Chemistry Midterm Review

Unit 1: Atomic Structure

Atomic Model and Spectroscopy

Electron Configuration
 Electrons occupy discrete energy levels where electrons are in constant motion creating an
electron cloud of possibility
 These electron clouds (orbitals) have specific shapes
o S = lowest, 1 per energy level
o P = next highest, 3 per energy level
o D = next highest, 5 per energy level
o F = highest, 7 per energy level
Quantum Numbers (n, l, ml, ms)
 N  first number, the number of the highest energy level
o Ex. 5s2 n=5
 L  second number, orbital angular momentum
o S=0
o P=1
o D=2
o F=3
 Ml  third number, orientation of electron in space (location in box)
o S=0
o P = -1, 0, 1
o D = -2, -1, 0, 1, 2
o F = -3, -2, 0, 1, 3
 Ms  last number, magnetic spin value
o Electron spinning up = ½
o Electron spinning down = - ½
Spectroscopy
 Electromagnetic spectrum  the light that is visible to us
o High frequency = shorter wavelength (UV)
o Low frequency = longer wavelength (IR)
 Photoelectron Spectrum (PES)  technique that allows use to determine the ionization energy
required to remove an electron from orbital
 UV Spectroscopy  technique used to determine what wavelengths are absorbed by a molecule
 IR Spectroscopy  technique used to study the different frequencies within a molecule

Bonding and Hybridization

Resonance Structure
 When there is more than one plausible Lewis structure for a given molecule
 The dominant resonance structure is calculated using formal charges:
o Formal Charge = Valence Electrons – Bonds – Lone Electrons
Bonding
 When orbitals combine, they form hybrid orbitals
 Hybrid orbitals are atomic orbitals since the number of orbitals in the atom remains the same
  Sigma bonds: a single bond that occurs on the same axis
 Pi bonds: any bond other than a sigma bond (triple or double bonds)
Hybridization
1. sp  2 electron domains
2. sp2  3 electron domains
3. sp3  4 electron domains

Bonding – Molecular Orbital Theory

Bond Order
 Bond order = (number of bonding electrons – number of antibonding electrons)/2
o Single = 1
o Double = 2
o Triple = 3
Bond Strength
 Bond strength is the energy required to break a bond
 The higher the bond order, the stronger the bonds are
Bond Length
 Bond length is the distance between the nuclei of covalently bonded atoms
 As bond order and bond strength increases, bond length decreases

VSEPR Theory
Bonding in Solids
Metallic Solids
 Metal + Metal
 Highest melting and boiling point as well as most conductive
o Loosely held electrons allows this
 Pure metal: consists of one metal molecule (ex. Gold, Aluminium)
 Alloys: mixtures of elementals where at least one is a metal
o Interstitial: atoms fill in the spaces between the original metal atoms (ex. Steel)
o Substitutional: atoms replace the original metal atom (ex. 14-karat gold)
 Homo-Lumo gap  determines how well a molecule conducts electricity
o Metallic solids have small gaps meaning they conduct well
Ionic Solids
 Metal + Non-metal
 Crystalline structure capable of conducting in aqueous form
o Lattice energy  the amount of energy required to separate ions so they are far apart
 Extended network of ions held together by ion-ion interactions
 Held together by electrostatic forces
 Brittle, high melting point
Covalent Network Solids
 Non-Metal + Non-metal
 Hard solids that weakly conducts electricity
 Semi-conductors with larger homo-lumo gap compared to metallic solids
Molecular Solids
 Solids held together by weak intermolecular forces
 Low melting and boiling point as well as least conductive, rather work as good insulators
 Ex. Ice
Structure of Solids
 Crystalline  ordered solids with well-defined shape
o Stronger forces = higher melting/boiling point and conductivity
 Amorphous  not ordered that do not have well-defined shapes or edges

Intermolecular Forces
Periodic Trends
 Ionization Energy (IE)  the amount of energy required to remove an electron from the outer
shell of an atom (smaller atom = higher IE)
 Electron Affinity (EA)  the amount of energy released when an electron is added (more energy
released = higher EA)
 Electronegativity (EN)  the amount of “pull” the nuclei has on surrounding electrons
London Dispersion Forces (LDFs)
 Temporary dipoles created by electron movement, present in all covalent molecules
 Weakest IMF
 Increase with molecular weight
 Decrease with increased branching

