General Chemistry II - Worksheet 1: Thermochemistry

Model 1: Calorimetry
Heat is not the same thing as temperature, even though in common usage these concepts are often used
interchangeable. Heat is the energy transferred from one object to another due to a difference in their
temperature. Heat, therefore, has units of energy (joules, J). An object at a higher temperature will transfer
energy to one at a lower temperature until they reach thermal equilibrium – until they are at the same
temperature.
The amount of heat gained (to raise the temperature) or lost (to lower the temperature) by an object can be
quantified with the following equations:
(1) 𝑞 = 𝑚𝐶∆𝑇 or (2) 𝑞 = 𝑛𝑐∆𝑇
where q is the heat change (in J), m is the mass (in g), n is the number of moles (in mol), C is the specific heat
capacity (in J g-1 K-1) and c is the molar heat capacity (J mol-1 K-1).
The change in temperature, ΔT, is always:
ΔT = Tfinal – Tinitial
Hence, if the temperature increases, ΔT is positive and, if the temperature decreases, ΔT is negative.
The two equations (1) and (2) will give the same value for q as long as the specific heat capacity is used when
you know the mass and the molar heat capacity is used when you know the number of moles.
The specific and molar heat capacities are a measure of how much energy is needed to raise the temperature
of 1 g or 1 mol, respectively, of an object by 1 K. Every object has a different heat capacity: some substances,
like metals, are easier to heat than others, like rocks.
Critical thinking questions
1. Assuming no chemical reaction is occurring, under what circumstances would you get a negative value for the heat,
q?

2. Provide an equation for converting between the specific heat capacity, C, and the molar heat capacity, c. (Hint: use
the relationship between the number of moles and the mass of a substance).

3. If the temperature of a substance increases from 25 °C to 35 °C, what is ΔT (in Kelvin)?

4. Given your answer to Q3, explain to your group whether it is necessary to convert temperatures to Kelvin when
working out ΔT.
5. The specific heat capacity of olive oil is 2.0 J g-1 K-1. How much energy has to be transferred to 2.0 g of olive oil
in a saucepan to heat it from room temperature to 130 °C? Assume that the room is at 25 °C.

6. The specific heat capacity of water is 4.18 J g-1 K-1. Is it easier or harder to heat water or olive oil?

7. The molar heat capacity of gold is 25.413 J mol-1 K-1. A necklace that weighs 1.2 g requires 0.426 J of energy to
heat by 2.00 K. Is the necklace pure gold? (Hint: you will first need to either convert the molar heat capacity to the
specific heat capacity using the equation you worked out in Q2 or convert the mass into the moles).
Model 2: Energy
When a physical or chemical change occurs in a system, energy is either absorbed or released. Energy is
required to break chemical bonds, and conversely, energy is released when bonds are made. Usually, a
chemical reaction involves both breaking and making bonds so energy can either be released or absorbed,
depending on whether the bonds that are made are stronger or weaker than the bonds broken. The energy
change in a chemical reaction often leads to a change in thermal energy: heat.

If the products are less stable (higher in energy) than the reactants, the reaction involves
an increase in the energy.

This energy must be supplied and so the reaction absorbs energy from the surroundings
making it feel colder.

If the products are more stable (lower in energy) than the reactants, the reaction
involves a decrease in the energy.

This energy is released to the surroundings making it feel hotter.

Critical thinking questions

1. Which of the two figures above corresponds to the following reactions?

(a) reactants → products + heat (b) reactants + heat → products

2. If ex is the Greek prefix for out and endo is the Greek prefix for in, which of the above reactions is
exothermic and which is endothermic? What do you think thermo means?

3. Will a beaker containing an endothermic reaction get colder or hotter?

The amount of energy absorbed or released by a reaction at constant pressure is called the enthalpy of reaction,
ΔH. When energy, as heat, is absorbed in a reaction, ΔH is positive. This occurs when the bonds made in the
products are weaker than those broken in the reactants.
4. If heat is released in a reaction, is ΔH positive or negative?

5. If heat is released in a reaction, are the bonds stronger or weaker in the products than in the reactants?

6. Is ΔH positive or negative for the two types of reaction:

(a) exothermic (b) endothermic
Model 3: Forming a Compound from its Elements
If a compound is formed from the elements it contains in their naturally occurring forms, the enthalpy change is called
the enthalpy change of formation (ΔfH). The naturally occurring forms of the elements at room temperature and
pressure are called the standard states of the elements and include, for example, graphite for carbon and O2(g) for
oxygen. CO2 contains carbon and oxygen and so ΔfH for CO2 is for the reaction in which it is formed from graphite and
O2(g):
C(s) + O2(g) à CO2(g) ΔrxnH = ΔfH (CO2(g)) = -393.5 kJ mol-1
The enthalpies of formation for many compounds are tabulated in databooks and on websites. One reason for this is that
they can be combined to predict the enthalpies of reactions which involve these compounds.
Critical thinking questions
1. Write down the reactions that correspond to the enthalpies of formation of (a) CH4(g) and (b) H2O(l).
(a) (b)

