CHEM 1101 – ACIDS, BASES, AND

AQUEOUS EQUILIBRIA
LECTURE 1

- Equilibrium
o Occurs when a reaction and its reverse reaction proceed at the same rate.
o As a system approaches equilibrium, both the forward and reverse reactions are occurring,
same rate
o Once equilibrium is achieved, the amount of each reactant and product remains constant.
o Use the double arrow

o At equilibrium.

- Haber Process

- Generalised Reaction
- Equilibrium can be reached from either direction
- Magnitude of K

- Homogeneous vs Heterogeneous
o Homogeneous equilibria occur when all reactants and products are in the same phase
o Heterogeneous equilibria occur when something in the equilibrium is in a different phase
o The value used for the concentration of a pure substance is always 1

- Kc
o Concentration of pure liquids and solids do not appear
o Numerical values are only meaningful when its associated with a particular chemical
equation
o Temperature dependent
o Units will vary depending on reaction
- Comparing Q and K
o Q=K is at equilibrium
o Q < K, forward reaction favoured
o Q > K, reverse reaction favoured
- Le Chatalier’s Principle
o If a system is at equilibrium is disturbed by a change in temperature, pressure, or the
concentration of one of the components, the system will shift its equilibrium position so as
to counteract the effect of the disturbance.
- Summary
o Chemical equilibrium rate of forward reaction = rate of reverse reaction
 o Dynamic equilibrium at molecular level, reaction does not stop. Need a closed system for
dynamic equilibrium
o Use the right arrow
o Keq = products/reactants
o Reaction quotient, Qc
o When Kc=Qc there is equilibrium
o Qc > Kc, product favoured
o Qc < Kc, reactant favoured
- Questions
o C
o B
o D
o B

LECTURE 2

- Change in reactant or product concentration

o Adding a reaction component will result in some of it being used up
o Removing a reaction component will result in more of it being produced
o Partial pressure is changed

- Change in volume or pressure

o Increase in volume – decrease in pressure and vice versa
o When gases are involved. Increase in volume favours the side with more moles and vice
versa
- Change in temperature
o If reaction is endo, increase in temp drives reaction forward/ towards products
o If reaction is exo, increase in temp drives reaction backwards/ to reactants
- Endothermic Equilibrium

- Catalysts
o Increase rate of both forward and reverse reactions
o Equilibrium is achieved faster, equilibrium constant is not affected
o Activation energy lowered, means it happens at a lower temp
- Arrhenius Acids and Bases
o An acid is a substance that, when dissolved in water, increases the concentration of
hydrogen ions. Never contain H+ ions, but have covalently bonded H atoms that ionise in
water
o A base is a substance that, when dissolved in water, increases the concentration of hydroxide
ions.
- Bronsted-Lowry Acids and Bases
o An acid is a proton donor
o A base is a proton acceptor
o Includes bases that do not contain OH in their formula
o Does not specify that the acids and bases have to be in a water solution
o A Bronsted-Lowry acid must have at least one removable proton to donate. (H +)
o A Bronsted-Lowry base must have at least one nonbonding pair of electrons to accept a
proton. (H+)

- Conjugate Acids and Bases

o They are a pair
o Reactions between acids and bases always yield their conjugate bases and acids.
LECTURE 3

- Relative Strengths of Acids and Bases

o Strong acids are above the H2O line
o The conjugate bases of strong acids do NOT act as bases in water.
o Strong bases are below the H2O line.
o The conjugate acids of strong bases do NOT act as acids in water
o Substances between the H2O are conjugate acid-base pairs in water.
o The stronger the acid, the weaker its conjugate bases are.

- Autoionisation of Water
o Water is amphoteric, sometimes called amphiprotic.
o In pure water, a few molecules act as bases and a few act as acids. This is autoionization.
- Ion Product Constant
o Equilibrium expression is, Kw = [H3O+][OH-]
o It is the ion product for water, Kw
o At 25°C, Kw = 1.0 × 10-14
- Aqueous Solutions
o Neutral solution, [H3O+] = [OH-]
o Acidic solution, [H3O+] > [OH-]
o Basis solution, [H3O+] < [OH-]
- pH
o method of reporting hydrogen ion concentration
o pH = -log[H+]
o Neutral is 7, acidic is below 7 and basic is above 7. All at 25°C
- pOH
o method of reporting hydroxide ion concentration
o pOH = -log[OH-]

-
- Strong Acids
o Exist totally as ions in aqueous solutions. Completely dissociates.

o HCl, HBr, HI, HNO3, H2SO4

o For monoprotic strong acids,

- Weak Acids
o Does not completely dissociate.

o Equilibrium constant is the acid-dissociation constant.

o The greater the value of Ka, the stronger the acid.

