
Electronegativity differences < 0.4  nonpolar covalent
Electronegativity differences = 0  totally covalent

Bond Polarity
-difference in electronegativity values of 2 elements
-high electronegativity  negative partial charge (-)
-low electronegativity  positive partial charge (+)
 Dipole Arrow: points towards more electronegative atom

-molecule that has center of positive charge & negative charge is polar  have dipole moment

2.2 Intramolecular Forces & Potential Energy

Bond Energy – E required to break the bond (above x-axis  less stable) (below x-axis  more stable)

No attraction/repulsion
Strong repulsion btw atoms btw atoms (PE = 0)
(PE increases - unstable)

Some attraction btw atoms w/

little repulsion (PE decreases)

Balance btw attraction &

repulsion of atoms
(Lowest PE, stable)

Bond Length: distance btw 2 bonded nuclei  occus at which PE of the structure is lowest (STABLE)
Bond strength: described by bond enthalpy (E required to break a bond)
Higher bond order = Shorter bond = Greater bond energy
Potential Energy: E stored in bonds btw atoms
 Bond Energy: E required when breaking a bond/E released when forming a bond
Bond form = E is released = negative bond E
Bond broken = E is absorbed = positive bond E

2.3 Structure of Ionic Solids

Ions – atoms that has lost/gained electrons (metal lose, nonmetal gain electron)
-few VE  lose VE to form cation many VE  gain VE to form anion
Group 1-13: form positive ions  take + charge of group number
Group 15-17: form negative ions  take - charge of group number
Group 14: do not like to lose/gain electrons  do not form ions & NO participate in ionic bonding
Polyatomic Ions: 2+ atoms that experience gain/loss of electrons together (as a unit)

Ionic Bonding
-result of ionization & attraction of ions due to +/- ions
1. Loss of electron by element A  oxidation
2. Gain of electron by element B  reduction
3. Attraction btw + and – ions formed

Ionic Solid
-lattice structure (repeating 3D units of cations & anions w/ strong coulombic forces)
-high MP & BP (ionic bonds must be broken for phase change  require high temp)
-do NOT conduct electricity in solid state (charged ions are fixed in place)
-conduct electrical current in molten/solution state (ions freely move & conduct electricity)
-many are soluble in polar solvent & insoluble in nonpolar solvents
-low volatility (tendency to vaporize)  strong electrostatic forces hold bonds together

Transition Elements
-oxidations are unexpected
-have ability to form multiple stable oxidations
 -unpaired electrons in d-shell
-diff oxidations of transition elements produce diff color variations

Lattice Energy
-E required to separate ions in soli crystal lattice into gaseous ions
-MORE charges or LESS internuclear distance  lattice E increases
-is negative (exothermic) when a bond is formed
-is positive (endothermic) when a bond is broken

Naming Ionic Compound

Group 1 & 2 + aluminum
1. Write name of metal
2. Write name of nonmetal & change ending to -ide
Ex) CaI2 – Calcium Iodide
Ex) Al2O3 – Aluminum Oxide

Transition Metals
1. Write name of metal
2. Determine oxidation # of nonmetal
3. Determine oxidation # of transition metal
4. Roman Numeral in parenthesis to identify oxidation # of metal
5. Write name of nonmetal & change ending to -ide
Ex) CuCl – Copper (I) Chloride
Ex) FeO – Iron (II) Oxide

2.4 Structure of Metals & Alloys

Metal
-composed of cations embedded in delocalized sea of electrons (electrons move around)
-# of valence electrons determines # of electrons in delocalized sea of electrons
-charge on cation & # of electrons increases  attraction increases
-ionic radius decreases  attraction increases
-luster, malleable (ions easily slide past), good conductor (delocalized electrons), high MP (strong
bond)

Metallic Bonding
-electrostatic attraction btw lattice of positive ions & delocalized electron
-all atoms in metallic bonds are alike (diffuse electron density)
-metallic atoms give up valence electrons  redistributed & shared by all
-strength dependent upon # of delocalized VE, charge of metal ion, ionic radius of metallic cation

Alloy
-combining 2+ metallic elements
-Interstitial: atoms of diff radii (smaller atoms fill spaces btw larger atoms)
-Substitutional: atoms of comparable radii (atom A substitutes for atom B in the lattice)

Ionic Covalent Metallic

Formation Anion & cation Shared electrons Cations in sea of mobile
transferred electrons valence electrons
Source Metal + nonmetal 2 nonmetals Metals only
Melting Point Relatively high Relatively low Generally high
 Solubility Dissolve best in water & Dissolve best in nonpolar Generally do not
polar solutions solvent dissolve
Conductivity Water solutions conduct Solutions conduct Conduct electricity well
electricity electricity poorly/not at
all
Other properties Strong crystal lattice Weak crystal structure Metallic properties
(luster/malleability)

2.5 Lewis Diagram

Lewis Diagrams
-shows representation of how atoms connect to form a molecule
-show the valence electrons of atoms in covalent molecules
-Lone pair = (VE – 8N)/ 2 (n = # of atoms attached to central atom)

Octet Rule: tendency of atoms to form stable arrangement (8 VE)

Exceptions:
1. Particles w/ odd number of valence e- (ex: ClO2, NO2, NO)
2. Atoms w/ less than an octet (ex: boron)
3. Atoms w/ more than octet (atom gains expanded valence shell – P, S, Xe)
*ONLY atoms of period 3+ can gave expanded valence shells

Writing Dot Structures

1. Determine # of valence electrons each atom contributes to the structure
2. Add up the total # of valence electrons
3. Adjust for charge if is a poly-atomic ion
Add electrons for – charges
Reduce electrons for + charges
4. Make the atom that is fewest in # of central atom
5. Distribute electrons so that all atoms have 8 electrons
6. Use double/triple pairs if short of electrons
7. If extra electrons, put them on central atom

Cation & Anion – should be placed in brackets w/ appropriate charge on outside of bracket
Ionic compounds – shown w/ all covalent bonds being drawn as normal
Ionic bond – denoted as ions in brackets are placed next to each other

2.6 Resonance & Formal Charge

Resonance: 1+ possible ways of drawing Lewis Diagram  show them all
-each resonance structure contributes to electronic structure Hybrid Structure

-use double arrows  indicate the real molecule is average of all three

Formal Charge
-hypothetical charge the atom would have if all of atoms had same electronegativity
-helps determine which one is the most valid structure
= (# VE) – (# bonds) – (# of non-bonding electrons)

Best Lewis Diagram: min # of nonzero formal charges

Nonzero formal charges must remain, negative charge must be assigned to most electronegative
atom
Sum of all individual formal charges must add up to charge of chemical species

2.7 VSEPR & Bond Hybridization

Valence Shell Electron Pair Repulsion
-predict geometric shapes of molecules
 -negative electrons repel each other  arrange themselves to minimize repulsion
Lone pair: non-bonding pairs – NOT involved in forming bonds

Molecular Geometry
-geometry of molecules edepend on # of electron domains (bond & lone pair) around central atom
-lone pair electrons occupy more space than bonding pairs  decrease bond angles btw bonding
pairs
-Electron repulsion degree: LP/LP > LP/BP > BP/BP

0 lone pair 1 lone pair 2 lone pair 3 lone pair 4 lone pair
2 Linear (180.0)
3 Trigonal Planar Bent (<120.0)
(120.0)
4 Tetrahedral (109.5) Trigonal Pyramidal Bent (104.5)
(< 109.5)
5 Trigonal Pipyramidal Seesaw (<120 & < 90) T-shaped (< 90.0) Linear (180)
(120 & 90)
6 Octahedral (90.0) Square pyramidal (<90) Square planar T-shaped (<90) Linear (180)
(90)

Polarity
-molecules w/ central atom symmetrically surrounded by identical atoms are nonpolar
-if surrounding atoms are identical & 0 lone pair  nonpolar molecule (lone pair = polar)
Nonpolar: symmetrical & idetical atoms
Polar: electron pull from central atom is not balanced  dipole moment

Bond Hybridization: atomic orbitals mix to form hybrid orbitals

-shape of hybrid orbital = mix of shapes of original orbitals
-# of hybrid orbitals = # of orbitals mixed
-CB  orbitals overlap  greater overlap = stronger bond
Sigma bond: overlapping of 1 orbital from each element = single bond
Pi bond: 2 lobes of an orbital of 1 element overlap vertically w/ 2 lobes of another element
overlapping of double bond
Sp hybridized (180), sp2 hybridized (120), sp3 hybridized (109.5)

