Chemistry Unit 3, Topic 1: Chemical equilibrium systems

Chemical equilibrium

 chemical systems may be

- open: allowing matter and energy to be exchanged with the surroundings
- closed: allow energy, but not matter, to be exchanged with the surroundings
 physical changes are usually reversible, whereas only some chemical reactions are reversible
(symbolised by ⇌ in balanced chemical equations)
- physical change: composition remains the same. It is a temporary change of forms, e.g., melting
- chemical change: formation of new substances after atoms are rearranged in a chemical reaction
 observable changes in chemical reactions and physical changes can be described and explained at
an atomic and molecular level
 over time in a closed system, physical changes and reversible chemical reactions reach a state of:
- dynamic equilibrium: rates of reaction forward and reverse reactions are equal
- relative concentrations of products and reactants define the position of equilibrium
 explain the reversibility of chemical reactions by considering the activation energies of the
forward and reverse reactions
- activation energy: energy required for a reaction to occur (energy required to break and reform
bonds).

- Can be endothermic (positive change in enthalpy, the energy stored within chemical substances)
or exothermic (negative change in enthalpy)

 analyse experimental data, including constructing and using appropriate graphical representations
of relative changes in the concentration of reactants and product against time, to identify the
position of equilibrium
- as more products are produced, greater chance of reactants being re-formed
- concentration-time graphs indicate the rate of reaction by the steepness of the curve
- point at which concentrations level off and become constant is equilibrium
- position of equilibrium compares the concentration products and reactants:
a) lies to the right, favours production of products
b) lies to the left, favours production of reactants
 we can test for extent of equilibrium depending on colour of the final solution, when
reactant and product colours are different.
Factors that affect equilibrium

Le Chatelier’s principle: When a change is made to an equilibrium system, the system will proceed in a way
that will partially oppose the effect of the change.

• explain and predict the effect of temperature change on chemical systems at equilibrium by considering
the enthalpy change for the forward and reverse reactions

- Exothermic (energy released) or endothermic (energy absorbed)

- Increasing the temperature increases the kinetic energy of all particles in the system.
- As a result, more particles have enough energy to satisfy the activation energy.
- There is an increase in the number of collisions that occur. This results in an increase in reaction
rate of both reactions (forwards and backwards).

• explain the effect of changes of concentration and pressure on chemical systems at equilibrium by
applying collision theory to the forward and reverse reactions

- an increase in reactants means there are more reactant particles, which results in more
collisions and thus more successful collisions, resulting in an increase in product concentration.

• apply Le Châtelier’s principle to predict the effect changes of temperature, concentration of chemicals,
pressure and the addition of a catalyst have on the position of equilibrium and on the value of the
equilibrium constant.

Concentration can be changed by a) adding or removing reactant or product, b) changing pressure and
volume or c) diluting aqueous solution (increasing volume!!)

- Answering for a): When reactant concentration is increased, the system partially opposes the
change by moving to the product side to decrease reactant concentration, resulting in a net
forward reaction.
- b and c) When the volume is doubled, the concentrations of all ions in solution are halved. The
system will partially oppose this change by moving to the side with the more particles. There is a
molar ratio for products to reactants is 2:1, so equilibrium favours the reverse reaction.
 Remember: abrupt vertical lines for all species when graphing concentrations vs time!!

Temperature:

- Energy can be considered to be a reactant in endothermic reaction and a product in exothermic

reaction
- Increase in energy shifts equilibrium to the side where energy is stored within the molecules
(products), while decrease in energy shifts equilibrium to side where energy is released from
molecules (reactants)
- Vice versa for exothermic reactions (e.g. energy stored in reactants, released in products)

Eventually, the system will re-establish equilibrium, though the concentration of the added species will be
increased from initially.

Catalyst: a substance that increases the rate of reaction without itself being consumed in reaction. Lowers
the activation energy of a system.

- Doesn’t partake in reaction and doesn’t affect position of equilibrium.