Dipole-Dipole
  In polar-covalent molecules, there are permanent dipoles
 Electrons are always being pulled in one direction resulting in the “ends” attracting one another
forming a link holding the molecules of same compound together
Hydrogen Bonding (NOFCl)
 Stronger than dipole-dipole and LDFs
 Results when hydrogen is bonded to a highly electronegative atom (NOFCl) within a molecule
 Large EN difference making hydrogen unable to hold electrons
Ion-Dipole
 Strongest IMF
 Occurs when an ion is attracted to the dipole of opposite charge in another molecule
 For example, when NaCL dissolves in water, the ions in the lattice break apart resulting in water
molecules surrounding the free floating ions
o The positive H atoms surround the negative Cl ion
o The negative O atoms surround the positively charged Na ion
Properties Explained by IMFs
 Viscosity  the measure of resistance of a liquid to flow
o Increased molecular weight and decreased temperature increases viscosity
 Vapour Pressure  the pressure exerted by the vapour when it is at equilibrium with the liquid
 Surface tension  the energy required to increase the surface area of a liquid
 Capillary Action  the amount of attraction of molecules between the same molecule or a type
of surface
o Cohesive force: forces that bind molecules to one another (water + water)
o Adhesive force: force the binds molecules to a surface (water + plant wall)
 Increased IMF strength = increased viscosity = decreased vapour pressure = increased surface
pressure = increased capillary action

Unit 2: Energy Changes & Rates of Reaction

Energy Transfer & Calorimetry
Exothermic vs. Endothermic
 Exothermic: release of energy from system into surroundings
 Endothermic: absorption of energy from surroundings into system
Energy of System and Surroundings
 System: the components of the reaction
 Surroundings: everything beyond the reaction
 System + Surroundings = Universe
 Q (system) = -Q (surroundings)
 When energy of system increases, energy of surroundings decrease
Types of Systems
 Open: energy and matter flowing in and out
o Ex. Wood burning (heat energy both in and out, light energy out)
 Closed: either energy or matter can move in or out, but not both
o Ex. Bomb calorimeter
 Isolated: ideal system which neither energy or matter can flow in and out
o Ex. Coffee Cup calorimeter
Heat Capacity
 The temperature change experienced when an object absorbs a certain amount of heat
 Specific Heat Capacity  the quantity of heat required to change the temperature of one gram
of a substance by one Kalvin or Celsius
Calorimetry
 Q = mc∆T
 Coffee Cup Calorimeter: an isolated system that is under constant pressure where you can
measure the temperature as the reaction progresses and then calculate the heat lost or gained
using Q
 Bomb Calorimeter: a closed system under constant volume where only energy is flowing rending
mass useless (Q = -c∆T)

Enthalpy
First Law of Thermodynamics
 Energy can be converted from one form to another but it is neither created or destroyed
Enthalpy (∆H)
 State function meaning the enthalpy of the system will not change unless the state of matter
changes
 ∆Hreaction = Hproducts - Hreactants
o ∆H > 0 = endothermic reaction
o ∆H < 0 = exothermic reaction
 ∆Hreaction = Breactant bonds broken – Bproduct bonds formed
o Another way of calculating the enthalpy of reaction using bond energy on a given table

Hess’s Law
Hess’s Law
 The final product of a reaction can be interpreted as the sum of several intermediate steps
 Ideally, we can determine the enthalpy of each reaction and add them up to find the final
enthalpy
 Hess’s Law of Summation: the enthalpy change of an overall process is the sum of the enthalpy
changes of its individual steps
Hess’s Rules
 If reactions are added, so are there ∆H values
 If you multiply or divide a reaction by a factor, you must multiply or divide the ∆H by that same
factor
 If you flip a reaction, the ∆H value sign changes
Standard Heat of Reaction
 ∆Hreaction = ∆Hproducts - ∆Hreactants