MCQ
Q: A particle-level diagram of a metallic element is shown above. Typically, metals are both malleable and
ductile. The best explanation for these properties is that the electrons involved in bonding among metal atoms
are
A: equally shared and form nondirectional bonds (free movement & no fixed directional bonds)

Q: Which molecule has angular (bent) geometry that is commonly represented as a resonance hybrid of 2+
electron-dot structures?
A: O3
3.1 Intermolecular Forces
Intramolecular Force Intermolecular Force
-hold atoms together (bond) -btw 2 atoms, ions, molecules
-molecular geometry, physical property, reactivity -much weaker than CB

Dipole-Dipole Attraction
-2 polar molecules (form due to permanent dipole – attraction btw partial + & - ends)
-strength depends on magnitude of dipole (amount of polarity – diff in electronegativity)
Greater dipole moment  Greater interaction

Dipole-Induced Dipole
-polar + nonpolar – dipole of polar molecule approaches nonpolar molecule
-e- of nonpolar molecule are repelled by negative part of polar molecule
-nonpolar molecule is forced to have dipole (induced dipole - TEMPORARY)

London Dispersion Forces (LDF)

-ALL molecules exhibit LDF – result of temporary dipole (distortion of electron cloud)
-structures w/ London forces generally have low MP & BP (require little E to break forces)
-strength of LDF depends on how easily electrons can disperse
Polarizability: ease w/ which charge distribution can be distorted by external magnetic field
*SEPT: Size UP  e- density UP  Polarizability UP  Temporary dipole UP  LDF UP
 3 Factors influencing magnitude of London Force
1. # of electron: more e-  VE farther from nucleus  weak attraction  polarizability increases
2. Size of electron cloud: larger cloud  less nuclear attraction  polarizability increases
3. Shape of molecules: straight molecule  electrons interact over entire length  greater force
-branched chain molecule  hinder interaction of molecules  decrease magnitude

Hydrogen Bonding
-unusually strong case of dipole-dipole (strongest IMF)
-H bonded to electronegative atom negative end of dipole of electronegative atom (F, O, N)
-reason of unusual strength of intermolecular forces btw water molecules
-large difference in electronegativity  electron pairs pulled away from H  exerts pull on lone pair
electrons in electronegative atom of neighboring molecule
-increases MP/BP - magnitude of increase depends on strength of HB

Ion-Dipole Interaction
-interaction btw ions & polar molecule
-ionic compounds dissolve  dipole of water interacts w/ ions  force separation

Vapor pressure: pressure exerted by gas when it is at equilibrium with its liquid
Volatility: ease of evaporating
Surface tension: ability for surface of liquid to resist external force
Viscosity: resistance to flow
Heat of vaporization: E required to evaporate a substance
IMF Increase  UP: MP/BP, surface tension, viscosity, heat of vaporization
 DOWN: vapor pressure, volatility
*At comparable size: HB > dipole-dipole > LDF

WATER – liquid water contains fewer than 4, BUT solid form – maximally hydrogen bonded
 Makes solid structure less dense than liquid (ONLY substance)

3.2 Properties of Solids

Ionic Solid
-repeating arrays of metal cation & nonmetal anion
-High MP & BP, low vapor pressure due to strong attraction btw ions
 -poor conductors in solid state & good conductors when liquid/aqueous
-brittle (repulsion of like charges caused when layers slide past each other)
-low volatility (tendency of substance to vaporize) – due to strong electrostatic forces
-insoluble in non-polar solvents (due to no attraction btw ionic compound & nonpolar solvent)

Molecular Solids
-formed by distinct CB nonmetal molecules which form molecular lattice structure
-formula represents actual # of atoms in each individual molecule
-relatively low MP/BP – weak IMF holding molecules together
-poor conductors of electricity in all states (e- are held tightly in CB)

Covalent Network Solid

-repeating network of CB  form enormous molecule
-formed by carbon & semimetals (silicon/germanium/boron) (Ex: SiO2)
-very high MP & hardness – CB are relatively strong
-poor conductors of electricity – electrons held tightly in CB
Diamond -sp3 hybridized in interlocked tetrahedral shape
-strong sigma bonds  hardness
-space btw orbitals make it impossible for electrons to move around
Graphite -each carbon is connected to 3 other carbons  sp2 hybridized
-pi bonds extend above & below plane  form huge pi bonding network
-Layers slide by each other  e- freely move around  good conductor

Metallic Solid
-consist of metallic crystal w/ spherical metal atoms packed together
-exhibit metallic bonding where VE are free to flow from atom to atom
-good conductors of heat & electricity (electrons are delocalized & freely move around)
-malleable & ductile – close packed atoms/ions move past one another easily
-MORE delocalized electrons  stronger metallic bond

GENERAL Order of Strength

Molecular < Ionic  metallic < covalent

3.3 Solids, Liquids, Gases

Solids
-vibrate in place – not much KE to move freely/break strong forces holding them together
-very little space btw particles  cannot be compressed
-rigid, fixed volume & shape

Crystalline solid – repeating 3D structure

Amorphous solid – particles are disordered

Liquids
-particles are still close together (unable to be compressed)
-molecules gained enough E to slide past each other
-take shape of container
-fixed volume
-temp range is determined by strength of IMF

Gases
-particles gained enough KE to overcome IMF holding particles together
-particles are far apart  can be compressed
-quick & random movement
-take shape of container & no regular arrangement of particles
-frequency & strength of collisions depend on temp, pressure, volume
3.4 Ideal Gas Law
Volume: amount of space occupied by gas
Temperature: measurement of average KE of gas molecules
Amount of gas: measured in moles
Pressure: force exerted by molecular collisions per unit of surface area

Ideal Gas Law P = pressure in Pa

V = volume in m3
n = moles of gas
T = temperature in K
Ideal Gas Assumptions R = gas constant = 0.08206 L atm/(mol K)
-particles occupy no volume
-particles have – IMF
-high T & low P  significance of any force of attraction is minimized
-high P & low T  gas particles move more slowly

Dalton’s Law of Partial Pressure

-sum of all partial pressures = total pressure
-partial pressure: pressure exerted by each gas if it were alone

Mole Fraction (Xi)

-used to determine mole ratio of 1 substance in mixture
 -equals moles A / total moles (applicable to pressure bc p is proportional to n)

3.5 Kinetic Molecular Theory

Kinetic Molecular Theory: summarizes ideal behavior of gases
1. Volume of individual particles is nearly zero (negligible)
2. Collisions of particles w/ container walls cause pressure exerted by gas
3. Particles exert no forces on each other
4. Average KE is proportional to Kelvin temp of a gas

Molecular Size
-larger particle  technically travel shorter distance btw collision
 so they should collide more often than smaller particle
 BUT containers are large & particles are tiny  size becomes negligible
 Ideality in gases assume that combined particle V is 0

Maxwell-Boltzmann Distribution
-shows how particle speed is distributed in sample
-x-axis: particle speed
-y-axis: how frequent that particle speed is found in sample
-area under curve = 100% of particles in the sample

Temp increases Gases w/ diff masses at same temp have diff average speed
-greater # of particles + higher speed -heavy gases move more slowly
-fewer particles will be slow -lighter gases move faster  curve stretches & flattens
-curve flattens & stretches to keep area constant

Kinetic Energy
-measured in Joules (J)
-KE is both determined by mass & velocity of particles
Rate of Effusion
-ability to diffuse through small hole
-related to size of particle (particle size increases  rate of effusion decreases)

Graham’s Law

3.6 Deviation from Ideal Gas Law

Real Gas Behavior
-all gases are able to condense  attractive forces (exert IMF on each other)
-molecules vary in size & have V
-significant attraction  # of collisions decrease  actual pressure decreases
 IDEAL gas: high T (negligible IMF), low P (great spaces btw molecules)

V Adjustment under high P

-high P  molecules occupy significant part of V of conatainer
-V of molecules must be substracted from total volume of container

Gas under High P & Low T

-V decrease  P increase  particles are closer to each other  IMF becomes significant
-decrease distance btw particles/decrease KE  experience attractive forces
 Particles have reduced collisions w/ wall  reduced P