Equilibrium constants

• understand that equilibrium law expressions can be written for homogeneous and heterogeneous
systems. The equilibrium constant (Kc), at any given temperature, indicates the relationship between
product and reactant concentrations at equilibrium

• deduce the equilibrium law expression from the equation for a homogeneous reaction and use
equilibrium constants (Kc), to predict qualitatively, the relative amounts of reactants and products
(equilibrium position)

- The equilibrium constant tells us what is ‘favoured’ at equilibrium / the extent of reaction. It also
signals the yield (how much product is made).
 If Kc > 104, contains significantly more products; forward reaction favoured.
 If Kc < 10-4 contains significantly more reactants; backward reaction favoured.
- The only factor that can impact the equilibrium constant is a change in temperature

• deduce the extent of a reaction from the magnitude of the equilibrium constant

We can compare the Kc value to another value called the reaction quotient (Qc)

- Qc shows the relationship between the concentrations of products and reactants during any
stage of the reaction. By comparing Qc with Kc, we can figure out what needs to happen for
equilibrium to be achieved (Kc).
- If Q > K, excess product -> the reverse reaction is preferred until equilibrium is reached
- If Q < K, excess reactant -> the forward reaction is preferred until equilibrium is reached
- The Kc value can indicate the equilibrium yield. In industry, a higher Kc value is desirable as it
means that we will have a high yield [of product].

• use appropriate mathematical representation to solve problems, including calculating equilibrium

constants and the concentration of reactants and products.

For calculation of concentration at equilibrium: The use of quadratic equations is not required; when Kc is
very small the follow assumption can be made: [initial reactants] ≈ [equilibrium reactants]

- Students should state when assumptions are used

Properties of acids and bases

• understand that acids are substances that can act as proton (hydrogen ion) donors and can be classified
as monoprotic or polyprotic depending on the number of protons donated by each molecule of the acid

- Monoprotic acids donate one (H+).

- Polyprotic acids donate multiple (H+) in stages (progressively). The likelihood of H+ donation at
each stage decreases as acids become weaker, and ⇌ is used

• distinguish between strong and weak acids and bases in terms of the extent of dissociation, reaction
with water and electrical conductivity and distinguish between the terms strong and concentrated for
acids and bases

- The strength of an acid depends on its ability to ionise/dissociate in solution (fully/partially:

usually with water as the solvent). Another way to define this is how easily acids lose/donate
their H+.
- The strength of a base depends on its ability to accept H+ (and thereby ionise).
- Concentration measures the amount of solute in a given volume. For acids and bases, this
indicates the amount of acid/base in a given volume.

Acids Bases
Strong HCl – hydrochloric acid NaOH – sodium hydroxide
HNO3 – nitric acid KOH – potassium hydroxide
H2SO4 – sulfuric acid Ba(OH)2
Weak CH3COOH – ethanoic/acetic acid NH3 – ammonia
+ general carboxylic acids amines
H2CO3 - carbonic acids (aqueous
CO2)

Common acidic reactions:

Note: acid-base reactions involve the transfer of hydrogen ions

pH scale

• understand that water is a weak electrolyte (liquid which contains ions and can be decomposed by
electrolysis) and the self-ionisation of water is represented by:

- All aqueous solutions contain both H3O+ and OH– ions. The Kw value is constant, therefore any
changes in the concentrations of either ion results in a fluctuation in the concentration of the
other ion:
 In a reaction involving an acid, [H3O+] will ↑, resulting in a ↓ in [OH– ].
 In a reaction involving a base, lots of OH– will be formed, therefore the [OH–] will ↑,
resulting in ↓ in [H+]
- Thus, Kw can be used to calculate the concentration of hydrogen ions from the concentration of
hydroxide ions in a solution

• understand that the pH scale is a logarithmic scale and the pH of a solution can be calculated from the
concentration of hydrogen ions using the relationship:

- pH measures the acidity of a solution. Because it’s a logarithmic scale, a change in pH by 1

changes the concentration of [H3O+] by a factor of 10.

