Chemistry 30 – Unit 8: Chemical Equilibrium (Acid-Base)

Explaining Equilibrium Systems (Reference Chapter 15.1)

• Recall collision-reaction theory.

Particles must collide (with
sufficient energy and orientation)
in order to react. What happens if
the products of a reaction begin to
collide?

• Not all reactions are quantitative, where the limiting reagent is

completely consumed.

• Many do not go to completion, ∴ have less than a 100% reaction, and

instead form equilibrium systems. But why?

1
• The characteristics of equilibrium systems include:

o They take place in closed system and all reactants and products are
present.

o Concentrations are constant.

o The equilibrium is dynamic.

 Reactants are becoming products and products are becoming
reactants at the same rate.

o No observable changes. (Looks like nothing is happening)

o Initially the rate of the forward reaction is fast, but it will eventually
slow down as reactants are consumed. The rate of the reverse
reaction starts slowly due to their being so few products present.
However, as the amount of product increases, the rate of the reverse
increases.

o Equlibrium systems are not necessarily 50/50. It is only the

RATES of the forward and reverse reactions that are equal.

2
• From the video, we see that a system reaches an equilibrium state in the
following manner.

• There are 3 types of equilibria:

A. Phase equilibrium – a single substance existing in more than one

phase in a closed system.

• Solid – liquid (melting/freezing)

o It is temperature dependent.
o Water at 0°C is an example. H2O(l)  H2O(s)

• Liquid – gas (evaporation/condensation)

o The container must be sealed to prevent the escape of gas. It is
not temperature dependent, but it is temperature specific.
o The rate of evaporation/condensation of water would change
depending on the ambient temperature, H2O(l)  H2O(g)

• Solid – gas (sublimation)

o Napthalene, C10H8 (s), otherwise known as moth balls, placed in a
sealed drawer (closed system). C10H8 (s)  C10H8 (g)

• FYI… it is possible for a substance to be

present in all 3 phases at equilibrium.
Each substance would require a unique
temperature and pressure. This is
called the triple point and for water
it is at 0.01°C and 0.006 atm.

3
B. Solubility equilibrium - when a chemical compound in the solid state
is in chemical equilibrium with a solution of that compound.

• This occurs in saturated solutions only, where the rate of

dissolving = the rate of crystallization.

• In chemistry 20, we tested dynamic equilibrium to explain saturated

solutions. What we didn’t discuss was that the solute and solution
were achieving an equilibrium system. See Fig 6 p. 225.

C. Chemical Reaction Equilibrium – Involves reactants & products of a

reaction.

• See Figure 4 on page 679 of the Nelson text on the

Hydrogen – Iodine Formation Reaction. H2 (g) + I2 (g)  HI(g)

• One would expect that the colour in the flask would continue to
fade, however it remains and becomes constant. This indicates
that HI(g) is decomposing at the same rate at which its produced.

• Note that in Figure 5 on p. 679 that the concentrations are constant

at equilibrium.
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Describing the Quantitative State of an Equilibrium System
• The actual yield of a chemical reaction at equilibrium is described by the
% Reaction calculation:

• Describes the extent to which a reaction goes to completion.

• Is temperature and concentration dependent.

• A 100% reaction would indicate a quantitative reaction whereas anything

less indicates an equilibrium system. Theoretical yield assumes a
quantitative reaction.

• Position of equilibrium (see Table 3 p 680):

5
Using ICE Tables to Solve Equilibrium Problems:
• An ICE table is a visual aid to organize and help solve equilibrium
problems. ICE stands for initial, change, and equilibrium.

Examples:

1. Study sample problem 15.1 on p 681.

2. 1.00 mol hydrogen gas and 0.75 mol iodine gas are placed in a 1.00 L
container and react to form 0.90 mol HI(g) at equilibrium. Calculate
equilibrium concentrations of the reactants. Organize your work in an
ICE table. Calculate the % reaction. (60%)

3. In a 2.00 L gaseous reaction system, 2.00 mol of methane is initially

added to 10.00 mol of chlorine gas. At equilibrium the system contains
1.40 mol of chloromethane, CH3Cl(g) and some hydrogen chloride,
HCl(g).

a. Write the balanced reaction equation, complete the ICE table

and calculate the maximum yield of chloromethane.
b. Calculate the percent yield at equilibrium and state whether
products or reactants are favoured.

Practice: Read p. 676 – 682 in Nelson Chemistry text and answer the
following on a separate sheet of paper.
1. Complete problems #3, 5 – 7, p. 682
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Equilibrium constant, K/Kc/Keq
o It is a general quantitative description of an equilibrium system at a
particular temperature and a constant value for ANY concentration at
that same temperature.

o This is called the equilibrium law expression.

o K will be a constant value for any equilibrium concentrations at that

temperature for that reaction.

o No units!!!

o Most of the time, if K > 1, then products are favoured.

o Condensed states (constant concentration) are not included: solids

and liquids. Only include substances of variable concentrations that
achieve equilibrium (gases and solutions).

o Exception: if all states are liquid then these can all be included (rare).