Ideal Gas Real Gas

-obeys ALL gas laws -obey gas laws ONLY under low P & high T
-V of particles is negligible -V is significant
-forces of attraction is negligible -force of attraction is significant at all T & P
-PV = nRT -does not obey ideal gas equation
3.7 Solutions and Mixtures
Matter
Mixture
Homogeneous mixture (solution) – visually uniform throughout
Heterogeneous (colloids & suspensions) – able to see diff components
Pure Substance - cannot be separated by physical means
Element (atom & element)
Compound (molecule & ion)

Solution (homogeneous mixture)

-can be solid/liquid/gas – uniform solution composition
*Heterogeneous mixtures have varying properties depending on location in mixture
Molarity (M) = moles of solute/liters of solution
Solute: what is being dissolved Solvent: what the solute has been dissolved in

Miscibility
-describe ability of 2 substances to mix w/o separating
-like dissolves in like
-tendency of polar solvents to dissolve polar solutes
-nonpolar solvents tend to dissolve nonpolar solutes

3.8 Representations of Solutions

Particulate Model
-represent interaction btw components of a mixture
-ion sizes
-orientation of solute ions & solvent particle
-represent [component]

3.9 Separation of Solutions & Mixtures

Chromatography
-method of separating mixture of solutions based on polarity differences of particles
Solvent = mobile phase Paper = stationary phase
Component parts of mixture travel at diff rates, based on size & polarity
Size: larger particles will move more slowly
Polarity: Polarity that matches solvent will move farther
Retention Factor: Rf = distance traveled by sample / distance traveled by solvent
-MORE similar in polarity  travel farther

Distillation
-separates chemical species using differential strength of IM attraction btw components
-use effects of these interactions on vapor pressures of components in mixture
-2 liquids MUST have diff boiling points
-mixture is slowly heated to temp between the boiling points of the liquids
-gas particles rise through the still head & meet cooler air

Thin Layer Chromatography

-unlike paper chromatography, separation occurs on thin plastic layer (extremely polar –
silica/alumina)
-separate sampes not colored to naked eye
-UV light is used w/ solvent that will fluoresce under UV light to see the substances
-dark spots are where components of mixture are
-used w/ amino acids

3.10 Solubility
Solubility
-extent to which a solute will dissolve into sovlent to form solution
-highly soluble: dissolve lots of solute
-slightly soluble: dissolve little solute
-insoluble: none dissolves
 Water dissolves various substances  the solution is aqueous

Substances w/ similar intermolecular attractions tend to be soluble in one another

Ionic compound: dissolve in polar solvents bc cations interact w/ negative poles of water molecules
while anions interact w/ + poles
Molecular compound: do not have dipoles & have predominantly London dispersion forces – tend to
dissolve in nonpolar solvents (larger & more polarizable electron cloud  more interaction w/
solvent)

“Like Dissolves Like”

-nonpolar solutes dissolve in nonpolar solvents
-polar solutes dissolve in polar solvents
-degree of polarity & presence of IMF determines solubility in a solvent

Hydration
-process where water molecules surround ions to dissolve them
-ionic solid is dissolved  ions become hydrated
 -water surrounds to ions  orient themselvesso that partial + end of water are closest to negative
ions & partial – end of water is closest to positive ions
-ion-dipole attraction

Solution Formation
1. Solute particles must separate (E required)
2. Solvent particles must separate (E required)
3. Solute & solvent particles must come back together (E released)
 Amount of E needed for each step depends on solvent & solute’s IMF’s
 Stronger IMF = MORE E required
 Diff do not dissolve bc there’s no enough E releaed in Step 3 to negate E required in step 1/2

Miscible – 2 substances can mix together

Immiscible – 2 substances cannot mix together

3.11 Spectroscopy & Electromagnetic Spectrum

Spectroscopy – study of matter’s interaction w/ electromagnetic radiation
-matter can absorb/emit radiation in diff regions of the spectrum

Microwave Radiation -transitions in molecular rotational level

-microwave radiation is lower in E than visible light
-MR strikes particles  cause rotation due to dipole & electromagnetic field
Infrared Radiation -transition in molecular vibrational level
-vibrational states of bonds require more E than molecular rotations
-analyze absorption, emission, reflection
-lighter atoms & stronger bonds tend to vibrate at higher frequency
Ultraviolet/Visible radiation -transition in electronic E level
-higher E  shorter wavelength  higher frequency
-allow deterination of [molecules] in solution
-photons are absorbed by compound causing e- to move to excited state

3.12 Photoelectric Effect

Photoelectric Effect – wavelength of photon is related to frequency of radiation
-a photon is absorbed/emitted by atom or molecule  E is increased/decreased by amount equal to E of
photon
-E is proportional to freqneucy & inversely proportional to wavelength

Ephoton = total energy of light

KEelectron = Kinetic energy of ejected electron
 = binding energy = E needed to remove electron

Absorbance
-measurement of light that is absorbed by solution
-measured by spectrophotometer/colorimeter
-more concentrated solution  less light can pass through solution
 -diff colors of solution absorb diff colors (wavelength) of light
Concentration = amount of particles distributed through solution (molarity)

Molarity (M)
-moles of solute / volume of solution
-moles/liter

1. Choose wavelength for measuring sample

-place sample into spectrophotometer
-generate graph of absorbance vs wavelength
-best choice is wavelength in which absorbance is close to 1

2. Create Calibration graph

-use standard solution concentration & corresponding absorbance
-graph should be linear & slope will give you molar absorptiviy constant
-more concentrated  more light is absorbed by solution

3.13 Beer-Lambert Law

Beer-Lambert Law
-relates absorption of light by a solution to 3 variables
-instruments (spectrophotometer/colorimeter) are used to determine absorbance of chemical species
(molecule/ion)

-molar absorptivity describes how intensely a sample of molecules/ions absorbs light of specific wavelength
-pathlength & concentration are proportional to # of absorbing species

Q: 1L sample of helium gas at 25’C and 1 atm is combined w. 1L sample of neon gas at 25’C and 1 atm. The
temp is kept constant. Which is true?
A: Average KE of the helium and neon atoms do not change when gases are combined (no change in temp)

Q: Infrared spectroscopy is useful tool for scientists who want to investigate structure of certain molecules.
Which best explains what can occur as result of a molecule absorbing photon of infrared radiation?
A: Energies of infrared photons are in same range as energies associated w/ diff vibrational states of chemical
bonds. Molecules can absorb infrared photons of characteristic wavelengths, thus revealing types and
strengths of diff bonds in molecules.

Q: What happens as photons of visible light are absorbed by dye molecules?

A: Certain electrons in the dye molecule move to a higher energy level, with the difference in energy btw lower
& higher E levels being the same as the energy of absorbed photons.
4.1 Introduction for Reactions
Physical Change
-substance undergoes physical process w/o changing composition of substances
-change phase, shape (cutting/tearing), size, volume, separation/formation of mixture
Ex) Separation of mixtures

Melting SL Absorb E

Freezing LS Release E
Vaporization LG Absorb E
Condensation GL Release E
Sublimation SG Absorb E
Deposition GS Release E

Chemical Change
-bonds are broken/new bonds are formed  a new substance is created
-change chemical properties (reactivity w/ acid, flammability)
-Heat/light/formation of precipitate = evidence of chemical change

Chemical Reactions
Synthesis (combination) – A + B  AB
-2+ substances react to form a single new substance
-Group A metal + nonmetal react = binary ionic compound

Decomposition – AB  A + B
-opposite of combination
-a single compound breaks down into 2+ simpler products
-products can be any combination of elements & compounds
-mostly require E in form of heat, light, electricity

Single Replacement – A + BC  AC + B
-1 element replaces 2nd element in compound
-check Activity Series to determine which elements w/ replace others
-more reactive elements will replace less reactive elements
Activity series: list metals in order of decreasing reactivity
Halogen – activity decreases as you go down group 7A (F – Cl – Br – I)

Double Replacement – AB + CD  AD + CB
-include acid/base & precipitation reaction
-exchange of positive ions btw 2 compounds
-usually take place in aqueous solution
-often produce precipitate/gas/molecule compound

Combustion of Hydrocarbon (or metal)