• use appropriate mathematical representation to solve problems for hydrogen ion concentration [H+
(aq)], pH, hydroxide ion concentrations [OH– (aq)] and pOH.
Brønsted-Lowry model

• recognise that the relationship between acids and bases in equilibrium systems can be explained using
the Brønsted-Lowry model and represented using chemical equations that illustrate the transfer of
hydrogen ions (protons) between conjugate acid-base pairs

• identify and deduce the formula of the conjugate acid (or base) of any Brønsted-Lowry base (or acid)

- Conjugate pairs:
 Conjugate base: Chemical species formed from an acid that has donated a proton, H+
 Conjugate acid: Chemical species formed from a base that has accepted a proton, H+
- Amphiprotic substances can act as both acids and bases (i.e. donate or accept protons):

• appreciate that buffers are solutions that are conjugate in nature and resist a change in pH when a small
amount of an acid or base is added; Le Châtelier’s principle can be applied to predict how buffer solutions
respond to the addition of hydrogen ions and hydroxide ions.

- Buffers are solutions that resists changes in pH when small quantities of acid or base is added to
a solution.

- Buffers are made from weak conjugate pairs:

 a weak acid and/or a salt containing the conjugate base
 a weak base and/or a salt containing the conjugate acid.
- Buffers work by neutralizing the acid/base added, i.e., removing the excess hydronium and
hydroxide ions.
 When an acid is added, the H+ ions react with the conjugate base to form water and the
weak acid. (Equilibrium shifts to the left to combat increase in H+ concentration, more
reactant is formed)
 When a base is added, the OH- ions will react with the weak acid to form water and the
conjugate base. (Equilibrium shifts to the right; as the base reacts with H+, concentration of
H+ decreases, more product is formed)
Dissociation constants

• recognise that the strength of acids is explained by the degree of ionisation at equilibrium in aqueous
solution, which can be represented with chemical equations and equilibrium constants (Ka)

- Acid-dissociation constant: the equilibrium constant for the dissociation of an acid in aqueous
solution
- measures a substances’ (acid’s) ability to dissociate in a solution and can help determine the
extent of the dissociation of an acid or base.

• determine the expression for the dissociation constant for weak acids (Ka) and weak bases (Kb) from
balanced chemical equations

• analyse experimental data to determine and compare the relative strengths of acids and bases

- Ka is a ratio of the products to the reactants. The more an acid dissociates into H3O+ and
conjugate base (A– ), the stronger the acid is, and consequently the greater the value of Ka .
- In other words, if Ka is large, the products are favoured; if Ka is small, the undissociated acid is
favoured. So, the larger the Ka value, the stronger the acid.
 Weak acids are defined as having Ka < 1
 Strong acids are defined as having Ka > 1
- The same for bases
- Because pH is related to the concentration of H3O + ions, pH is a function of Ka. It is important
to realise that as pH decreases, Ka increases.

• use appropriate mathematical representation to solve problems, including calculating dissociation

constants (Ka and Kb) and the concentration of reactants and products

- The connection between Ka, Kb, Kw, pH (and pOH) is the concentration of hydronium [H3O+]

Calculating Ka of a weak acid, given the pH and the initial concentration of the weak acid.

1) Write out balanced chemical equation and expression for dissociation constant
2) Find hydronium [H+] concentration using pH
3) Use ICE table to determine concentration of conjugate base at equilibrium, and then the weak acid
by subtracting according to the molar ratio (relative to [H+])
4) Substitute equilibrium concentrations into dissociation expression for Ka

Calculating pH from Ka:

Acid-base indicators

• understand that an acid-base indicator is a weak acid or a weak base where the components of the
conjugate acid-base pair have different colours; the acidic form is of a different colour to the basic form

Weak acid indicator: Weak base indicator:

- Acid-base indicators: a chemical substance that changes colour at different pH values.

- Similar to buffers, indicators are often weak acids / bases.
- (very similar in terms of Le Chat, with addition of acid/base changing H3O+ concentration, thus
shifting equilibrium position. Difference is that the weak acid and conjugate base have colours)

 When the solution is acidic and the [H3O+] is high, there is a shift to the left, causing a colour
change (causing increase in HIn concentration)
 When the solution is basic and the concentration of [H3O+] is lower, there is a shift to the
right, causing a colour change (causing increase in In- concentration)

• explain the relationship between the pH range of an acid-base indicator and its pKa value (???)

• recognise that indicators change colour when the pH = pKa and identify an appropriate indicator for a
titration, given equivalence point of the titration and pH range of the indicator.