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Examples: Study the examples on p. 684 & 685 of the Nelson text.
1. Write the equilibrium expressions for the following reactions:
a) N2(g) + O2(g)  2NO(g)
b) 2Fe3+(aq) + 2I-(aq)  2Fe2+(aq) + I2(aq)
c) CaCO3(s)  CaO(s) + CO2(g)
d) 4NH3(g) + 5O2(g)  4NO(g) + 6H2O(g)
e) NH3(g) + H2S(g)  NH4HS(S)

2. Calculate the equilibrium constant, K, for the following reactions:

a) PCl5(g)  PCl3(g) + Cl2(g) where the equilibrium concentrations are

1.2x10 -2 mol/L PCl5; 1.5x10 -2 mol/L PCl3; and 1.5x10 -2 mol/L Cl2.

b) Iodine and bromine react to form iodine monobromide, IBr(g). At

350 °C and equilibrium mixture in a 2.0 L flask was found to contain
0.024 mol of iodine, 0.050 mol of bromine and 0.38 mol of iodine
monobromide. What is the magnitude of Kc for the reaction?

3. Considering the information and equations given, complete the ICE

tables and calculate the values of the equilibrium constants and the %
reactions.

a)
A(g) + B(g)  2C(g) + D(g)
Initial (mol/L) 6.0 6.0 0 0
Change (mol/L)
Equilibrium (mol/L) 4.0
K= % reaction =

b)
W(g) + X(g)  3Y(g) + 2Z(g)
Initial (mol/L) 4.0 5.0 0 0
Change (mol/L)
Equilibrium (mol/L) 1.5
K= % reaction =

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 c)
M(g) + N(g)  P(s) + 2Q(g)
Initial (mol/L) 5.0 6.0 0 0
Change (mol/L)
Equilibrium (mol/L) 3.0

K= % reaction =

4. At a given temperature, the Kc for the following reaction:

2 HI(g)  H2(g) + I2(g) is 0.0140. If the equilibrium concentrations of H2(g)
and I2(g) are both 2.00 x 10-4 mol/L, find [HI] at equilibrium.
(1.69 x 10-3 mol/L)

5. H2S(g) is added to an empty sealed flask and reaches the following

equilibrium state: 2 H2S(g)  2 H2(g) + S2(g) The initial concentration of
H2S(g) is 5.24 x 10-3 mol/L. At equilibrium, the concentration of H2S(g) is
2.32 x 10-3 mol/L. Calculate the equilibrium constant. (2.31 x 10-3)

6. Given the reaction: CuO(s) + CO(g)  Cu(s) + CO2(g) Keq = 0.520 at

800.0°C what are the equilibrium concentrations of the gases if
0.500 mol of CO(g) is placed in a 500.0 mL flask with excess solid
CuO at 800.0°C?

7. Given the following reaction: A(g) + B(g)  C(g) + D(g) where K = 4.00. If
the initial concentrations of A and B are 1.00 M, calculate the
equilibrium concentrations of A, B, C and D.

8. In a 500 mL stainless steel reaction vessel at 900°C, carbon

monoxide and water vapour react to form carbon dioxide and
hydrogen. Evidence indicates that an equilibrium system was
achieved with only a partial conversion of reactants to products.
Initially 2.00 mol of each reactant is placed in the vessel. Kc = 4.20 at
900°C. What amount concentration of each substance will be present
at equilibrium? (CO = [1.31], H2O = [1.31], CO2 = [2.69], H2 = [2.69])

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 9. 1.00 mol of C is added to a two litre container and comes to the
following equilibrium:

A(g) + B(g)  C(g).

At equilibrium there is 0.50 mol of C(g). Calculate the value of the

equilibrium constant for the formation of C. (K = 4.0)

10. For the following reaction: 2 HBr(g)  H2(g) + Br2(g) where K = 36 and
the initial concentration of HBr is 0.15 M calculate all equilibrium
concentrations. (HBr = [0.012], H2 = [0.069], Br2 = [0.069])

Practice: Read p. 683 – 688 in Nelson Chemistry text and answer the
following on a separate sheet of paper.

1. Complete problems #1, 3 – 10, p. 688

2. Equilibrium worksheet in D2L
3. Complete lab exercise 15B in lab journal.

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 Qualitative Change in Equilibrium Systems
(Reference Chapter 15.2)

• How do changes imposed on an equilibrium system affect the

equilibrium position?

o According to Henri Le Chatelier:

“ …when changes are imposed on a system that has achieved

equilibrium, the system will shift in a direction that tends to
oppose the change until a new equilibrium is reached.”

• Known as Le Chatelier’s Principle, application of this requires three steps:

o An initial equilibrium state.

o Identify the imposed stress & determine the equilibrium shift (le
Chatelier) during the non-equilibrium state.

o A new equilibrium state (and consequences of the shift)

• There are 3 methods to shift the position of the equilibrium. One can:

1. Change the concentration of a reactant or product.

o Increasing the concentration of a substance shifts the equilibrium to

the side opposite that substance.

o Decreasing the concentration of a substance shifts the equilibrium

to the side it is on.

o The initial and final K values are the same.

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 o Consider the Haber process, used to manufacture ammonia from
nitrogen and hydrogen gasses.

N2(g) + 3 H2(g)  2 NH3(g)

o If hydrogen is added, hydrogen concentration is increased, to the
initial equilibrium system of this Haber reaction, how would the
system respond according to Le Chatellier’s principle?