-element/compound reacts w/ oxygen
-produce E in form of heat/light
-always involves oxygen as reactant
-products are mostly CO2 & H2O
-hydrocarbon: compound composed of hydrogen & carbon
-CxHy + O2  CO2 + H2O

4.2 Net Ionic Equations

Balanced Equation
-can represent physical processes
-indicate identity of reactants and/or products
-same # of atoms present before & after change
-mass is conserved

Balanced Molecular Equation – show all species participating in reaction

-indicate that mass is conserved

Complete Ionic Equation

-show how ionic compounds dissociate into their ions when dissolve in water
-include spectator ions – exist on both sides & not directly involved in reaction

Net Ionic Equation – do not include spectator ions

-useful to represent only substances undergoing chemical change

4.3 Representations of Reactions

Various ways to Represent Reactions
1. Use chemical symbols to indicate reactants, products, states of matter
2. particulate models – represent chemical reaction / physical process

1. Relative Location
A. Phases of matter
-solid particles – close contact in an order that maximizes attraction & minimize repulsion
-liquid particles – close but show some disorder (movement)
-gas particles – spread out as far as possible to fill the space they are in
-aqueous solutions
-if only show solute particles – should show dissociated, individual ions to include charge
-if including solvent – solvent particles should be oriented w/ dipoles in correct direction
-if solute particles are ions – water molecules should be oriented correctly
B. Context clues
-surface or interstices of an alloy
-precipitate (solid particles should be at bottom once they have settled)
-interfaces – where 2 diff substances meet

2. Amount
-use proper # of atoms of each element
-use relative amounts of atoms when given a quantity
-observe law of conservation of mass

3. Species
-use distinct shapes, symbols, colors, shades to identify atoms/ions of diff elements
-show charges & align them appropriately
-use partial charges on polar molecules if there are IMF
-align charges & dipole moments properly to maximize attraction & minimize repulsion
-use appropriate sizing
-atoms of same element = roughly same size
-atoms of if elements – follow atomic/ionic trends on periodic table for relative size

4.4 Physical & Chemical Changes

Physical process – involves changes in IMF
-bonds are not broken/formed & chemical composition is unchanged

Chemical reaction
-involves breaking and/or formation of chemical bonds (diff composition)
-chemical composition is changed

4.5 Stoichiometry
Stoichiometry – study of relationships btw relative quantities of substances in chemical reaction
Limiting reactant: completely consumed
Excess reactant: leftover reactant

Theoretical Yield – predicted/calculated mass

-amount of product that you should be able to make based on amounts give in problem

Actual Yield – amount that you actually make in the experiment

Percent yield = actual yield / theoretical yield X 100%
Polyatomic Ion Formula
 Ammonium NH4+
Carbonate CO32-
Hydrogen Carbonate HCO32-
Cyanide CN-
Thiocyanate NCS-
Hydrogen Carbonate HCO3-
Acetate C 2H 3O 2-
Hydroxide OH-
Chromate CrO42-
Dichromate Cr2O72-
Permanganate MnO4-
Nitrite NO2-
Nitrate NO3-
Phosphate PO43-
Hydrogen Phosphate HPO42-
Dihydrogen Phosphate H2PO42-
Sulfite SO32-
Sulfate SO42-
Hydrogen Sulfate HSO4-
Peroxide O22-
Oxalate C2O42-
Thiosulfate S2O32-
Hypochlorite ClO-
Chlorite ClO2-
Chlorate ClO3-
Per-chlorate ClO4-

Acid Name Formula

Hydrochloric acid HCl
Nitric acid HNO3
Phosphoric acid H3PO4
Sulfuric acid H2SO4
Ethanoic acid CH3COOH
Hydrofluoric Acid HF
Hydrobromic acid HBr
Hydroiodic acid HI
Nitrous Acid HNO2
Sulfurous acid H2SO3
Acetic acid CH3COOH
Hypochlorous acid HClO
Chlorous acid HClO2
Chloric acid HClO3
Perchloric acid HClO4
Carbonic acid H2CO3

4.6 Introduction to Titration

Titration – known [ ] solution is combined w/ unknown [ ] solution to determine amount of moles in the
unknown
Titrant – solution of known concentration (in burette)
Analyte – solution of unknown concentration (in flask)
Equivalence point – moles of titrant & moles analyte are stoichiometrically equivalent
End point – point at which indicator changes color
Indicator – show color change at/near equivalence point
Titration curve – determine equivalence point of titration
-point where pH change is creates
= V of titrant needed to react w/ analyte in stoichiometric ratios

A + B  AB
nA = nB
MAVA = MBVB (IF 1-to-1 mole ratio btw acid & base)

2A + 3B
(1/2)MAVA = (1/3)MBVB

Types of Titrations
1. Acid-base titration
-either acid or base can be titrant
-acid-base indicator change color at pH close to 7 is added to determine end point of strong acid/base
reaction
-pH meters are used sometimes to determine equivalence point
2. Redox titration
-color change is produced when oxidation states of a metal ion in reaction change
3. Precipitation titrations
-titrant reacts w/ ions in analyte  precipitation can occur
-formation of precipitate/color change signal end point

Titration Procedure
1. Measure volume of acid solution of unknown concentration is added to flask
2. Several drops of indicator are added to solution while flask is gently swirled
3. Measured V of base of known concentrations are mixed into acid until indicator barely changes color

Standard solution: solution of known [ ]

-indicator must change color at/near pH of equivalence point
-end point: point at which indicator changes color
-pH meter: monitor acid/base titration

4.7 Types of Chemical Reactions

Acid-Base Reaction - solutions of acid & base are mixed  neutralization reaction occurs
-proton (H+) is transferred from 1 species (acid) to another (base)

Bronsted-Lowry Acid-Base reaction: transfer of 1+ protons from acid to base

-Bronsted-Lowry acid: proton donor
-Bronsted-Lowry base: proton acceptor

Conjugate Acid-Base Pair

-Acid transfers proton to base  acid becomes conjugate base
-Base accepts proton from acid  base becomes conjugate acid
*Strong acid/base form weaker conjugate pair

Oxidation-Reduction Reactions (REDOX)

-transfer of 1+ electrons btw reactants
-oxidized: lose electron -reduced: gain electron
-reducing agent: substance that undergoes oxidation  oxidized
-oxidizing agent: substance that undergoes reduction  reduced

Oxidation Number – assigned to each atom  identify oxidized & reduced species
Elemental Form 0
 Atomic ion Charge on the atom
Group I (Li, Na, K, Rb, Cs) – alkali +1
Group II (Be, Mg, Ca, Sr, Ba) – alkaline earth +2
H +1 when bonded to nonmetal & -1 when bonded to metal
O -2 in compound (-1 when peroxide form O22-)
F -1 in compound
Neutral Compound Sum of all oxidation # of atoms/ions is 0
Ionic Compound Sum of all oxidation # of atoms = charge on polyatomic ion

Precipitation Reaction
Precipitate: insoluble ionic compound results from mixing ions in aqueous solution
-sodium, potassium, ammonium are soluble  never form precipitate
-Na+, K+, NO3-, NH4+

4.8 Intro to Acid-Base Reaction

Neutralization reaction: solutions of acid & base are mixed
Bronsted-Lawry acid-base reactions: transfer of 1+ protons (H+)
Bronsted-Lowry acid: proton donor
Bronsted-Lowry base: proton acceptor
-acid & conjugate base differ by just a proton
-base & conjugate acid differ by just a proton
*Water accepts protons from & donate protons to dissolved species  amphiprotic

4.9 REDOX Reaction

Oxidation-Reduction Reaction
-REDOX reaction  electrons are transferred from 1 species to another
-oxidized: substance that loses election
-reduced: substance that gains electron

1. Write oxidation & reduction half-reaction

2. Write balanced net ionic equation for oxidation-reduction reaction

5.1 Reaction Rates

Kinetics: study of rates of chemical reaction
-rate of CHANGE of reactant/product [ ] per unit of time (unit: molarity/time)
-determined by stoichiometry in balanced chemical equation
-rate of reaction is influenced by reactant [ ], temp, surface area, catalyst, envi factors

Collision Theory: rate of reaction is influenced by anything that affects # or force of collisions

