Lecture 1: Collision Theory

1. Describe what interactions are involved in a physical vs. a chemical change.

Physical Change Chemical Change

● No bonds are broken or formed ● Bonds are broken or formed between molecules or atoms
○ Composition/identity stays the same ○ One substance with a certain set of properties is turned into
● Ending materials are the same as the beginning materials a different substance with different properties
○ Properties are the same ● Evidence for chemical changes - temperature changes, light given off,
● Move molecules around unexpected color changes, bubbling, different smell or taste, a
● Examples: changes of state, separation of a mixture, physical precipitate forms
deformation, making solutions ● More difficult to reverse
● Reversible

2. Write reactions to illustrate changes of state.

a. Vaporization = liquid to gas
b. Melting = solid to liquid
c. Condensation = gas to liquid
d. Sublimation = solid to gas
e. Deposition = gas to solid

3. Define temperature and how it relates to kinetic energy.

a. ΔHrxn = sum of BE for reactants - sum of BE for products
b. Temperature - a measure of kinetic energy at the molecular level
i. It is proportional to the amount of kinetic energy per atom
c. Heat - transfer of energy in the form of molecular level kinetic energy
i. If heat is added to a system…
1. There will be an increase in kinetic energy (therefore an increase in temperature)
2. It will be converted to potential energy
3. Then it is converted to work against external pressure, making the system expand
d. When the temperature is applied to a system, the molecules gain more kinetic energy because they are excited
by the addition of heat as energy

4. Define activation energy and explain how changing temperature affects particle
collisions and the rate of reaction.
a. Activation energy = energy necessary in order for a reaction to take place
i. Provide enough kinetic energy to overcome the potential energy barrier
b. Increase temperature, increase the frequency of particle collisions (particles moving faster), increase rate of
reaction

5. Describe how particle orientation affects whether or not a reaction will occur.
a. Must reach a geometric arrangement of atoms that will promote the weakening of the breaking bond and
formation of the new bond
b. Collisions must have the correct orientation to react
i. They will collide but not react if the arrangement is not proper

6. Explain how some particles can react even when the average kinetic energy of the
system is less than the activation energy for the reaction.
a. As they collide, some particles gain more than the average kinetic energy of the system at the expense of other
molecules. These extra-energetic molecules are then able to react.

7. Describe how concentration influences rates within a gas-phase reaction.

a. Concentration determines the rate of collisions
i. Rate of collision is proportional to the number of atoms
1. More molecules per unit of volume
ii. Rate of reactions is also proportional to the concentration of the number of atoms
 8. Interpret and draw thermal energy distribution graphs.
a. As the distribution is shifted to higher energies, a greater fraction of molecules
have energy in excess of the activation energy. The probability that a collision
leads to a reaction will increase with increased temperature.

Lecture 2: Introduction to Free Energy

1. Connect your understanding of potential energy from Chem 150
to the new concept of bond dissociation enthalpy.
a. Bond dissociation enthalpy = the energy needed to break one mole of the
bond to give separated atoms
b. Potential energy = energy stored in molecular bonds
i. This energy must be released or absorbed in order to form or break bonds, respectively
ii. Breaking bonds increases potential energy and absorbs heat
iii. Forming bonds reduces potential energy and releases heat

2. Calculate the enthalpy of a reaction (ΔH°) from bonds broken and bonds formed.
a. ΔH° = bonds broken - bonds formed
i. If -ΔH° = exothermic
ii. If +ΔH° = endothermic

3. Describe the difference between endothermic and exothermic reactions.

Endothermic Reactions Exothermic Reactions

● Heat energy in (ΔH° is positive) ● Heat energy out (ΔH° is negative)

● Bond-breaking costs more energy than what is provided in bond- ● More energy is released by the formation of new bonds than is
making consumed by breaking bonds

● Weaker bonds are traded for stronger bonds

4. Define enthalpy and explain how it relates to free energy.

a. Enthalpy = heat content of a system
i. Heat exchanged between the system and surroundings at constant pressure
ii. Thermodynamic quality defined by H = U + pV
1. Enthalpy = internal energy + pressure(volume)
a. pV is included because some heat energy must be converted to mechanical work
energy for pushing away the surroundings when volume increases
b. When volume decreases, surroundings are doing work on the system
iii. Since the average molecular kinetic energy depends on temperature, chemical energy at a constant
temperature will not change kinetic energy but will release heat if the total potential energy within all
of the bonds goes down
1. Will absorb heat if the total PE of the chemical bonds goes up and becomes less negative
(breaking bonds, forming weaker bonds)

5. Describe the difference between spontaneous and non-spontaneous processes.

a. See Lecture 3, Learning Goal 2.