2. Change the temperature.

o Increasing the temperature in any reaction shifts the equilibrium to
the side opposite the energy term. Decreasing the temperature in
any reaction shifts the equilibrium to the side containing the energy
term.

o The K value will change with temperature changes.

o Exothermic reactions have energy as a product, endothermic

reactions show energy as a reactant. (…as viewed from the forward
reaction)

o In the exothermic reaction between

sulphur dioxide and oxygen, sulphur
trioxide is produced along with an
excess of energy. How would the
initial equilibrium state respond if the
temperature of the reaction was
reduced?

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3. Change the pressure/volume of the gas components.

o There are 3 ways to change the pressure of a gas equilibrium

system:
o Add or remove a gas reactant or product.
o Add an inert gas.
o Change the volume (and therefore pressure) of the
container.

o Decreasing the volume (P) shifts the equilibrium to the side with
the least # of moles of gas.

o Increasing the volume (P) shifts the equilibrium to the side with
the greatest # of moles of gas.

o Why? Recall the ideal gas law:

𝑷𝑷𝑷𝑷 = 𝒏𝒏𝒏𝒏𝒏𝒏

𝑹𝑹𝑹𝑹
𝑷𝑷 = 𝒏𝒏 � � ∴ 𝑷𝑷 ∝ 𝒏𝒏
𝑽𝑽
o Consider the calcium carbonate decomposition equilibrium:

13
 o Consider the N2O4 (g)  2 NO2 (g)
equilibrium system. N2O4 (g) is
colourless. NO2 (g) is a brown-red
gas. In the images of the syringe,
volume of the syringe is decreased.
Note and explain the changes.

o The initial and final K values are the same

o Look at the following video:

Catalysts and Equilibrium Systems

• A catalyst is a substance that is added to a reaction to increase its rate,
but it is not consumed. It lowers the activation energy.

• A catalyst has no effect on an equilibrium system since it makes both the

forward and reverse reactions easier by the same amount.
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Examples:

1. Predict the effect upon the system, if the following changes are
imposed. Describe the effect and graph the reaction as it re-
establishes equilibrium.

Cu(s) + 2Ag+(aq)  Cu2+(aq) + 2Ag(s) (graph each of the following)

IMPOSED
PREDICTION GRAPH
CHANGE

Add AgNO3(s)

Add AgCl(s)

Add
Cu(NO3)2(s)

Add Ag(s)

Add NaCl(s)

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 C2H4(g) + 3O2(g)  2CO2(g) + 2H2O(g) ∆H = -1323 kJ

IMPOSED
PREDICTION GRAPH
CHANGE

Temperature is
increased

Temperature is
decreased

2 CO(g) + O2(g)  2 CO2(g)

IMPOSED
PREDICTION GRAPH
CHANGE

Decrease the
volume
(read p 694)

Increase the
volume

Add an inert gas

such as He(g)
with no
volume change

16
• Throughout the examples, it should be apparent that K is only
temperature dependent. It is independent of concentration and
pressure/volume changes.

Practice: Read p. 690 – 699 in Nelson Chemistry text and answer the
following on a separate sheet of paper.

1. Lab 15.2 p. 50
2. Complete problems #1 – 3, p. 695; #1 – 7, p. 699
3. Lab assignment 15C
4. Pre-lab Le Chatelier’s Principle Lab p. 52 of lab journal

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 Chemistry 30 – Unit 8: Chemical Equilibrium (Acid-Base)
Water Ionization and Acid-Base Strength (Ref: Chap 16.1)

• Before we get to the water ionization constant, we need a little chem 20

refresher…

o What is an acid?

 Acids begin as molecular or ionic compounds. In order for the

compound to behave as an acid, a couple of things have to
happen:

• The molecule must also contain a “loosely held” hydrogen AND it

has to be soluble in water, therefore aqueous (aq), in solution!

• If it can’t dissolve, even a little bit, it cannot create an acidic

solution.

 So how does a “potential acid” produce the hydronium ion, H3O+,

in solution?

• Regardless of the molecular or ionic nature of the “acid,” it reacts

with water, in a process called ionization, to create hydronium in
solution.

1
  Note, when acids ionize in aqueous solutions, they produce the
hydronium ion, H3O+… not just a highly reactive proton, H+. This
was known as the modified Arrhenius definition in chem 20.

o What is a base?

 Bases are either ionic compounds that contain the hydroxide ion,
OH-, or molecules.

 To create a basic solution from an ionic hydroxide compound, it first

must dissolve and then dissociate into its respective ions.
Because OH- is part of the compound, it creates OH- (aq) in solution.
the base is ionic,

 If the potential base is a molecule, it too must be soluble in water

and then ionize in a reaction with water to create hydroxide ions in
solution.

Water Ionization Constant, Kw

• When pure water is tested with very sensitive instruments, it is always
shown to be slightly conductive. Remember that conductivity requires
the presence of ions in solution.

• Therefore, pure water must contain ions. This is explained by the very
slight equilibrium system that exists for pure water.

2
• The ionization of water into ions is very small. This means that the
equilibrium favours the reactants to a very LARGE extent! (See p. 713)

• The value of the equilibrium constant, called Kw, is 1.00 x 10-14 for the
ionization of water.

• Therefore the equilibrium law expression is: KW = [H3O+] [OH-] = 1.00 x

10-14 @ SATP only! This is because equilibrium constants are
temperature dependent.

Examples:

1. A 0.25 M HCl solution has a hydronium ion concentration of 0.25

mol/L. Determine the concentration of hydroxide ions in the solution.
(4.0 x 10-14 mol/L)

2. If 3.65 g of HCl(s) is dissolved in 2.00 L of pure water at SATP,

calculate the hydronium and hydroxide ion concentration.

