Equilibrium Overview

Vocabulary
Thermochemistry: the study of energy changes during a chemical reaction

Stress: sharp changes up or down indicating the addition or removal of a species

Gradual Change: signify the system is reacting/shifting to a new equilibrium

Non-Spontaneous: 0% yield (use ↛)

Reactants favoured: less than 50% yield (use )
Products favoured: more than 50% yield (use )
Quantitative: more than 99.9% yield (use →)

Equilibrium Types
Dynamic Equilibriums
• Balance of two opposite processes

Phase Equilibrium
• Single chemical substance existing in more than one phase/state

Solubility Equilibrium
• Single chemical dissolved in a solvent, where excess solute is in contact with a saturated
substance

Chemical Reaction Equilibrium

• Static state between reactants and products (forward and reverse reactions happen at the same
rate)
• Does NOT imply equal amounts of P and R)

A system at equilibrium must be CLOSED, will have constant amounts, and be at a constant
temperature

Le Chatelier’s Principle
Concentration Changes
Substance Addition: system shifts away from substance
Substance Removal: system shifts toward substance

Graphing
• Addition: immediate change in concentration of substance on graph
• Effect: the effect on other chemicals in the system is a gradual change on the graph
Temperature Changes
Temperature : system shifts away from the side with energy
Temperature : system shifts toward the side with energy

Graphing
• Effect: graph the effect on other chemicals in the system as a gradual change

Volume/Pressure Changes
Pressure (Volume ): system shifts away from the side with the most moles of gas
Pressure (Volume ): system shifts toward the side with the most moles of gas

Graphing
• Pressure/Volume Change: immediate change in concentration of ALL substances on graph
More Pressure → concentration of all substances increases
Less Pressure → concentration of all substances decreases
• System Shift: graph the shift as gradual change on the graph

NOTE: if no gas is present, or there are equal moles of gas on each side of the equation, then no
change to the equilibrium will occur

Other Changes
Addition of a Catalyst: NO CHANGE
Addition of a Small Amount of an Inert Gas: NO CHANGE
Equilibrium Constant (Kc)
• A mathematical relationship for each closed equilibrium system, at a given (constant) pressure
Gives the relationship between the extent of the forward reaction and the value of Kc
‣ Kc > 1 → large value; favours products
‣ Kc < 1 → small value; favours reactants
The greater the value of Kc , the more the products are favoured
• Equation includes all chemical species that can change concentration (gases and solutions)
Includes gases (g) and solutions (aq)
• Equation does NOT include any substance with “fixed” concentrations (solids and liquids), and
shows only the species in the form that they exist, that are a part of the reaction (no spectator
ions are included)
• Kc has no units
• Values hold true when the temperature is constant, and the concentration of any one substance
does not drastically change
• Independent of any catalyst used in the reaction or time taken to reach equilibrium

[C]c [D]d
aA + bB cC + dD ➡ Kc = ————
[A]a [B]b

Ice Tables
• Equilibrium systems do not have limiting reagent/reactants, so calculations are no done
stoichiometrically. Instead, ICE tables are used
ICE stands for Initial, Change, Equilibrium
‣ Information from the question should be used to fill in as much of the table as possible
‣ The amount on the change line will always be the same ratio as the mole ratio of the
balanced equation
The values are for concentrations (in mol/L) of reactants and products

Ionization Constants
Water Ionization Constant (Kw)
• Even highly purified water shows a slight conductivity due to the ionization of water
Ionization of Water: H2O(l) + H2O(l) H3O+(aq) + OH-(aq)
• As a result, we get the equation: Kw = [H3O+(aq)] · [OH-(aq)] = 1.00 x 10 -14 at SATP
• This value holds true for most aqueous solutions (unless very concentrated), so we can use the
value to calculate [OH-(aq)] with [H3O+(aq)] or vice versa

NOTE: remember that temperature changes the value of any equilibrium constant; we will always
assume SATP conditions, unless otherwise stated
pH Square
• Shows the relationship between pH, pOH, [H3O+(aq)] , and [OH-(aq)]
• As a result, you can calculate the concentration of hydronium ions and hydroxide ions if pH or
pOH is given
• The water ionization constant (Kw)is included in the pH square
The relationship between [H3O+(aq)] and [OH-(aq)]

10 -pH = [H3O+(aq)]
pH [H3O+(aq)]
-log[H3O+(aq)] = pH

[H3O+(aq)] · [OH-(aq)] = 1.00 x 10 -14

pH + pOH = 14

10 -pOH = [OH-(aq)]
pOH [OH-(aq)]
-log [OH-(aq)] = pOH

Acid Ionization Constant (Ka)