6. Define what a state function is and give examples.

a. State functions = values that depend on the state of the substance, and not on how that state was reached
i. Examples: density, enthalpy change

Lecture 3: Free Energy Continued

1. Define enthalpy, entropy, and free energy as well as describe the relationship
between them.
a. Enthalpy (H) = amount of energy released or absorbed during a chemical reaction
b. Entropy (S) = a measure of disorder/freedom/diversity at the molecular level
 i. If +ΔS, more likely to be spontaneous
ii. If -ΔS, less likely to be spontaneous
c. Free energy = energy that may be converted into work at constant temperature and volume
d. The change in free energy, ΔG, is equal to the sum of the enthalpy plus the product of the temperature and
entropy of the system

2. Explain the difference between spontaneous and non-spontaneous processes and

how this connects to ΔG.
a. ΔG = 0, system is in equilibrium so the concentrations of reactants and products will remain constant

Spontaneous Non-spontaneous

● Occurs naturally without additional input of energy ● Needs energy added to be able to proceed with the reaction

● Will happen sooner or later if conditions stay the same - not related ● +ΔG = endergonic
to kinetics or reaction rate ○ Not spontaneous in forward direction
○ Spontaneous in reverse direction to make more reactants
● Dependent on the amount of heat released or absorbed due to the
change

● -ΔG = exergonic
○ Spontaneous in forward direction to form more products

3. Predict changes in enthalpy and entropy for a given reaction.

a. ΔG = ΔH - TΔS
i. ΔH units = kJ/mol
ii. ΔS units = J/mol*K
iii. T units = K
iv. ΔG units = kJ/mol
b. Entropy
i. More complex molecules = more microstates = more entropy
ii. Increases with volume
c. Enthalpy
i. Extensive property
ii. Temperature independent
iii. Depends on initial and final states only

4. Develop criteria for determining whether a reaction will be spontaneous or not at

high or low temperatures.
-ΔH +ΔH

+ΔS Spontaneous at all T Spontaneous at high T

-ΔG TΔS is large

Exothermic Endothermic

Raises entropy Raises entropy

-ΔS Spontaneous at low T Not spontaneous at all T

TΔS is small +ΔG

Exothermic Endothermic

Lowers entropy Lowers entropy

5. Apply the concept of temperature dependence of spontaneity and describe what is

meant by entropy- or enthalpy-driven reactions.
a. Entropy-driven reactions = increase in ΔS, endothermic
b. Enthalpy-driven reactions = decrease in ΔH, exothermic
 6. Describe how enthalpy changes with protein folding (considering both the
interactions along the protein chain and those with the solvent).
a. Hydrophobic side chains in amino acids and proteins will tend to want to cluster together
i. Why hydrophobic groups are on the inside of the protein
b. Polypeptides that can move around fold into specific 3D shapes for proteins so there is a decrease in entropy in
the system
c. Reaction is exothermic
d. Product protein has a more stable configuration than the polypeptide chain
i. Entropy increases but is spread out

7. Explain the hydrophobic effect and draw simple diagrams to back up your
explanation.
a. +ΔG = not spontaneous
i. Endergonic
b. -ΔH = exothermic overall
c. -ΔS
d. As a hydrocarbon dissolves in water, a more
highly ordered state is reached
i. Clathrate structures (ordered cages of
water surrounding a solute hydrocarbon) are formed
ii. Hydrocarbons have low solubility in water - hydrophobic portions of the molecule will tend to want to
cluster together
1. Basis of protein folding
e. Aggregated solute is surrounded by ordered water
f. There is also free water
g. The free water surrounds the separated solute particles to reach a more ordered state

Lecture 4: Intro to Equilibrium

1. Define dynamic equilibrium and the law of mass action.
a. Dynamic equilibrium = forward reaction rate equals the reverse reaction rate
i. Concentrations of the reactants and products are constant - no net increase
ii. ΔG = 0
b. Law of mass action = AKA law of chemical equilibrium
i. Relationship between the product of the equilibrium concentrations of the products and the
equilibrium concentrations of the reactants