-reactant [ ] Aqueous [ ] up  more collisions  higher reaction rate

-temp -high temp  more & stronger collision  high reaction rate
-surface area -more surface area  more collisions  high reaction rate
 -catalyst -change rate of reaction by changing mechanism

5.2 Introduction to Rate Law

Rate Law: expresses rate of reaction as proportional to [ ] of each reactant raised to a power
-describes how rate of reaction is proportional to [ ] of each reactant raised to power
-sum of powers of reactant [ ] in rate law = overall order of the reaction

Rate Constant: proportionality constant in the rate law  temp dependent

Overall Order = sum of exponents from rate law

Instantaneous rate: reaction rate at any given time (equal to slope of [ ] – time curve at any point)

5.3 Concentration changes Over Time

Zero Order First Order Second Order
-a plot of [X] vs time is linear -plot of ln[X] vs time is linear -plot of [X]-1 vs time is linear
-Rate = k[A]0 = k -Rate = k[A]1 -Rate = k[A]2
-1 -1
-units for k = mol L s -units for k = s-1
-change [A] NOT affect rate -proportional change
[A]t = -kt + [A]0 ln[A]t = -kt + ln[A]0
-units for k = L mol-1 s-1

Half Life: amount of time it takes for radioactive sample to decay to half its original amount
5.4 Elementary Reactions
Elementary Reaction: process in a chemical reaction that occurs in single event/step
-overall chemical reaction consists of 1+ elementary reaction/step
-rate law for overall reaction must be determined using experimental data

Molecularity – defined by the number of particles that participate as reactants in elementary step
Unimolecular: involve only 1 particle  decomposition/nuclear decay/isomerization
Bimolecular: involve 2 colliding molecules
Termolecular: involve 3 colliding particles (VERY rare)

Intermediate: neither reactant nor product  formed during reaction & consumed by the reaction
*Intermediate should NOT appear in rate law  substitute to other [ ]

Rate Determining Reaction

-slowest step of reaction determines rate of reaction
-IF 1st step is slow, overall rate for reaction will be based on stoichiometry of 1st reaction
A + A  B (slow)
B + C  D (fast)
Rate = k[A]2
 -IF subsequent elementary reaction is slow, you have to add all of reactants up to slowest step &
cancel any intermediates to determine rate of reaction
A + A  B (fast)
B + C  D (fast)
Rate = k[A]2[C]

5.5 Collision Model

For a reaction to occur, reactant particles must…
1. Collide
2. Have proper orientation
3. Have sufficient energy (overcome activation energy)

Activation Energy (EA)

-min E that colliding particles need for reaction occur
-reaction cannot occur unless molecules possess sufficient E to get over EA barrier
-IF do not meet min E threshold, the particles bounce off one another w/o reaction taking place
-we can heat the sample to increase # of particles w/ E greater than EA

5.6 Reaction Energy Profile

Reaction Energy Profile: graphically represent reaction
x-axis: reaction coordinate
y-axis: PE (kJ/mol)

Ea increases  lower reaction rate

Enthalpy of reaction (H) = PE difference btw product & reactant

H = Eproducts - Ereactants
 Exothermic Endothermic
-product has lower PE since energy is -product has higher PE since energy is
released  negative enthalpy absorbed  positive enthalpy

Transition State (Activated Complex): intermediate pint btw 2 stable compounds

-bonds in reactants are broken & bonds in products are formed
-reactants collide w/ enough E  proceed over this TS energy hump for products
-E of transition is greater  few collisions have enough E  reaction rate is slower
-E of transition is smaller  more collisions have enough E  reaction rate is faster

5.7 Intro to Reaction Mechanism

Reaction Mechanism
-the sequence of events that describes actual process by which reactants become products
Catalyst: increase reaction rate by stabilizing transition state OR forming a new transition state
-present at the beginning & end of an experiment
Intermediate: temporary substance formed and consumed in the mechanism

Mechanism: a series of elementary steps that propose the steps by which the particles collide

5.8 Reaction Mechanism & Rate Law

-the rate of a reaction can be no faster than the SLOWEST step  rate determining step
-rate law cannot be determined from overall, balanced equation
-rate law can be determined from elementary step in mechanism
-molecularity greater than bimolecular has very low probability of occurring

5.9 Steady-State Approximation

Equilibrium: rate of forward reaction = rate of reverse reaction
-observed rate constant = combination of rate constants from steps in a mechanism
-equilibrium step can be used to eliminate intermediate in the rate law expression

5.10 Multistep Reaction Energy Profile

Each step of mechanism is associated w/ its own activation energy barrier
-PE of intermediate is in valleys between activated complexes
-reactions w/ catalyst will typically require at least 2 steps
5.11 Catalysis
Catalyst lowers PE for activated complex  increase reaction rate
-formation of more stable activated complex
-increased collision frequency
-improved orientation effects

Catalysis: process by which a catalyst changes rate & mechanism of chemical reaction
1st step: adsorption of reactant molecules onto active sites on the catalyst molecules
2nd step: products detach from the catalyst

Homogeneous Catalysis: reaction is the same phase as the catalyst  can mix w/ reactants uniformly
Heterogeneous Catalysis: reaction is diff phase than the catalyst

Enzyme
-speeds up reaction by binding w/ 1+ reactants
-reactants can be in favorable orientation OR require lower E to react
-substrate fits into active site of enzyme like a key that fits into a lock

Acid-Base Catalysis
-create new intermediate by forming CB btw catalyst & reactant
-proton is transferred btw the species
-gives new elementary steps involving new intermediate that did not form in uncatalyzed pathway
-sometimes, hold reactants together & help bonds to break (heterogeneous catalysts often)

6.1 Endothermic & Exothermic Process

Thermodynamics: Study of energy & energy conversions
Enthalpy (H) = Net Energy change (heat exchanged at constant pressure)
System: part of the universe we are studying
Surrounding: includes everything external to system (including us & thermometer)
Open system: can exchange E & matter with surroundings
Closed system: can exchange E BUT not matter w/ surroundings
Isolated system: matter can neither enter nor exit, only move around inside
Enthalpy of product > enthalpy of reactant +H (endothermic)
Enthalpy of products < enthalpy of reactant -H (exothermic)

Exothermic Flow
-heat: released into surroundings (everything external to system)
-work done BY system

Endothermic Flow
-heat: absorbed into the system
-work done ON system
**When we measure temp changes during chemical reaction, we are measuring the surroundings

6.2 Energy Diagrams

Energetically Favorable
-PE of products < PE of reactants  more stable
-energy is released from system into surroundings
-negative change in enthalpy
-Exothermic

Energetically Unfavorable
-PE of products > PE of reactants  less stable
-E is drawn in from surroundings into system
-positive change in enthalpy
-Endothermic

6.3 Heat Transfer & Thermal Equilibrium

Heat Transfer
-Temp = measure of average KE
-high temp system  molecules have higher average KE
-low temp system  molecules have lower average KE

-high temp system comes into contact w/ low temp system

-molecules collide
-higher KE molecules transfer E to lower KE molecules
-higher KE molecules slow down & lower KE molecules speed up
 Energy is transferred

Thermal Equilibrium
-both systems are at the same temp & average KE
-no exchange of energy occurring

6.4 Heat Capacity & Calorimetry

Heat Capacity
-amount of E required to raise temp one degree (Celsius/Kelvin)
-intensive property (does not change w/ change in system)
-unit: Joules/gram Celsius (Kelvin)
Increase Heat Capacity  increase heat that can be absorbed
High heat capacity  lower change in temp with a given amount of heat

Specific Heat (amount given is in grams) Molar Heat (amount given is in moles)

Calorimetry: method used to measure heat changes in experiment

Calorimeter: measure amount of heat transferred during reaction (isolated system)

Q = mCT
Q = Change in heat
m = mass in grams
c = specific heat
T = temp change
qlost = -qgained

1st Law Thermodynamics: E cannot be created or destroyed

-it’s conserved in physical/chemical change

6.5 Energy of Phase Changes

Forces of attraction are broken

-heat is required
-melting & vaporization.