- Strong Bases
o Are soluble hydroxides. These substances dissociate completely in aqueous solution.

o Na+, K+, Ca2+, Sr2+, and Ba2+

- Weak Bases
o Do not dissociate fully in aqueous solution
o Have an equilibrium constant called base dissociation constant.
- Calculating pH of weak acid using Ka

-
LECTURE 5 SUMMARY –

- Lewis acid base theory

o A Lewis Acid is an electron pair acceptor
o A Lewis Base is an electron pair donor
- All Bronsted-Lowry acids/bases are also Lewis ones
o BF3 meets Lewis but not Bronsted-Lowry
- Buffer solution is a weak acid and its conjugate base. Needs a relatively high concentration of the
weak acid and its conjugate base, ideally HA = A-
- Two ways to prepare a buffer
o Mix weak acid and the salt of its conjugate base or a base and its conjugate acid.
o Add a strong acid and partially neutralise a weak base or add a strong base and partially
neutralise a weak acid.
- Henderson equation
o Buffer range – controlled by pKa of weak acid
o Buffer capacity – controlled by the A-/HA
o Optimal pH – pK = pKa
o Generally, the pH of a buffer is usually within +/- 1 pH unit from the pKa.

LECUTURE 6 –

- Titration
o An acid (or base) solution of known concentration is slowly added to a base (or acid) solution
oj unknown concentration.
o A pH meter or indicators are used to determine when the solution has reached the
equivalence point:
▪ Amount of acid equals that of the base OR all reactants are converted into products
- Titration Strong Acid and Strong Base
o Start of titration to near equivalence point, pH goes up slowly.
o Just before and after equivalence point, pH rises rapidly
o At equivalence point, pH = 7
o As more base added, pH drops off

- Titration Weak Acid and Strong Base

o Use Ka to find initial pH
o Find pH in “buffer region: using stoichiometry and Henderson equation
 o At equivalence point. pH>7. Use conjugate base to determine pH
o As more base is added, pH levels off

- Weak Acid titration compared to Strong Acid titration

o Solution of weak acid has higher initial pH than strong acid.
o pH change near equivalence point is smaller for a weak acid.
o pH at equivalence point is greater than 7 for a weak acid.
- Choosing Indicators
o Ensure the equivalence point falls withing the colour-change interval.
ENTHALPY

- Process taking place at constant pressure, only work is pressure-volume work, we can account for
heat flow by measuring enthalpy
- Enthalpy – internal energy plus product of pressure and volume
- H = E + PV

- When delta H is positive, process is endothermic

- When delta H is negative, process is exothermic (enthalpically favourable)
- Enthalpy of reaction
o Enthalpy of the products minus the enthalpy of the reactants.
o H products – H reactants
o Delta H is called the enthalpy of reaction or heat of reaction
- Truths
o An extensive property
o Delta H for reaction is equal in size, opposite sign, to delta H for reverse reaction
o Delta H for reaction depends on state of products and reactants
- Enthalpies of Formation

o
o Defined as enthalpy change for the reaction where 1 mol of compound is made from its
constituent elements in their standard state.
o Unit: kJmol-1

o (H2O(l)) = -285.8 kJmol-1

H2(g) + ½ O2 (g) → 1 H2O(l)

o (N2 (g)) = 0
N2 (g) → N2 (g)
- Enthalpy of Combustion
o Defined as the enthalpy change when one mole of a compound is completely burnt in oxygen
with all reactants and products in their standard state under standard conditions

o (C6H12O6 (s)) = -2801 kJmol-1

C6H12O6 (s) + 9 O2 (g) → 6 H2O (l) + 6 CO2 (g)
 - First Law of Thermodynamics
o Energy cannot be created of destroyed; it is a constant
o Energy can be converted from one form to another or transferred from a system to the
surroundings or vice versa
- Enthalpy vs Entropy
o Enthalpy is the heat absorbed or released by system during constant pressure process
o Entropy is measure of randomness in a system
o Both have a role in determining whether a process is spontaneous

SPONTANEOUS PROCESSES

- Proceed without any outside assistance

- Processes that are spontaneous in one direction are non-spontaneous in the reverse
- Temp and pressure affect spontaneity
- Entropy
o Measure of randomness of a system
o State function:

o Found by heat transfer from surroundings at given temperature

- Second Law of Thermodynamics

o Entropy of the universe increases in any spontaneous processes

- Molecular Scale

- Statistical Thermodynamics
o Bulk properties of substances
o Microstate: single possible arrangement of position kinetic energy of molecules.
- Boltzmann’s Use of Microstates
o So many possible microstates, impossible to look at every one
o W represents number of microstates
o Entropy measures how many microstates are associated with particular macroscopic state
 o Connection between number of microstates and entropy of system:

- Entropy Change
o Final value minus initial value will give overall change
o An increase in number of microstates results in positive entropy change (more disorder)

- Effect of Volume and Temp change on System

o Increase volume, more positions possible for molecules, means more microstates –
increased entropy
o Increase temp, average kinetic energy increases. Greater distribution of molecular speeds.
Leads to more possible kinetic energy values, more microstates, increases entropy.
- Entropy on Molecular Scale
o Number of microstates and therefore the entropy tends to increase with increases in temp,
volume, and number of independently moving molecules
- Entropy and Physical States
o Entropy increases with freedom of motion of molecules
o S(g) > S(l) > S(s)
o Entropy of system increases for processes where:
▪ Gases form from either solids or liquids
▪ Liquids or solutions form from solids
▪ Number of gas molecules increases during chemical reaction
- Third Law of Thermodynamics
o Entropy of pure crystalline substance at absolute zero is 0.
o All atoms or molecules in perfect lattice at 0 K; there will only be one microstate.

20/04

- Standard Entropies
o Reference for entropy is 0K, not 298K
o Standard molar entropy for a gas is generally greater than for liquids and solids
o Standard molar entropies increase with molar mass
o Standard molar entropies increase with number of atoms in a formula
- Entropy Changes

o
Where n and m are the coefficients in the balanced chemical equation.

- Entropy Change in Surroundings

o Heat that flows into or out of the system changes the entropy of the surroundings
o For isothermal process (constant temp)

o At constant pressure, q sys is delta H for the system

o Universe is composed of the system and the surroundings,

o
o For spontaneous processes
- Gibbs Free Energy
o If delta G is negative, forward reaction is spontaneous
o If delta G is 0. System is at equilibrium
o If delta G is positive, reaction is spontaneous in reverse direction
o For spontaneous process (delta G < 0), at constant T and P, delta G is the maximum useful
work obtained from a system (-w).

- Free Energy Changes

o Analogous to standard enthalpies of formation, also have free energies of formation,

and free energies of combustion,

o If delta G is less than zero, sign of enthalpy and entropy and magnitude of temperature
matters to spontaneity.
- Free Energy and Equilibrium
o Under any conditions, standard or non-standard, the free energy change can be found with:
 Q is the reaction quotient and R is the gas constant.
o Under standard conditions, all concentrations are 1M, so Q=1 and lnQ=0.

o Therefore:
o At equilibrium Q=K and delta G = 0

o Larger Gibbs free energy, large Keq

LECTURE 13

- Lecture 12 Summary
o Assigning oxidised numbers
▪ If oxid number for element increases, element is oxidised
▪ If oxid number for element decreases, element is reduced
o Species is oxidised when it loses its electrons
o Species is reduced when it gains electrons
o Half-Equations
▪ Contains electrons. Balance oxid and reduced half-equations separately
o Can only combine two half-equations by first making number of moles electrons equal on
one side
- Voltaic (electrochemical) cells
o In spontaneous redox reactions, electrons are transferred, and energy is released.
o Oxidation occurs at anode
o Reduction occurs at cathode
o When electrons flow, charges aren’t balances. Salt bridge used to keep charges balanced.

- Electromotive Force
o Electrons flow spontaneously one was in a redox reaction, from high to low potential energy.
 o The potential difference between anode and cathode in cell is called electromotive force
(emf)
o Also called cell potential, Ecell
o Measures in volts. One volt is one joule per coulomb (1V = 1J/C)
- Standard Reduction Potentials
o Values are compared to the reduction of hydrogen as a standard.

- Standard Hydrogen Electrode

o SHE
o The reduction potential for hydrogen is 0V

- Standard Cell Potentials

o Can be found through this equation

o Cell potential is an intensive property. Means changing the stoichiometric coefficient in half-
equation does not affect the standard reduction potential.
- Oxidising and Reducing Agents
o More positive value of E” red, the greater tendency for reduction under standard conditions.
o Strongest oxidisers have most positive reduction potentials, most easily reduced
o Strongest reducers have most negative reduction potentials, most easily oxidised
- Free Energy and Redox
o Spontaneous redox reactions produce positive cell potential, or EMF
o Since Gibbs free energy is measure of spontaneity, positive EMF corresponds to negative
delta G

o
o F is Faraday’s Constant : quantity of electrical charge carried by 1 mole of electrons
- Nernst Equation