• Equilibrium constant for a weak acid
Strong acids react completely (stoichiometrically - 99.9%) in water, therefore all acid
molecules react to form H+(aq)/H3O+(aq) ions and the reactants and products have a 1:1 ratio
• The Ka values on the Table of Relative Strength (pg. 9-10) are found by comparing acids at the
same concentration
A higher value means a greater reaction with water, and as a result a “stronger” weak acid
A lower value means it has less of a reaction with water and is a “weaker” weak acid
• We assume that this value remains constant for changes in concentration of the acid and
conjugate base
• Since weak acids only partially react in water, they are in an equilibrium (acid-base equilibrium)
and we can use the Ka value, and an ICE table to determine concentration, and/or pH

Equation Simplification
• Where the initial concentration of the acid molecule is more then 1000x greater than the value
of Ka we can assume that the concentration of the acid at equilibrium is essentially the same as
the initial concentration of the acid
• This means that the equation can be simplified because x is so small that the change in the
initial concentration is disregarded [Acid] initial
——————— > 1000 ➡ [Acid] equilibrium = [Acid] initial - x
Ka
[Acid] initial
——————— < 1000 ➡ [Acid] equilibrium = [Acid] initial - x
Ka
Base Dissociation Constant (Kb)
• Equilibrium constant for a weak base
The hydroxide ions are the strongest base, all other bases above OH- on the Table of
Relative Acid Strength are considered to be weak bases
• As you go up the Table of Relative Acid Strength, their conjugate bases become increasingly
weaker
A lower Ka value means it has a greater affinity to be a base and is therefore a “stronger”
weak base
A higher Ka value means it has a lower affinity to be a base and as a result is a “weaker”
weak base
• If pH is given, be sure to calculate [H3O+(aq)] or pOH first, and then calculate the [OH-(aq)]

The Relationship Between Ka and Kb

• If we were to calculate the Ka of an acid and the Kb of it’s conjugate base, the product will be Kw

Kw |
Kb = ——— | Ka · Kb = Kw
Ka |

Acid-Base Definitions
Arrhenius’ Definition
• Previous method of defining acids and bases
Acids: forms H3O+(aq) when the substance reacts with water (HX(aq) + H2O(l) → X(?) + H3O+(aq) )
Bases: forms OH-(aq) when the substance reacts with water (X(?) + H2O(l) → HX(aq) + OH-(aq) )
• Has it’s limitations as it could not explain…
Acid-base reactions not in water
Amphoteric entities

Proton Transfer Concept (Bronsted-Lowry)

• This is how we identify acids and bases in today’s world
Concept does not define each substance as an acid or base, but rather identifies the entity
to be acting as an acid or base in a particular reaction
This is beneficial because it defines acids and bases in terms of chemical reaction taking
place, rather than the previous definition which relied on the reaction’s products
• Both Bronsted and Lowry independently developed this concept
Bronsted-Lowry Acid: acts as a proton donor in a reaction
Bronsted-Lowry Base: acts as a proton acceptor in a reaction
• For aqueous acid-base reactions, the water acts as a solvent but is not necessary for the
reaction to occur
• This theory is still limited because it does not explain why entities act as proton acceptors/
donors and does not explain which reaction will occur in a new situation
Types of Acids and Bases
Conjugate Acids & Bases
• Conjugate acids and bases are pairs of substances which differ by only a proton (H+(aq))
• Bronsted-Lowry concept always leads to reversible reactions and an equilibrium
Each equilibrium has two B-L acids and two B-L bases (one of each on both sides)
If a reactant can donate a proton, its product can accept a proton, and vice-versa

Acids
Strong Acids
• Will almost completely ionize in water (≈100% reaction)
Has a very large Ka value (Ka > 1)
Conjugate base has a small Kb value
• Hold onto their proton weakly
Conjugate base is weaker than water (not good at attracting/accepting proton(s))

Weak Acids
• Only partially ionize in water
Ka value is small (Ka < 1)
Conjugate Kb value is large
• Hold onto their proton strongly
Conjugate base is strong (good at attracting/accepting proton)

Bases
Strong Bases
• Will almost completely ionize in water (≈100% reaction)
Large Kb value
Small conjugate Ka value (Ka < 1)
• Attracts protons strongly
Conjugate acid is weak (holds onto proton strongly)