3. If 1.00 g of solid NaOH is added to 400 mL of water at SATP,

calculate the hydronium and hydroxide ion concentration.

4. If the concentration of calcium hydroxide is 4.00 mmol/L calculate the

hydronium and hydroxide ion concentration under SATP conditions.
(8.0 x 10-3 mol/L [OH-], 1.3 x 10-12 mol/L [H3O+])

Practice: Read p. 712 – 716 in Nelson Chemistry text and answer the
following on a separate sheet of paper.

1. Complete problems #1 – 5, p. 716

2. Lab assignment 16A
3
Communicating concentration: pH & pOH
• Review pH and pOH calculations on pp 716-717.

pH = -log[H3O+] pOH = -log[OH-]

[H3O+] = 10-pH [OH-] = 10-pOH
Kw = [H3O+][OH-]
pH + pOH = 14.00

• Significant Digits and

pH/pOH:

o Any digit to the left of

the decimal of a
logarithmic value (pH
and pOH) is NOT
significant.

o ALL digits to the right of

the decimal are
significant including 0.

Examples:

1. Complete the following table:

[H3O+] pH [OH-] pOH SIG DIGS

10-4 4 10-10 10 0
3
12
0.01
6.1
-3
2.2 x 10

4
 1. Complete the following table: (solutions)

[H3O+] pH [OH-] pOH SIG DIGS

10-4 4 10-10 10 0
10-3 3 10-11 11 0
10-2 2 10-12 12 0
1 x10-12 12.0 0.01 2.0 1
1 x10-8 7.9 8 x10-7 6.1 1
2.2 x 10-3 2.66 4.6 x10-12 11.34 2

2. What mass of NaOH(s) must be dissolved to make 1.00 L of solution

with a pH of 13.12? (5.3 g)

Practice: Read p. 716 – 718 in Nelson Chemistry text and answer the
following on a separate sheet of paper.

1. Complete problems #7, 9 p. 718

2. Problem #8 (recognize “odd” pH and pOH values. Hint: see pH table
on p. 4 of notes)

5
Acid Strength as an Equilibrium Position

• Recall from Chem 20:

THEORETICALLY EMPIRICALLY
o React quantitatively o High conductivity
STRONG
(100%) with water to o Very low pH
ACIDS
produce H3O+(aq) o Fast rate of reaction
o Low conductivity
o React incompletely
WEAK o pH closer to 7 than SA of
(<50%) with water to
ACIDS equal concentration
produce H3O+(aq)
o Slow rate of reaction

• How does this relate to equilibrium?

o Since weak acids react incompletely with water they are therefore
equilibrium systems!

STRONG ACID WEAK ACID

• STRONG ACIDS: [H3O+] = [ACID] (complete reaction with water)

o HA(aq) + H2O(l) → H3O+(aq) + A-(aq)

• WEAK ACIDS: [H3O+] <<< [ACID]

o HA(aq) + H2O(l)  H3O+(aq) + A-(aq)

6
• Since % ionization is an equilibrium position and equilibrium position
changes with concentration, temperature and pressure/volume, then %
ionization is only valid under static conditions such as SATP.

• To calculate the % ionization, 𝝆𝝆 (rho), of a weak acid equilibrium

system:

𝒂𝒂𝒂𝒂𝒂𝒂𝒂𝒂𝒂𝒂𝒂𝒂
% 𝒓𝒓𝒓𝒓𝒓𝒓 = 𝒙𝒙 𝟏𝟏𝟏𝟏𝟏𝟏
𝒕𝒕𝒕𝒕𝒕𝒕𝒕𝒕𝒕𝒕𝒕𝒕𝒕𝒕𝒕𝒕𝒕𝒕𝒕𝒕𝒕𝒕𝒎𝒎𝒎𝒎𝒎𝒎

∴
�𝑯𝑯𝟑𝟑 𝑶𝑶+
(𝒂𝒂𝒂𝒂) �
% 𝒊𝒊𝒊𝒊𝒊𝒊𝒊𝒊𝒊𝒊𝒊𝒊𝒊𝒊𝒊𝒊𝒊𝒊𝒊𝒊 = 𝝆𝝆 = 𝒙𝒙 𝟏𝟏𝟏𝟏𝟏𝟏
�𝑯𝑯𝑨𝑨(𝒂𝒂𝒂𝒂) �

Examples:

1. Calculate the % ionization of a 0.15 M weak acid solution if the pH is

3.32. (0.32%)

2. A weak acid has a concentration of 0.10 M and a % ionization of

5.6%. Calculate the pH of the solution. (2.25)

Practice: Read p. 718 – 721 in Nelson Chemistry text and answer the
following on a separate sheet of paper.

1. Complete problems #6, p. 716; #1 – 14, p. 721

7
 The Bronsted-Lowry Acid-Base Concept (Ref: Chap 16.2)

• Acids and bases have always been “tricky” to define:

o Greek & early theories only described properties and effects; vinegar
vs. soap. (i.e. acids taste sour, bases are slippery)

o Lavoisier (1800s) suggested that oxygen was the component of acidic

compounds that provided acidic properties. Wrong, but the first
attempt at a systematic explanation.

o Davy later identified that hydrogen seemed to be the common

component in acids, but not all hydrogen-containing compounds are
acids.