2. Use the law of mass action to write an

equilibrium constant expression for any
reaction and calculate the value from
provided data.
a. aA + bB ⇋ cC + dD
b. K = {C}c{D}d / {A}a{B}b
i. K = equilibrium constant
ii. Unitless
c. Do not include terms for solid or liquid phases
d. Large K = concentration of products predominate
e. Small K = concentration of reactants predominate,
reaction produces almost no products
f. The K of the forward reaction is inverted to give us the K of the reverse reaction

3. Calculate the reaction quotient (Q) and use it to determine the direction of the
reaction.
a. K - constant of a certain reaction when it is in equilibrium
b. Q - activities of reactants and products at any stage in the reaction
c. Q=K
i. Concentration of products and concentration of reactants are equal to the equilibrium concentrations
ii. System is at equilibrium
d. Q<K
i. Concentration of products is less than equilibrium concentration
ii. Forward reaction will occur
iii. More products formed
e. Q>K
 i. Concentration of products is more than equilibrium concentration
ii. Reverse reaction will occur
iii. More reactants formed

4. Calculate equilibrium concentrations or the equilibrium constant depending on the

information provided.
a. ICE tables

Lecture 5: Le Chatelier's Principle and the Connection Between Free Energy and
Equilibrium
1. Predict how changes in concentration, temperature, and the presence of a catalyst
affect equilibrium.
a. Le Chatelier’s - when chemical equilibrium is disturbed, the reaction will find a new equilibrium by moving in the
forward or reverse direction to counter the disturbance
b. Changes in concentration
i. Increase reactant concentration or decrease product concentration > reaction shifts towards the right
to favor the products
1. Forward reaction favored
2. Eventually decreases reactant concentration and increases product concentration to return
to equilibrium
ii. Increase product concentration or decrease reactant concentration > reaction shifts towards the left to
favor the reactants
1. Reverse reaction favored
2. Eventually decreases product concentration and
increases reactant concentration to return to equilibrium
iii. Amount of each substance is different but the ratio of the amount of
each remains the same
c. Changes in temperature
i. Forward reaction is exothermic
1. Reducing the temperature is similar to removing a product
which favors the production of more products
ii. Reverse reaction is endothermic
1. Increasing the temperature is similar to adding a product
which favors the production of more reactants
iii. Shifts the equilibrium and changes the K value
1. K decreases when there is an increase in temperature
and equilibrium shifts towards reactants
2. K increases when there is a decrease in temperature and equilibrium shifts towards
products
d. Changes in pressure
i. A change in the pressure on a liquid or solid has a negligible effect
ii. As pressure increases, the same number of molecules is now confined in a smaller space
1. Favors the reaction in which products have fewer moles
iii. As pressure decreases, the container volume increases and the overall number of gas molecules
would increase
1. Favors the reaction in which products have more total moles
e. Presence of catalyst
i. Causes both forward and reverse reaction to speed up equally, thus achieving equilibrium faster
ii. Has no effect on position of equilibrium

2. Calculate new equilibrium concentrations from any of the above changes.

3. Describe how certain changes cause the equilibrium to shift in one direction or the
other and propose an explanation for why this happens (rates of reactions and
collisions).
a. Given a certain probability of collisions within a fixed volume, a higher concentration will inevitably result in more
effective collisions. Thus, if the concentration of a reactant increases, it will have more effective collisions with
its counterpart reactant creating more products. In order to reach equilibrium again, the system will shift in the
forward direction. This same concept applies in the reverse direction.
 4. Graphically represent how changes in concentration or temperature affect
concentrations.

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Use the Van't Hoff equation to relate equilibrium constant to temperature.
a. ln(K2/K1) = (-ΔHº/R)(1/T2 - 1/T1)

6. Describe what is meant by the standard state. Give examples of elements and
compounds in their standard states.
a. Molecules in the state you would expect to find them in
b. H2 (g), H2O (l), Ni (s), AgCl (s), CO2 (g), NaCl (s)

7. Write and apply the mathematical relationship between ΔG° and K.

a. ΔGº = -RTlnk
i. R = 8.3145 J/mol*K

8. Explain the difference between ∆G° and ∆G.

a. ΔGº = the energy it takes per mole to convert some of the reactants to products under conditions where all the
reactants and products are in their standard states
i. Q = 1, T = 298.15 K
ii. -ΔGº > reaction goes spontaneously forward
1. K > 1
iii. +ΔGº > reaction goes spontaneously backwards
1. K < 1
b. ΔG = change in Gibbs free energy per a moles of A, b moles of B, etc reacting at any fixed set of concentrations
i. Greater for solids than liquids at the same temperature

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