Forces of attraction are formed

-heat is released
-freezing & condensation
Gaseous system – high PE
Solid system – low PE

Heat of Fusion: amount of heat needed to melt substance

Heat of vaporization: amount of heat needed to boil substance
Molar enthalpy of fusion = E required to melt a substance
Molar enthalpy of vaporization = E required to vaporize a substance
E released when freezes = E required to melt a substance (opposite sign)
E released when condenses = E required to vaporize (opposite sign)

6.6 Intro to Enthalpy of Reaction

Enthalpy Change of Reaction (Hrxn)
-gives amount of heat E released/absorbed by chemical reaction at constant pressure
-represents difference in enthalpy btw reactant & product
Exothermic: heat = product (-H) heat is produced  exothermic
Endothermic: heat = reactant (+H) heat is consumed  endothermic

6.7 Bond Enthalpies

Bond Energy = E stored in a bond
Negative  E released to form a bond
Positive  E required to break a bond
Bond Order increases  Bond E increases

Hrxn = (BE of bonds broken) + (BE of bonds formed)

positive negative

6.8 Enthalpy of Formation

Standard Enthalpy of Formation (Hf)
= enthalpy change that occurs when compound is formed from elements
-estimate overall enthalpy change of a reaction
Bond Breaking: endothermic process (H is +) (E transferred from surroundings to system)
Bond Forming: exothermic process (H is -) (E transferred from system to surroundings)

Standard State
For gases: 1 atm of pressure
For liquids & solids: most common, stable form at 1 atm and 25’C
For solutions: a concentration of 1M

Pure element in its standard state: Hf = 0

Pure element not in standard state: Hf =/= 0

6.9 Hess’s Law

 -Change in enthalpy is the same whether reaction takes place in 1 step OR a series of steps
-overall enthalpy change of a reaction = sum of H values of each smaller step

7.1 Intro to Equilibrium

Reversible Changes
-all phase changes are reversible
-dissolved salts can precipitate out of solution & dissolve again
-gases can come out of solution be reabsorbed into solution

Forward reaction: left-to-right reaction

Reverse reaction: right-to-left reaction

Loss & gain of protons (H+) in acid-base reaction

Loss & gain of electrons (e-) in redox reaction

Equilibrium: rates of forward & reverse reactions are equal

-[reactant] & [product] do not change
-is dynamic  forward & reverse reactions do not stop once equilibrium is reached

Physical equilibrium: occurs due to physical changes in reactant (chemical change)

Chemical equilibrium: occurs when new chemical product is a made chemical change
Dynamic equilibrium: both forward & reverse reactions continue to occur even in equilibrium state

7.2 Direction of Reversible Reaction

Rate of forward reaction > Rate of reverse reaction  forward is favored
Rate of forward reaction < Rate of reverse reaction  reverse is favored

7.3 Reaction Quotient & Equilibrium Constant

Reaction Quotient (Q)
-represent relative Q of reactants & products at any given point in a time as (products : reactants)
-at equilibrium, Q = K (equilibrium constant)

*Solid & Pure Liquids are NOT included in reaction quotient (only gase & aq)

Equilibrium Constant (K)

-we use equilibrium constant K when system is at equilibrium

Kc Value Interpretation
Kc > 1 Reaction nearly goes to completion Favor product
Kc < 1 Reaction proceeds only in small amount Favor reactant
Kc = 1 [product] = [reactant]
(0.001 or smaller  barely proceeds at all)
(1000 or more  goes to completion)

7.4 Calculating Equilibrium Constant

Temp changes  affect value of K

7.5 Magnitude of Equilibrium Constant

K>1 [product] > [reactant] products are favored

K1 [product]  [reactant] same order of magnitude
K<1 [product] < [reactant] reactants are favored

K is extremely large  reaction goes to completion

K is extremely small  forward reaction essentially does not take place
7.6 Properties of Equilibrium Constant
Reverse Reaction  take inverse of the value of K
Kreverse = 1/Kforward
Koverall = K1 x K2 x K3…
Chemical reaction is multiplied  K is raised to the power of that factor

7.7 Calculating Equilibrium Concentration

At equilibrium, Q = K at equilibrium
Q>K [product] must decrease OR [reactant] must increase
Q<K [product] must increase OR [reactant] must decrease

Equilibrium conditions are diff from initial conditions

ICE (initial, change, equilibrium) tables are used to organize equilibrium calculations

A B AB
Initial xM xM xM
Change -/+ M -/+ M -/+ M
Equilibrium M M M

7.9 Intro to Le Chatelier’s Principle

Le Chatelier’s Principle
-if a stress is placed on a system, the system will react in such a way as to relieve stress
-we can stress a system by changing molarity, partial pressure, temp, volume, and/or pressure
-when equilibrium system is stressed, system will shift to reduce the stress & re-establish equilibrium

Change in Concentration
*do not affect Kc
[reactant] increase  shift to the right
[product] increase  shift to the left

Change in Pressure
-increase P/decrease V  shift to the direction w/ fewer moles of gas to minimize pressure

Change in Temp
-increase temp  shift reaction to endothermic side
-decrease temp  shift reaction to exothermic side

Addition
Add Catalyst  increases rate in BOTH directions  NO stress
Add solid  solids are NOT included in equilibrium constant expression  no stress
7.10 Reaction Quotient & Le Chatelier’s Principle
Q > Kc [product] is greater than equilibrium  reverse reaction is favored until equilibrium is reached
Q < Kc [reactant] is greater than equilibrium  forward reaction is favored until equilibrium is reached
Q = Kc the system is at equilibrium and forward & reverse occur at equal rates

7.11 Intro to Solubility Equilibria

Solubility (S): Amount of a salt that will dissolve to form a saturated solution at given temp

7.12 Common-Ion Effect

In the presence of common-ion  solubility decreases

7.13 pH and Solubility

-Qsp < Ksp shifts to consume reactant & form product  undersaturated  NO precipitate
-Qsp ≥ Ksp shifts to consume product & form reactant  oversaturated  FORM precipitate
Ksp > 1: soluble salt

7.14 Free Energy of Dissolution

Spontaneity: describe if reaction will take place
Entropy Dissolution (Sdissolution)
Entropy: measure of dispersal of E & matter
Free Energy Dissolution (Gdissolution)
G = H - TS

8.1 Intro to Acids & Bases

Acid Base
-release H+ ions in solution (proton donor) -release OH- ions in solution (proton accepter)
-pH < 7 -pH > 7
-Blue litmus red -red litmus blue
-phenolphthalein is colorless -phenolphthalein is pink
-methyl orange is red -methyl orange is yellow

pH = -log[H3O+]
pH scale simplifies scale based on
large range of molarity values
[H3O+] up = pH down  More acidic
[H3O+] down = pH up  More basic

pH Calculation
Kw (water constant)
-significance of autoionization: there is H+ & OH- ions present in all solutions  relative [ ] will be linked by their
equilibrium constant
-Kw = [H3O+][OH-] = 1 x 10-14M at 25’C
-[H3O+] = 1 x 10-7M [OH-] = 1 x 10-7M
-both pH & pOH are 7.00
-pKw = pH + pOH = 14 at 25’C
-temp increases  Kw increases  [H3O+] [OH-] increase (favor endothermic)
*Sig fig for pH, pOH, pKw – ONLY # after decimal point is significant

8.2 pH & pOH of Strong Acids & Bases

Strong Acid
-completely ionize in aqueous solution to produce H3O+
Ex) HCl, HBr, HI, HClO4, HNO3, H2SO4
[H3O+] = Mstrong acid
pH = -log[H3O+] = -log Mstrong acid
Monoprotic Strong Acid: [acid] = [H3O+]

Strong Base
-completely dissociate in aqueous solution to produce hydroxide ions
Ex) LiOH, NaOH, KOH, Ba(OH)2, Sr(OH)2 other group I & II hydroxides
[OH-] = Mstrong base x number of OH- ions per mole
-Group 1 – [OH-] after dissociation is equal to original base molarity
-Group 2 – [OH-] after dissociation is equal to twice the original base molarity

Weak Acid
-ionize only a small percentage of molecules when dissolved in water
-HA(aq) + H2O(l) H3O+(aq) + A-(aq)
-acid dissociation constant (Ka) = [H3O+][A-] / [HA]
pKa = -logKa (Ka = acid-ionization constant)
[H+] = (Ka x Ca)1/2 Ca = initial concentration of the weak acid
-smaller Ka, larger pKa, weaker acid
Weak Base
-react w/ water to produce hydroxide ions (ONLY in a small percentage)
-B + H2O HB+ + OH-
-base dissociation constant (Kb) = [HB+][OH-] / [B]
pKb = -logKb (Kb = base-ionization constant)
-smaller Kb, larger pKb, weaker base