• (Modified) Arrhenius Theory:

Acid
 any substance that reacts with water to produce hydronium
ions (H3O+) in solution.

Base
 any substance that reacts with water to produce hydroxide ion
(OH-) in solution.

• However none of these work in all acidic or basic situations. Therefore,

the Acid-Base Theory needs to be expanded because:

o Not all reactions of acids and bases involve reaction with water.

o Amphiprotic species (substances that can act as EITHER acid or

base) need to be further explained. Why can some species act as
both an acid and a base?

o The Bronsted-Lowry concept provides much greater accuracy and

explanation of what is acid and what is base… and explains the why.

8
Proton-Transfer Theory:
• The Bronsted-Lowry concept is based upon the idea of proton transfer.

o Bronsted-Lowry acid: A molecule or ion that can transfer a proton to

another substance, or in other words, a “proton donor.”

o Bronsted-Lowry base: A substance that can accept a proton in a

chemical reaction, or in other words, a “proton acceptor.”

• Therefore, in a proton transfer reaction at equilibrium, both forward and

reverse reactions involve Bronsted-Lowry acids and bases.

• See the equilibrium equation for acetic acid (vinegar) on p. 724 of the
text:

9
EXAMPLES: Identify the Bronsted-Lowry acid and base in each reaction.

1. H3PO4(aq) + H2O(l)  H2PO4-(aq) + H3O+(aq)

2. CO32-(aq) + H2O(l)  HCO3-(aq) + OH-(aq)

3. H3PO4(aq) + CO32-(aq)  H2PO4-(aq) + HCO3-(aq)

4. HCl(aq) +NH3(aq) → NH4+(aq) + Cl-(aq)

5. H3O+(aq) + OH-(aq) → H2O(l) + H2O(l)

• From the examples above:

o Water is amphoteric/amphiprotic. It can act as an acid in some

reactions and as a base in others by donating a proton in some
reactions or accepting a proton in others.

o Water does not have to be a reactant. Therefore this goes beyond

the of hydrolysis and the Arrhenius definition of acids and bases.

• Study the examples on pp 722-723. Note that the hydrogen

carbonate ion (HCO3-) in baking soda is also amphiprotic /
amphoteric.

10
Conjugate Acids & Bases

• Conjugate pairs are substances that only differ by only one proton.

• Acid-base reaction always contain 2 conjugate acid-base pairs. One

pair is stronger than the other.

• Equilibrium always favours the SIDE with the weaker acid and
the weaker base!

Examples: Identify the conjugate acid-base pairs in the following:

1. HA + HOH  H3O+ + A-

2. HA- + HB-  H2A + B2-

11
STRONG ACIDS:

HX(aq) + H2O(l) → H3O+(aq) + X-(aq)

SA SB WA WB

• Note that the reaction of a strong acid with water is quantitative which
means that the reverse reaction X- + H3O+) is not significant. The
conjugate acids of the strong acids are weaker bases than water and are
considered to be neutral. All other anions are weak bases.

WEAK ACIDS:

HX(aq) + H2O(l)  H3O+(aq) + X-(aq)

• The stronger the acid, the weaker the conjugate base & vice versa.
See Acid-Base Table in Data booklet.

• Study Figure 5 p. 725

Practice: Read p. 722 – 731 in Nelson Chemistry text and answer the
following on a separate sheet of paper.

1. Complete problems #3 and 4 on p. 724; #7 and 8 on p. 726

2. Complete lab exercise 16B.

12
Predicting Acid-Base Reaction Equilibria

• In a Bronsted-Lowry acid-base reaction, the reaction is ultimately a

competition for a proton between all the potential acids and potential
base. Who wins?

o Simple. The proton, H+, is always transferred from the strongest

acid  strongest base.

• So how do we identify the strongest acid and the strongest base???

Refer to data booklet!

• Use the 5 step method to write acid – base reactions.

1. List all entities as they exist in solutions (Table 1 on p. 728)

2. Label each entity as either an acid, a base or neutral. If

amphiprotic label as both an acid and a base.

3. Label the strongest acid (SA) and the strongest base (SB).

4. Write a Bronsted-Lowry balanced equation. (Proton transfer

equation from SA  SB)

5. Predict the position of the equilibrium (Learning Tip p. 729).

13
Examples: Example 16.1 p. 729

1. Sodium hydroxide solution is neutralized with vinegar.

List entities: Na+(aq) OH-(aq) CH3COOH(aq) H2O(l)

A A
Identify Acids and Bases: Na+(aq) OH-(aq) CH3COOH(aq) H2O(l)
B B

SA
+
Identify SA & SB: Na (aq) OH-(aq) CH3COOH(aq) H2O(l)
SB

Write balanced equation to show proton (H+) transfer:

CH3COOH(aq) + OH-(aq)  CH3COO- (aq) + H2O(l)

Write balanced equation with predicted eq’m position:

>50%
CH3COOH(aq) + OH-(aq)  CH3COO- (aq) + H2O(l)

14
 2. Aqueous ammonia is mixed with nitric acid.

3. Build an acid-base table from the following reaction information:

(Similar to 16D)

HA + B-  HB + A- reactants are favoured

HC + D-  HD + C- products are favoured

HD + B-  HB + D- products are favoured

4. Sodium hydrogen phosphate solution is mixed with vinegar.

Practice: Read p. 722 – 731 in Nelson Chemistry text and answer the
following on a separate sheet of paper.