Entropy
Entropy (∆S)
 The degree of randomness in a system or how ordered a system is
 Increased temperature = increased entropy
 Entropy increases when matter changes
o Solid  Liquid  Gas
o Stronger bonds = less entropy
Spontaneity
 Spontaneous reaction: a process that requires no external force to begin the reaction
 Non-spontaneous reaction: a process that will not occur unless some external action is
continuously applied
Reversibility
 Reversible: a spontenous process can process in both the forward direction (to products) and
backwards direction (to reactants)
 Irreversible: cannot be reversed since the reactants/surroundings have been altered and the
system cannot restore to its original states
Second Law of Thermodynamics
 Entropy of the universes increases for any spontaneous process
 Entropy increases when:
o Pure liquids or liquid solutions (aqueous) are formed from solids
o Gasses are formed from either liquids or solids
o The number of gas molecules increases as a result of a chemical reaction
o Temperature of a substance increases, increasing kinetic energy
 ∆Sreaction = ∆Sproducts - ∆Sreactants

Gibbs Free Energy

Gibbs Free Energy (∆G)
 Allows us to determine the spontaneity of a reaction
o If ∆G is negative, spontaneous forwards, favouring products
o If ∆G is positive, spontaneous backwards, favouring reactants
o If ∆G = 0, reaction is at equilibrium
 ∆G = ∆H – T∆S
Standard Free Energy
  ∆Greaction = ∆Gproducts - ∆Greactants

Rates of Reaction and Rate Laws

Reaction Kinetics and Rates
 The rate at which a reaction occurs
 A rate refers to something that happens over time
 Factors affecting rate:
o Physical States: solids have the lowest rate while gasses have the highest due to kitetic
energy difference
 The more reactant molecules collide with one another, the more they reactant
(collision theory)
 Homogenous Reaction: reactants are all in the same phase
 Heterogeneous Reaction: reactants are in different phases
o Concentration: increased concentration = increased rate of reaction
 The more molecules of reactants, increased frequency of collisions and
therefore increased rate (collision theory)
o Temperature: increased temperature, increased kinetic energy, increased frequency of
collisions, increased reaction rate
o Catalysts: speed up reactions by adding external energy increasing kinetic energy
Measuring Rates
 Change in reactants (rate of disappearance) or change in products (rate of appearance)
 Average rate = change in concentration at time one / change in time
o Slope
o If measuring change in reactant concentration, add negative sign since they are
disappearing
Rate Law
 Rate = k[A]m[B]n
o Where k is the reaction constant
o A and B are the concentration of reactants
o M and n are the order (coefficient) of each respective reactant
Reaction Orders
Order Rate Law Integrated Rate Law Straight Line K= Units of K
0 Rate = k [A]t = -kt + [A]o [A] vs time -slope Mol L-1 s-1
1 Rate = k[A] ln[A]t = -kt + ln[A]o Ln[A] vs time -slope s-1
2 -1 -1 -1
2 Rate = k[A] [A]t = kt + [A]o [A] vs time slope L Mol s-1

Collision Theory and Reaction Mechanisms

Collision Theory
 Molecules must collide in order for a reaction to take place
 There is a minimum amount of energy required for a reaction to take place (Activation Energy)
 Correct orientation of reactant molecules is required for the reaction to take place
Reaction Mechanisms
 Rate Determining Step: the step that takes the longest amount of time
 Intermediate: a compound that is produced then later consumed in a following reaction
 Catalyst: a compound present as a reactant in step one then as product in the ending step
Elementary Processes
  The steps in a reaction mechanism which describe any molecular event that significantly alters a
molecule’s energy or geometric shape or produces a new molecule
Molecularity
 Unimolecular: process in which a single molecule dissociates (1 reactant, decomposition)
 Bimolecular: a process which involves the collision of 2 molecules (2 reactants)
 Termolecular: involves the simultaneous collision of 3 molecules (3 reactants)
Rate Laws for Elementary Processes
 Rate laws for elementary processes are determined by their molecularity
 Uni: rate = k[A]
 Bi: rate = k[A]2, if two the same reactants, or rate = k[A][B], if two different reactants
o Same as termolecular
Catalysts
 Homogeneous Catalyst: same state as the reactants
 Heterogeneous Catalyst: different state as the reactants

Entropy, Gibbs, Enthalpy