Larger Ka Stronger Acid lower pKa

Smaller Ka Weaker Acid higher pKa
Larger Kb Strong Base lower pKb
Smaller Kb Weaker Base higher pKb

8.3 Weak Acid and Base Equilibria

Equilibrium constant does NOT change when molarity values change
Percent ionization DOES change when molarity values change

-solution is diluted  ALL molarity values decrease

-acid dissociation: numerator decreases more than denominator
-Qa < Ka
-reaction shifts to consume reactant & form product until Q = K
-% ionization increases as molarity decreases

-weak acid equilibrium calculations are solved using the same approach as other systems
-mole ratio for weak acid equilibrium reactions is always 1:1:1 since only 1 transfer of H+ at a time
-% ionization of reaction compares molarity of H+ transferred to original molarity of weak acid present
-% ionization is DEPENDENT on molarity of weak acid (inverse relationship)

8.4 Acid-Base Reactions & Buffers

Strong Acid + Strong Base
H+(aq) + OH-(aq)  H2O(l) (neutralization)
 pH of resulting solution is determined from [excess reagent]
1. Find moles of acid & base
2. Find amount of excess leftover after neutralization
3. Divide moles of unreacted excess reagent by total volume of solution  find molarity
4. Use pH scale to answer the question

Weak Acid + Strong Base

-resulting solution is basic
-HA(aq) + OH-(aq) A-(aq) + H2O(l)

IF weak acid is in excess  resulting solution is buffer solution

Buffer: solution containing relatively high concentrations of conjugate acid-base pair
 resists changes to pH when small amount of strong acid/base is added

IF strong base is in excess

-pH of resulting solution is calculated from M of solution formed from excess moles of base divided
by total V of solution

IF weak acid & strong base are equimolar

 -pH of resulting solution is determined by conjugate base of weak acid
-use ICE table to find equilibrium [ ] of OH-
-Find Kb to use as K constant
-use moles of conjugate base & total V to find initial molarity

Weak Base + Strong Acid

-resulting solution is acidic
-B(aq) + H3O+(aq) HB+(aq) + H2O(l)

IF weak base is in excess

-resulting solution is buffer solution
-use Henderson-Hasselbalch equation to determine pH of resulting solution
IF strong acid is in excess
-pH of resulting solution is calculated from M of solution formed from excess moles of hydronium ion
divided by total volume of solution
IF weak base & strong acid are equimolar
-reaction is at its equivalence point
-moles of acid & base are equal

Weak Acid + Weak Base

-it depends on the pKa & pKb values
-HA + B  A- + HB+
-the resulting solution will react to reach equilibrium
HA(aq) + B(aq) A-(aq) + HB+(aq)

Dilution: V1M1 = V2M2

Stoichiometry: any strength acid + base will proceed to make product until limiting runs out
Equilibrium: if weak acids/bases are involved then may need to do equilibrium calculation

Factors Affecting Acid Strength

1. To transfer H+, acid must have polarity  strength increases
2. BUT IF H-X bond is too strong  acid is weak
3. Stable (weak) conjugate base  strong acid

8.5 Acid-Base Titrations

-at V greater than half-equivalence point, conjugate acid is the dominant species
-at equivalence, conjugate acid is the only species (pH is determined from reaction btw conjugate acid & H2O)
-for weak base, region around half-equivalence point = buffer zone

Titration Curve
-plot pH against V of titrant added
-summarize results from a titration
*Equivalence point  stoichiometric balance when [H+] = [OH-]
 ONLY for strong acid/strong base titrations will pH = 7 at equivalence point
*End point: point at which indicator changes color (all of substance being quantified has been
reacted)

Half Equivalence point: when HALF of acid/base is neutralized

-equal [ ] of each species in conjugate acid-base pair
Ex) weak acid, [HA] = [A-]
pH = pKa + log[A-]/[HA]
Monoprotic Acid
-1 acidic hydrogen

Polyprotic Acid
-have more than 1 ionizable H (H2SO3)
-titration curves can be used to determine # of acidic protons

Organic Acid
-carbon backbone, usually contain COOH (carboxyl group)
-generally very weak

Amphoteric – can behave either as acid or base (ex: water)

8.6 Molecular Structure of Acids & Bases

Binary Acid
-chemical structure of acids control relative strength
-Bond length/strength, electronegativity of atoms in compound affect degree of dissociation

Oxyacid
-ternary (made from 3 elements) acid w/ 1+ oxygens in its structure
-increasing # oxygen atoms in acid means stronger acid (increased stability & resonance)
-additional oxygen tends to increase acid’s strength due to additional Electronegativity
-inductive effect: attraction of electrons in adjacent bonds by more electronegative atoms

Strong Acid – can experience inductive effect due to highly electronegative oxygen atoms
-polarity in the molecule draws electrons away from hydrogen atom  easily ionizable
-have very weak conjugate bases that are very stabilized

Weal Acid – do not experience strong induced dipole force

-less polarity in the molecule results in hydrogen ion being more attracted to oxygen  less ionizable

Strong base – attract protons

-strength of base is influenced by…
1. How easily the lone pair picks up hydrogen ion
2. The stability of ions being formed
-conjugate bases of carboxylic acids, anions of weak acids, organic amines ALL act as bases
 -have very weak conjugate acids

Electronegative elements tend to stabilize conjugate base relative to its conjugate acid  increase acid
strength

Carboxylic Acid
-consist of carbon that is double-bonded to oxygen & single-bonded to another oxygen
-R group represents remainder of the molecule
-double bonded oxygen shows inductive effect by drawing electrons & weakening O-H bond

8.7 pH & pKa

pH < pKa acid form has higher [ ] in original solution
pH > pKa conjugate base form has higher [ ] in original solution

Acid-Base Indicator: substances that exhibit diff properties in protonated & deprotonated states

Indicator:
-weak organic acid/base that change color when pH = pKa
-HIn  H+ + In- (In = indicator)
-Midpoint: [HIn] = [In-] pH = pKa [H+] = Ka
Strong Acid + Strong Base = equivalence point pH = 7
Weak Acid + Strong Base = equivalence point pH > 7
Weak Base + Strong Acid = equivalence point pH < 7

8.8 Properties of Buffers

Buffer: solution that is resistant to change in pH upon addition of strong acid/base
-contain weak acid + conjugate base OR weak base + conjugate acid
-acid capable of reacting w/ added OH- ions & base that can consume added H3O+ ions
-acid & base must not react w/ each other

4 ways to make buffer

1. Partial neutralization of weak acid w/ strong base
2. Partial neutralization of weak base w/ strong acid
3. Weak acid + salt of conjugate base
4. Weak base + salt of conjugate acid

Buffer System
-acidic buffers maintain pH < 7 provide reservoir, ready to react w/ OH- or H+
-basic buffers maintain pH > 7 provide reservoir, ready to react w/ H+ or OH-
[H+] x [OH-] = 1 x 10-14

2 Types of Buffers
1. Weak Acid & Conjugate Base
-buffer solution w/ pH < 7
-IF acid is added  combines its free H+ w/ ions from conjugate base  make weak acid
 -IF base is added  OH- ions from the base react w/ H+ in weak acid dissociation

2. Weak base & Conjugate Acid

-buffer solution w/ pH > 7

8.9 Henderson-Hasselbalch Equation

-describe relationship btw pH of buffer & pKa of acid & [ ] ratio of conjugate acid-base pair
-qualitatively determine info about a reaction
pH = pKa conjugate base & acid [ ] are equal [HA] = [A-]
pH > pKa conjugate base [ ] > acid form [HA] < [A-]
pH < pKa conjugate base [ ] < acid form [HA] > [A-]
*EVENTUALLY, IF [Acid] ≫ or ≪ [base]  mixture loses its ability to function as buffer

8.10 Buffer Capacity

Buffer Capacity
-amount of acid/base that can be added to buffer system w/o pH changing by more than pH of 1
-higher [ ], more effective buffer at resisting changes in pH
-increasing p [ of buffer components keeps pH of buffer the same BUT increases amount of acid/base
the buffer can neutralize
-diluting a buffer solution will NOT change its pH