1. Complete problems # 9 – 17, p. 731; #1 – 8, p. 735.

2. Complete lab assignments 16C and 16D in lab journal.
3. Prelab 16.2 in lab journal.

15
 Acid-Base Strength and the Equilibrium Law (Ref: Chap 16.3)
• Recall:

o For a strong acid, the [H3O+] = [strong acid]initial

o For weak acids, the [H3O+] << [WA] since the weak acid does not
ionize completely and ∴the K for the acid is << 1.

• Quantitatively, we can describe acids two ways:

1. % Ionization (% Reaction of an Acid)

 Strong acids ionize >99% (Quantitative)
 Weak acids ionize <50% (An Equilibrium system)
 Like % reaction, % ionization is only valid at a particular
concentration.

2. Ka – which is constant at a given temperature

The Acid Ionization Constant, Ka

• The Ka values in your data table are a special case of the equilibrium law
for an acid reacting with water in solution.

o Note that the greater the Ka value the stronger the acid. Therefore,
the higher the acid in the table the stronger the acid.

o Some Tables give percent reaction (ionization) but these will vary with
concentration.

• There are two types of calculations:

A. Where pH/[H3O+] is given or

B. Where pH/[H3O+] is to be calculated

16
A. Calculations where pH/[H3O+] is given:
Examples: Study the examples on p. 738 – 739 and complete the
following:

1. The pH of a 0.10 mol/L H3PO4(aq) solution was measured to be 1.70.

a. Write a balanced Bronsted-Lowry equation and write an equilibrium

law expression.
b. Sketch an ICE table for the reaction.
c. Determine the equilibrium concentration of H3O from the pH.
d. Calculate Ka (0.0050 ∴ 5.0 x 10-3)
e. Calculate % ionization (20%)

2. Boric acid, H3BO3(aq) used for contact lenses has a concentration of

0.10 M and a pH of 5.16.

a. Calculate the Ka. (4.8 x 10-10)

b. Calculate the % ionization. (0.0069%)

3. Calculate the equilibrium concentration of a weak acid whose Ka is

2.1 x 10-5 and pH is 2.87. (8.7 x 10-2)

4. What is the initial concentration of the above acid? (8.8 x 10-2)

B. Where pH/[H3O+] is to be calculated:

Examples: Study the examples on p. 740 – 742 and complete the
following:

1. Calculate the pH of a 0.30 mol/L CH3COOH(aq) which has a

Ka = 1.8 x 10-5 (2.63)

Write your Ka equilibrium expression… what do you notice?

17
But, the quadratic can be avoided if we assume “x” is so small that it
is safe to ignore. When is this valid?

Ka = [H+]2/[WA]

If the initial concentration of the weak acid [WA] is at least 1000X

greater than its Ka value, you may assume that the initial and
equilibrium concentrations of the weak acid are numerically equal.
This is known as the “RULE OF 1000.”

Check the ratio [Weak Acid]/Ka > 1000 and determine if the
generalization is valid:

[𝑊𝑊𝑊𝑊] [0.30]
𝐶𝐶𝐶𝐶𝐶𝐶 𝑥𝑥 𝑏𝑏𝑏𝑏 𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖? = = 𝟏𝟏𝟏𝟏𝟏𝟏𝟏𝟏𝟏𝟏
𝐾𝐾𝑎𝑎 1.8 𝑥𝑥 10−5

Ratio is > 1000, so “x” is safe to ignore in the previous problem!

OR

Ignore x immediately and check the validity of your solution using the
5% IONIZATION RULE. If the % ionization of the acid is less than 5%
then it is assumed that the initial and equilibrium concentration
difference “X” is negligible and the assumption was valid.
+
�H3 O(aq) �
% ionization = ρ = x 100
�HA(aq) �

[2.32 𝑥𝑥 10−3 ]
% ionization = ρ = x 100 = 0.77%
[0.30]

The percent ionization/reaction is less that 5% therefore the

assumption is valid.

18
Examples:

1. What is the pH of 0.010 mol/L H2CO3(aq) in a system at 298.15 K?

(4.17)

2. Calculate the pH and % ionization of a 2.0 mol/L HF(aq) at 298.15 K

(1.45, 1.8%)

3. Calculate the pH and % ionization of a 0.10 mol/L HF(aq) at 298.15 K.

(2.10, 7.9%) Do you trust your answer? Why or why not?

Practice: Read p. 737 – 743 in Nelson Chemistry text and answer the
following on a separate sheet of paper.

1. Complete problems # 1 – 9, p. 743

2. Complete “Strengths of Acids” worksheet on D2L.

19
Base Strength & the Ionization Constant, Kb

• Strong bases:

o Ionic hydroxides, soluble metal oxides (See example on p. 744)

• Weak bases: certain molecular compounds and anions (except for the
conjugate bases of the strong acids)

o Hydrolyze (meaning that they react with water) INCOMPLETELY to

form hydroxide ions. (Chem 20)

o Since these reactions are incomplete then they form equilibrium

systems.

o E.g. NH3(g), NaF(s)

pH/pOH IS GIVEN, p. 745

EXAMPLES: Study the example on pp. 745-746

1. The pH of a 0.10 mol/L NaNO2(aq) is 7.63. Calculate the Kb.

(1.8 x 10-12)

a. The percent ionization of the above reaction is? (0.00043%)