Weak Bases
• Only partially ionize in water
Kb value is small (Kb < 1)
Large Ka value (Ka < 1)
• Not good at accepting protons
Conjugate base is strong (high affinity for accepting a proton)
Intermediate Acid-Base Compounds
Amphoteric/Amphiprotic Entities
• Amphoteric: substance with the ability to act as an acid or a base (empirical definition)
• Amphiprotic: Entities that can donate or accept a proton (theoretical definition)
• Compound’s behaviour is determined by it's Ka and Kb values; the higher of the two values
determines it’s natural behaviour
Ka > Kb → naturally acts as an acid in water
Ka < Kb → naturally acts as a base in water
• The first reaction (with higher Kc value) is more predominant

Example: HCO3- H2CO3(aq) + OH-(aq) Kc = 2.2 x 10 -8

HCO3- + H2O(l) OR higher Kc value → more prominent reaction
2-
CO3 (aq) + H3 O+ (aq) Kc = 4.7 x 10 -11

• However, when the ion reacts with a stronger acid, or stronger base, it can partially neutralize
the solution
HCO3- + H3O+(aq) H2CO3 + H2O(l)

HCO3- + OH- (aq) CO3 2- (aq) + H2O(l)

Polyproptic Acids and Bases

• Substances which can donate or accept more than one proton (H⁺) in a consecutive manner
Polyprotic acids can lose multiple protons
Polyprotic bases can accept multiple protons
• They can undergo multiple ionization stages
The reaction with the higher Kc value will be more predominant
• Mid-stage entity is an amphoteric entity (in the case below it is HCO3- )

Example:

CO3 2- + H2O HCO3- + OH- ➡ HCO3- + H2O H2CO3 + OH-

Polyprotic Base Amphoteric Entity Amphoteric Entity Polyprotic Acid

Predicting Acid-Base Reaction Equilibria

• Bronsted-Lowry definition does not explain this so we use imperial evidence to
Observed Evidence: The strongest acid will react with the strongest base in a reaction
mixture
• By combining the collision-reaction theory and B-L concepts, we are led to one overall
prediction that matches observable evidence
• All entities must be listed as they exist in aqueous solution according to the following…
Substance Dissolved Kind of Species in Example(s)
Solution

Ionic Compounds Ca(HCO3)2(aq) → Ca2+ (aq), HCO3- (aq)

(including hydroxide cation + anion
(dissociation)
compounds) NH4OH(aq) → NH4+ (aq), OH- (aq)

Ionic Oxides (only if

cation + hydroxide Na2O(aq) → Na+ (aq), OH- (aq)
soluble)

Strong Acids hydronium ion + anion HCl(aq) → H3O+ (aq), Cl- (aq)

Weak Acids Molecule or ion HF(aq) → HF(aq)

(no change)

Weak Bases Molecule or ion NH3(aq) → NH3(aq)

(no change) HCO3(aq) → HCO3(aq)

Steps to Predicting the Prominent Acid-Base Reaction

1. List all entities as they exist in aqueous solution
2. Label each species as an acid, base, or both (using B-L definition)
3. Identify the strongest acid (SA) and the strongest base (SB) using the table on page 8-9 in data
booklet
4. Write the balanced reaction to show the proton transfer from the strongest acid to the strongest
base
SA SB
5. Predict the position of the equilibrium + +
a) SA above SB → products favoured (>50% yield) SB SA

b) SA below SB → reactants favoured (<50% yield) Products Favoured Reactants Favoured

Assumptions to Determine Predominant Reaction

• Water in any reaction can complicate the prediction
All strong acids will completely ionize in water and should be written as H3O+(aq) ions
‣ Conjugate bases of the 6 strong acids are weaker than water and therefore do not act as
bases (use water as the weakest base in this instance)
The strongest base is the hydroxide ion, (OH -(aq) ), so stronger bases dissolved in water (ex.
oxides) will react to form hydroxide ions
• Equations must only represent a single proton transfer between two entities, neither of which is
water
• The strongest acid and the strongest base are present in significant amounts, with
approximately equal concentrations
• Reactions between hydronium, and hydroxide are quantitative
When a strong base and strong acid are added together, the reaction yield is >99.9%
Indicators
• Bronsted-Lowry conjugate pairs that display at least one (usually two) noticeable colour(s)
Some may also show an intermediate colour
• Different indicators have different strengths (Ka values), so they change colours at different pH
values (can be chosen to match either equivalence point on a titration curve, but the
second, stronger pH change is usually chosen)
Solution of Excess Hydronium Ions (acid)
‣ According to Le Châtelier’s Principle, if there is an excess of hydronium ions, there is an
increase in H3O+(aq) concentration
‣ The equilibrium will shift away from the excess/addition of H3O+(aq) , and towards the
indicator is in its acidic form
Solution of Excess Hydroxide Ions (base):
‣ According to Le Châtelier’s Principle, if there is an excess of hydroxide ions (increase in
OH-(aq) ), the hydronium ions will be neutralized to form water, decreasing the
concentration of H3O+(aq)
‣ The equilibrium will shift towards the decrease in H3O+(aq) , and therefore the indicator is
in its basic form