Buffer has more conjugate acid than base  greater buffer capacity for added base than added acid
Buffer has more conjugate base than acid  greater buffer capacity for added acid than added base

Optimum buffer: buffer that is most effective when pH is equal to pKa

-optimal pH of buffer is equal to pKa of acid/base used to prepare buffer

9.1 Intro to Entropy

Entropy: dispersal of matter/energy in a sample of matter (amount of disorder)
-positive value  system increased in entropy
-negative value  system decreased in entropy

Temp Increase
-direct link btw temp & KE  movement of particles from one place to another
-increasing temp affects molecular vibration, rotation, electron level, electron spin
 INCREASES DISORDER

Change in State
-phase change from S  L or L  G result in dispersal of matter
-individual particles become freer to move & occupy larger volume
-entropy of gas increases when V increases bc molecules can move within a larger space at same
speed
-total # of moles of gaseous products > total # of moles of gaseous reactants  entropy increases

Substance Mix to form Solutions

-mixtures have higher entropy than pure substances in general
-dissolving can be hard to predict since water molecules are concerned
-increase in disorder experienced by the solute
Increased # of moles

Increased V of gas

Microstate
-actual chemical system contains huge # of possible sections called microstates
-particles/energy in system are more spread out into microstate  higher entropy
-particles/energy in system are less spread out amongst microstate  less entropy
-place same amount of gas into 2 containers w/ diff volumes at same temp  gas in container w/
larger volume has greater entropy (greater disorder of matter in larger container)
-based on kinetic molecular theory, system w/ higher temp has greater KE of particles  this energy
distributed into particles will be greater  greater entropy as temp increases

9.2 Absolute Entropy & Entropy Change

Entropy change – calculated from absolute entropy of species involved before & after process occurs
-entropy is expressed in joules / Kelvin
-most substances have nonzero value for absolute entropy
-# of moles of each substance must be considered when calculating entropy

9.3 Gibbs Free Energy & Thermodynamic Favorability

Gibbs Free Energy Change
-describes whether a reaction is thermodynamically favorable or unfavorable
Standard State: pure substance, solutions of 1.0 M concentration Or as gases at pressure of 1.0 atm

Driven by enthalpy ONLY negative H & S

Driven by entropy ONLY positive H & S
Driven by BOTH negative H, positive S

9.4 Thermodynamic & Kinetic Control

Kinetic Control
-thermodynamically favorable BUT do not appear to make products are measurable rate
-catalyst may be used to decrease activation energy BUT has no effect on thermodynamic favorability
-high activation energy
-unfavorable orientation
-high # of particles must collide simultaneously

9.5 Free Energy & Equilibrium

Thermodynamically favored (G < 0) means the products are favored at equilibrium (K > 1)
At equilibrium, no net change in [reactant] or [product] occurs  and
-R has to be 8.314 J/mol K
-T has to be in Kelvin
-G has units of J/mole

Reaction Quotient (Q)

Q<K approaching equilibrium from reactant side
Q=K equilibrium reached
Q>K approaching equilibrium from product side
Gactual = G + RTlnQ

G is negative K>1 favor product

G is positive K<1 favor reactant
G = 0 K=1 equilibrium

9.6 Coupled Reactions

Process w/ positive G value is thermodynamically unfavorable
2 paths to make such a process occur:
1. External source of energy  Ex: sunlight/electrical power source
2. Thermodynamically unfavorable reaction can be coupled to another favorable reaction

Coupled Reaction
-2 reactions that share common intermediate (product of 1 reaction is a reactant in the other)
-Hess’s law is applied to determine free energy change
-typically used to drive unfavorable reactions that are industrially important

9.7 Galvanic & Electrolytic Cell

Electrochemical cell: device that converts chemical E into electrical E or vice versa (REDOX reaction)
Galvanic cell: involve thermodynamically favorable reaction
Electrolytic cell: involve thermodynamically unfavorable reaction
Electrode: conductor of electricity used to make contact w/ non-metallic part of circuit
Electrolyte: solution which will conduct electricity

Galvanic (voltaic) Electrolytic

 -thermodynamically favorable reaction -Thermodynamically unfavorable reaction
-cathode (+) & anode (-) -cathode (-) & anode (+)
-Salt Bridge: allows ion movement btw half-cells -power source is needed
-cation move into reduction half-cell -reaction occurs in single chamber (no salt bridge)
-anion move into oxidation half-cell -electrons flow from anode to power source & from
 allow charge balance to be maintained & is power source to cathode
necessary for current to flow in circuit -occurs in ionic solution/liquid
-produce electrical energy (+ voltage value) -cations flow to cathode, anions flow to anode to
-2 compartments w/o power source maintain charge balance
-positive cell potential -use electrical energy – negative cell potential
-oxidation at anode, reduction at cathode
-require ion flow in cell for reaction to occur (cation  cathode, anion  anode)

Cell Diagram Convention

Single line = phase boundary
Double line = salt bridge
Aqueous solution goes next to salt bridge
Anode on left & cathode on right
Arrow shows electron flow

Dry Cell: voltaic cell in which electrolyte is a paste

Fuel Cell: voltaic cells in which fuel undergoes oxidation & from which electrical E is continuously obtained
-do not have to be recharged

Electrolytic Cell: electrochemical cell used to cause chemical change through application of electrical E
-use electrical energy to make non-spontaneous redox reaction proceed to completion
-electrolysis: process in which electrical energy is used to bring about chemical change

9.8 Cell Potential & Free Energy

Standard Reduction Potential: electric potential difference btw oxidation & reduction process in half-cell
-symbol for reduction potential: E (unit = volts, V)
-to compare reduction potentials, standard reduction potentials are used (under standard condition)

Cell’s standard potential (E cell)

-calculated from reduction half-reaction standard potentials at cathode & anode

-
-half-reaction occur in at anode – oxidation (minus sign accounts for reversal of reduction potential)
-electrical potential does not depend on amount of substance reacting (do NOT multiply values of
half-reaction potentials by coefficients in overall cell reaction)

Thermodynamic favorability
-thermodynamically favorable reactions have positive overall cell potentials
 therefore, all voltaic cells have positive cell potentials
-thermodynamically unfavorable reactions have negative overall cell potentials
 therefore, all electrolytic cells have negative cell potentials

Nernst Equation

n = # of moles of electrons transferred

 F = faraday’s constant (96485 Coulombs / mole e-)
E = voltage

9.9 Cell Potential Under Nonstandard Conditions

-Cell Potential (Ecell) depends on [ ] or pressure of reactant & product
-standard conditions are 1.0 M solutions & 1.0 at gases (Q = 1)
-cell operates  reactants are consumed & products are produced  [ ] change  cell potential change
-changing mass of solids does not affect cell potential  does not affect Q

Deviation from standard condition that takes cell FURTHER from equilibrium than Q = 1
 increase magnitude of cell potential relative to E

Deviation from standard condition that takes cell CLOSER to equilibrium than Q = 1
 decrease magnitude of cell potential relative to E

Nernst Equation: Eactual = E-(RTlnF)lnQ

Q = [products] / [reactants]
R has to be 8.314 J/mol K
T has to be in Kelvin

Q<1 lnQ (negative) E > E

Q=1 lnQ = 0 E = E (standard condition)
Q>1 lnQ (positive) E < E

-Voltaic Cell: increase Q = decrease Ecell (vice versa)  refers to |Ecell| bc cell potentials are negative
-NEVER use Le Chatelier argument when discussing nonstandard cells (NOT at equilibrium)
-changing mass of solids does not affect cell potential
*Decrease Q relative to its value in standard cell moves it further from K  value of cell potential increase

9.10 Electrolysis & Faraday’s Law

Faraday’s Law q=lxt
Charge = Current x Time

Current: (ampere)
Charge: (Coulomb)
Time: (sec)

Charge carried by one e- = 1.6023 x 10-19 C

1 mole e- = 96485 coulombs
1 Faraday’s constant = 96485 C/mol e-

Solving Problems
-attention to units & use of dimensional analysis
-current is in units of Amperes (A) = equivalent to Coulombs/second (C/s)
-time needs to be in seconds
-Faraday’s constant is charge per mole of electrons (96485 C/mol e-)
-moles of electrons per mole of reaction is determined from chemical equation
-moles & molar mass are used to convert btw grams & moles