The indicator will change colour when: [HIn] = [In-]

- In other words, the colour change occurs: Ka = [H3O+] (as shown below when cancelling occurs)
- Because the number can be small, we can also use pKa to illustrate the strength of an acid. The
smaller the pKa, the stronger the acid.

Consider the equilibrium equation:

Different indicators change colour over different pH ranges. Colour change can be considered to take place
over a range of pKa ± 1.
Volumetric analysis

• distinguish between the terms end point and equivalence point

Equivalence point: point in a titration where reactants have reacted according to the molar (stoichiometric)
ratio of the balanced chemical.

End point: point in titration when the indicator changes colour

• recognise that acid-base titrations rely on the identification of an equivalence point by measuring the
associated change in pH, using chemical indicators or pH meters, to reveal an observable end point

- In titration, a solution with a known quantity is titrated against a solution of an unknown

concentration.
- Depending on the amount of known solution used to neutralize the solution, known as a titre,
calculations can be performed to determine the concentration of the unknown solution.
- The titre will also depend on the stoichiometric ratio (write out balanced equation first!!!)

• sketch the general shapes of graphs of pH against volume (titration curves) involving strong and weak
acids and bases. Identify and explain their important features, including the intercept with pH axis,
equivalence point, buffer region and points where pKa = pH or pKb = pOH
Buffer region: section of titration curve that is relatviely flat because adding more acid or base does not
drastically affect the pH

- the pH is quite resistant to change, thus [H3O+] and [OH-] increase less than expected.
- Within the buffer region is the buffer point or half equivalence point, where half the amount of
the contents in the flask have reacted.
 i.e. enough reactants have reacted, meaning that half of the acid-base has been neutralised.
 Concentration of the titre is half the concentration of the unknown analyte
- At the buffer point, the concentration of [HA] and [A- ] cancel out, we are left with Ka = [H+] or
pKa= pH. The same would be true for pOH and pK

• use appropriate mathematical representations and analyse experimental data and titration curves to
solve problems and make predictions, including using the mole concept to calculate moles, mass, volume
and concentration from volumetric analysis data.

Consider the titration of a solution of phosphoric acid (H3PO4) with a solution of sodium hydroxide (NaOH):

1) If you know the volume and concentration of phosphoric acid, you can calculate the number of
moles of phosphoric acid from the formula: n = C × V
2) Then you can use the stoichiometric ratio in the balanced chemical equation to calculate the number
of moles of sodium hydroxide.
3) If the volume of the sodium hydroxide is also accurately known, you can determine the
concentration of this solution.

• Mandatory practical: Acid-base titration to calculate the concentration of a solution with reference to a
standard solution.
For a substance to be used as a primary standard, the substance must:
• be pure and found in a stable form.
• not react with the atmosphere (e.g. moisture, carbon dioxide etc.).
• be soluble in solution.
• be readily available and inexpensive.
• be able to be weighed accurately (high known mm to reduce error).
Errors and misconceptions with standard solutions:

Students often make two common errors and misconceptions when preparing and discussing standard
solutions.

1) Not washing the volumetric flask before adding the solute. It is essential to wash the flask because it
may contain impurities that will contaminate the solution and may result in a reaction within the
flask.
- First, rinse the flask with water to dissolve any water-soluble impurities. Then wash it with the
solvent. If the solvent is water, wash the volumetric flask a second time.
- A common misconception is that washing the flask with water will dilute the solution within the
flask. But if the flask is first washed with water and then the solute is added, more water must
be added to finish making the solution. Having water in the volumetric flask before adding the
solute will not affect the concentration of the standard solution.
- I believe burette and pipette must be rinsed with solution to prevent errors.
2) Adding the solvent to the volumetric flask first. The solute must be added to the volumetric flask
before the solvent. A common misconception is that, to make a 250 mL solution, you need 250 mL of
solvent. But, as shown in Figure 3, this is incorrect because the solute has volume too. Ammonium
dichromate is added to the volumetric flask and water is added to make up to 250 mL. The solute
and solvent have a combined volume of 250 mL. Thus, the solute must be added before the solvent.