2. The pH of a 0.15 M NaF(aq) is 8.20. Calculate Kb and % ionization.

(1.7 x 10-11, 0.0011%)

3. If the Kb of a weak base is 2.1 x 10-6 and the pH is 10.21 what is the
initial concentration of the base?

20
 pH/pOH IS TO BE CALCULATED, p 746

• To solve for Kb of a “conjugate base” divide the Ka of its “acid formula”

into Kw
o Kw = Ka x Kb (see p 747)
o Kb = Kw/Ka

EXAMPLES: Study the examples on pp 747-748

1. Calculate the Kb of the hydrogen carbonate ion at 298 K. (2.2 x 10 -4)

2. Calculate the Kb of the hydrogen sulfite ion at 298 K. (7.1 x 10 -13)

3. Study the example on pp 748-749. Calculate the pH of 0.10 mol/L

NH3(aq). (11.13) Are you confident in your previous answer? Why or why
not?

4. A certain 0.010 M weak base has a Kb of 1.9 x 10-2. Calculate the pH of

the solution. Is the answer accurate? Explain.

21
Practice: Read p. 744 – 750 in Nelson Chemistry text and answer the
following on a separate sheet of paper.

1. Complete problems # 10 – 13 on p. 746. (In #12, [OH-] = 1.1 x 10-5,

[C2H5COO-] = 0.157)

2. Complete problems # 1 – 8, 10 on p. 750. (In #4, the Ka for boric acid

is in appendix.)

22
 Interpreting pH Curves (Reference: Chap 16.4)
• Write the net ionic equation for the reaction of the continuous addition of
strong base, NaOH(aq), to a strong acid, HCl(aq). Sketch the pH curve.

Label the equivalence point and the entities present in the solution
before the equivalence point, at the equivalence point and after the
equivalence point. Choose an appropriate indicator.

• Equivalence Point (theoretical) – The volume and pH where

stoichiometric equivalent amounts have reacted. Both reactants have
been consumed and only products remain. THE PROTON TRANSFER
IS COMPLETE and the reaction is quantitative.

• Endpoint (empirical) – the observed colour change of the indicator or

rapid change in pH.

o So what’s the difference???

o Endpoint (Indicator) and Equivalence Point (Volume) are ideally

identical within a small uncertainty of measurement. It takes a small
amount (one drop?) of excess titrant to cause a noticeable colour
change.

23
Acid-Base Indicator Equilibrium
• Indicator - Substance that changes colour when reacted with an acid or
a base. Bronsted-Lowry concept defines an indicator as a conjugate
weak acid-base pair:

HIn(aq) + H2O(l)  In-(aq) + H3O+(aq)

Cloour #1 Colour #2

• Consider Le Chatelier’s Principle to explain how they work:

1. Add H3O+: Shifts left and Colour #1 appears

2. Add OH-: Consumes H3O+ and shifts right and Colour #2 appears

Example:

1. Identify the acid-base conjugate pairs for the phenol red indicator and
label the colours.

Practice: Read p. 751 – 754 in Nelson Chemistry text and answer the
following on a separate sheet of paper.

1. Complete problems # 1 – 4, p. 754

Polyprotic Entities and Sequential Reactions

• Polyprotic species are molecules that are able to either donate or

accept more than one proton. Examples include: H2CO3(aq),
HOOCCOOH(aq), HPO42-(aq), CO32-(aq), etc…

• The first proton accepted or donated will always be easier to

accept/donate than the second or third. (See p. 756)

• Each quantitative step will have a visible endpoint. If the reaction is

at equilibrium then there will be no visible endpoint and the graph
will be closer to horizontal. The number of endpoints corresponds
to the number of quantitative steps.

24
Example:

1. Write the 2 Bronsted-Lowry quantitative equations for the titration of

sodium carbonate with hydrochloric acid. (This means that there is a
continuous supply of hydrochloric acid. i.e. It is available in “infinite”
quantity). The pH curve on p 755 indicates that there are two
quantitative steps. Use the Five-Step Method.
SA A
Na+(aq) CO32-(aq) + -
H3O (aq) Cl (aq) H2O(l)
SB B

I. H3O+(aq) + CO32-(aq) → HCO3-(aq) + H2O(l)

This step is quantitative

Because it’s a titration, acid continues to be added from the buret.
SA A A
+ 2-
Na H3O (aq) Cl (aq) H2O(l) HCO3-(aq)
(aq) CO3 (aq)
+ -

all gone B SB

II. H3O+(aq) + HCO3-(aq) → H2CO3(aq) + H2O(l)

The hydrogen carbonate ion is the new stronger base as the carbonate
ion is gone. According to a pH curve (Figure 7, p. 755), it reacts
quantitatively with the hydronium ion, as it is a strong enough proton
acceptor.

There isn’t a third reaction, as water is now the only potential base
present.

The net ionic equation is: 2 H3O+(aq) + CO32-(aq)  H2CO3(aq) + 2 H2O(l)

25
Examples: Use the 5 step method to determine the net equation for each.
Sketch the pH curve.

1. Sulfurous acid is titrated to completion with sodium hydroxide.

2. Sodium ascorbate is titrated with hydrochloric acid to the second

endpoint. (Hint: see Acid-base table in your data booklet)

3. Sulfuric acid is titrated with hydrochloric acid. Sulfuric acid is

polyprotic, but the pH curve indicates that there is only one
quantitative step. Explain.