Example: HPh(aq) + H2O(l) → Ph-(aq) + H3O+(aq)

acidic phenolphthalein basic phenolphthalein
(colourless) (bright pink)

Buffer Solutions
• When a partial reaction between the strongest acid and the strongest base creates a mixture
with significant amounts of weak conjugate acid-base pairs
The mixture can maintain a nearly constant pH when diluted, or when a small amount of a
strong acid or base is added
‣ If more base (OH-(aq) ) was added, it would react with the acidic compound and the pH
would only change slightly
‣ If more acid (H3O+(aq) ) was added, it would react with the basic compound and the pH
would again, only change slightly
• Can be identified as the flat portion(s) of the pH curve
Occurs BEFORE a sharp change in pH (equivalence point)
About half-way between the start of a buffer point and its end, approximately half of the
acid/base molecules have reacted/been neutralized
‣ There is approximately equal amounts of acid and base molecules → [base] ≈ [acid]
If the compound is polyprotic, it will donate/accept more than one proton in a series of
single-proton transfer reactions
‣ The sequential reaction(s) will also have buffer regions, they must be before the final
equivalence point/sharp change
• A buffer can be prepared by mixing solutions of an amphiprotic ion with a strong acid or base
(depending on the buffer pH desired)
• Routinely used to calibrate pH meters for accuracy
Buffer Capacity
• The limit of a buffer to maintain a pH level
• Occurs when one of the entities of the conjugate acid-base pair is greatly diminished, causing
the buffer to fail to maintain the equilibrium

pH/Tritiation Curves
• Continuous change in pH of an acid-base titration, until the titrant is in a large excess
• Only quantitative reactions produce detectable equivalence points in acid-base titrations

Terms
Endpoint
• Point of titration where the addition of the titrant stops
• Is defined empirically, often by a change in colour, or some other significant change to the
mixture’s physical properties

Equivalence Point
• Point in a chemical reaction where chemically equivalent amounts of the reactants have
combined
• Is defined theoretically by the stoichiometric ratio

Shapes of pH Curves & Corresponding Acid/Base Strength

Strong Acid w/ Strong Base
• Quantitative reaction (>99.9% yield)
• Equivalence point will have a pH of 7
• Doesn’t matter which is the sample or titrant

Strong Acid w/ Weak Base

• Weak base should be used as the sample, with strong acid as the titrant
• Quantitative reaction (>99.9% yield)
Equivalence point will have a pH < 7
Depends on base used and Kb

Weak Acid w/ Strong Base

• Weak acid should be used as the sample, with strong base as the titrant
• Quantitative reaction (>99.9% yield)
Equivalence point will have a pH > 7
Depends on acid used and Ka

Weak Acid w/ Weak Base

• Reaction is non-quantitative (<99% yield) so the endpoint is hard to detect
Polyprotic Entities
• Scientists believe that polyprotic substances accept/donate more than one proton and do so in
a series of single-proton transfer reactions
• Each proton transfer diminishes the strength of the new acid or base greatly
Approximately 100 to 100 000 times weaker
# of equivalence points = # of proton transfer reactions that occur

• Diprotic substances usually show two equivalence points (indicated by 2 sharp changes in pH)

Specific Examples
1. Sulfuric Acid (the only diprotic strong acid)
a) It’s first proton transfer is quantitative in water and forms hydrogen sulfate
b) Hydrogen sulfate is a relatively “strong” weak acid so the second proton transfer is usually
quantitative when reacting with a base (meaning two complete proton transfers)
2. Phosphoric Acid (triprotic)
a) The first two proton transfers are quantitative
b) The third proton transfer is in equilibrium (indicated by gradual decrease in pH, rather than a
sharp change in pH)

Net Reaction
• Multiple proton transfer reactions can be combined to form an overall/net reaction (if each
individual reaction is quantitative)
• For titrations, only quantitative reactions can be considered when determining the net reaction
Example:
CO3 2- (aq) + H3O+(aq) HCO3-(aq) + H2O(l)

HCO3-(aq) + H3O+(aq) H2CO3 (aq) + H2O(l)

——————————————————————————————

CO3 2- (aq) + 2H3O+(aq) H2CO3 (aq) + 2H2O(l)