Practice: Read p. 755 – 759 in Nelson Chemistry text and answer the
following on a separate sheet of paper.

1. Complete problems # 5 – 10, p. 759

26
pH Curve Shape vs. Acid & Base Strength
• You must be able to sketch a titration curve and indicate the relative pH
at the equivalence point.

• The pH at the equivalence point is determined by the entities

present at the equivalence point.

• See p. 761-762 for titration pH generalizations: (determined by the

hydrolysis of the salt produced – that is, what is present in the solution at
the equivalence point)

• Summary:
TITRATION ENDPOINT pH
SA-SB 7
SA-WB <7
SB-WA >7

Examples: Write the net equation, sketch the curve, indicate the relative
pH at the equivalence point, choose an indicator and indicate the entities
present before, at and after each equivalence point. Label the buffering
region(s).

1. NaCH3COO(aq) titrated with HCl(aq)

2. CH3COOH(aq) titrated with NaOH(aq)

3. Sodium carbonate is titrated with hydrochloric acid (2 quantitative

steps)

Practice: Read p. 760 – 763 in Nelson Chemistry text and answer the
following on a separate sheet of paper.

1. Complete problems # 11 – 15, p. 762

27
pH Curve Buffering Regions & Buffer Solutions
• Buffer:

• Theoretical: A solution consisting of a weak acid and its conjugate

base in approximately equal concentrations ([WA] ≈ [CB]). They are
both present in solution.

• Empirical: A solution capable of absorbing small amounts of strong

acid or base with only a small change in pH.

• A buffering region on a pH curve is where both weak acid and conjugate

base are present.

• The 5-step method can be used to obtain a Bronsted-Lowry equation to

explain the action of the buffer. Study examples on p. 764 and Fig 16.

• Natural buffers in the human body:

• H2PO4-(aq) – HPO42-(aq) (cell cytoplasm)

• H2CO3(aq) – HCO3-(aq) (blood and other bodily fluids).
• See Table 1 p 765.

28
Practice: Read p. 760 – 763 in Nelson Chemistry text and answer the
following on a separate sheet of paper.

1. Complete problems #18 – 21, p. 766; #2 – 10, p. 767.

TITRATION

• Use 5 step method and ionic equations to solve titration problems… be

consistent. Do not use non-ionic equations!!!

• Reactions must be quantitative since stoichiometry assumes

complete conversion to products.

• The number of endpoints must be known to obtain the correct equation

(how many protons were transferred/accepted???).

• To determine the number of endpoints use:

1. pH curve
2. The number of endpoints might be given

EXAMPLES:

1. 50.0 mL of 0.250 mol/L sodium carbonate is titrated with nitric acid to the
second endpoint. Calculate the concentration of the acid and its pH.
(0.954 mol/L, 0.020)

Titration of 50.0 mL of 0.250 mol/L sodium carbonate with nitric acid

TRIAL 1 2 3 4
FINAL BURET READING (mL) 26.6 52.9 29.1 55.2
INITIAL BURET READING (mL) 0.4 26.6 1.8 29.1
AMOUNT OF HNO3(aq) (mL) 26.2 26.3 27.3 26.1

2. 25.0 mL of 0.49 mol/L acetic acid solution is titrated with 26.0 mL

strontium hydroxide solution to neutralization. Calculate the
concentration of strontium hydroxide. (0.24 mol/L)
29
 Let’s review…

1. Determine the Ka for an acid HY(aq) if the initial concentration was 0.22
mol/L and the pH at equilibrium was 4.92. (6.6 x 10-10).

a. What is the percent ionization? (0.0055%)

2. What is the hydronium ion concentration for 0.010 mol/L HOCl(aq) at

25°C? (2.0 x 10 –5 mol/L)

3. What is the equilibrium concentration and Ka for 0.10 mol/L HF(aq) at

25°C if the pH = 2.10? (0.092, 6.9 x 10-4)

4. For HNO2(aq) at room temp, the pH reading was 2.40. What is the initial
concentration? (0.032)

5. Nicotinic acid HC2H4NO2(s) is a B vitamin. It is a weak acid with Ka 1.4 x

10-6. Calculate the pH of a 0.10 mol/L solution. (3.43)

6. The pH of a 0.050 mol/L sulfurous acid sample is calculated to be 1.58,

but is measured at 1.69. Explain the difference in pH values.

7. What is the pH of a 0.150 mol/L hypochlorous acid sample used in

bleaching? (4.111)

8. Methyl alanine, CH3NH2, is the amino acid responsible for the fish odour
and will behave as a weak base in aqueous solution. If its concentration
is 0.100 mol/L and pH is 10.80 calculate the Kb. (4.0 x 10-6)

9. Calculate the pH and pOH of a 0.200 mol/L ammonia solution. (pH –

11.276, pOH – 2.724)

10. 10.70 g of ammonium chloride are dissolved in water to make 2.00 L

of solution. Calculate the pH. (5.126)

11. A 0.80 mol/L HX(aq) solution has a pH of 3.75. Calculate Ka.

(4.0 x 10-8)
30
Practice: Read p. 759 – 779 in Nelson Chemistry text and answer the
following on a separate sheet of paper.

1. Attempt problems:
a. Chapter 15 Review on p. 705.
b. Chapter 16 Review on p. 772.
c. Unit 8 Review on p. 774.

2. Log into Quest A+ website and attempt diploma-style problems on

acid-base equilibrium.

31