2. Why are ΔfH° (O2(g)) and ΔfH° (H2(g)) both equal to 0 kJ? (Hint: what is the reaction in each case?)

Model 4: Calculating the Enthalpy of Reaction using ∆fH

To determine the overall value of ΔH for a reaction, we can imagine the reaction taking place in two steps:
(i) The reactant molecules are broken apart into the corresponding elements in their naturally occurring
forms. This is the opposite process to the formation of the reactant molecules from their elements and
requires an enthalpy change equal to −ΔfH (reactants)
(ii) These elements are then reassembled to make the product molecules. The enthalpy change for this
process is equal to +ΔfH (products)
Using this method, the equation for the enthalpy of reaction becomes:
ΔrxnH° = ΔfH° (products) – ΔfH° (reactants) (1)
The enthalpy change for the combustion of methane is represented on the energy level diagram below. On the left,
CH4(g) and O2(g) are broken up into their elements in the standard states, graphite (C(s)), H2(g) and O2(g). This is the
reverse of their formation so the energy required is –ΔfH° (reactants). On the right, CO2(g) and H2O(g) are formed from
the same elements in the same states so the energy change is + ΔfH° (products).

-∆fH
-2∆fH ∆ fH
2∆fH
Critical thinking questions
1. What is ΔrxnH° for the reaction CH4(g) + 2O2(g) à CO2(g) + 2H2O(l)?

2. Use equation (1) and the data below to calculate ΔrxnH° for the reaction MgO(s) + CO2(g) à MgCO3(s).
ΔfH°: MgO(s) = -602 kJ mol-1, CO2(g) = -394 kJ mol-1 and MgCO3(s) = -1096 kJ mol-1

Nitrogen dioxide, NO2, is a prominent air pollutant. At low temperatures, it is in equilibrium with its dimer, N2O4.
Starting from NO2, the formation of the dimer can be studied using one of the two equations below:

2NO2(g) à N2O4(g) (A)

NO2(g) à ½ N2O4(g) (B)

Starting from the dimer, the formation of NO2 can be studied using one of the two equations below:

N2O4(g) à 2NO2(g) (C)

½ N2O4(g) à NO2(g) (D)

3. Use equation (1) to calculate ΔrxnH° for reaction A. ΔfH°: NO2(g), 33 kJ mol-1, N2O4(g) 9 kJ mol-1.

4. Explain in words the origin of the sign of ΔrxnH° in terms of the chemical changes in the reaction.

5. Use equation (1) to calculate ΔrxnH° for reaction B. How is the value related to your answer to Q3?

6. Use equation (1) to calculate ΔrxnH° for reaction C. How is the value related to your answers to Q3 and Q5?

7. Explain in words the origin of the sign of ΔrxnH° and in terms of the chemical changes in the reaction.

8. Without doing any calculations, work out the value of ΔrxnH° for reaction D.
Exam type questions
• A mass of 1.250 g of benzoic acid (C7H6O2) underwent combustion in a bomb calorimeter. Marks
If the heat capacity of the calorimeter was 10.134 kJ K–1 and the heat of combustion of 4
benzoic acid is –3226 kJ mol–1, what is the change in internal energy during this reaction?

Answer:

Calculate the temperature change that should have occurred in the apparatus.

Answer:

Marks
• The specific heat capacity of water is 4.18 J g–1 K–1 and the specific heat capacity of copper 2
is 0.39 J g–1 K–1. If the same amount of energy were applied to a 1.0 mol sample of each
substance, both initially at 25 °C, which substance would get hotter? Show all working.

Answer:
 Marks
• Ammonium perchlorate mixed with powdered aluminium powers the space shuttle booster rockets:
3
2NH4ClO4(s) + 2Al(s) → Al2O3(s) + 2HCl(g) + 2NO(g) + 3H2O(g)
Given the following thermochemical data, how much heat would be released per gram of Al(s)?

ΔH fo (H2O(l)) = –285.1 kJ mol–1 ΔH fo (Al2O3(s)) = –1669.8 kJ mol–1

ΔH fo (NO(g)) = 90.4 kJ mol–1 ΔH fo (NH4ClO4(s)) = –290.6 kJ mol–1
ΔH fo (HCl(g)) = –92.3 kJ mol–1 o
ΔH vap (H2O) = 44.1 kJ mol–1

Answer:

Marks
• The thermite reaction is written below. Show that the heat released in this reaction is sufficient for
6
the iron to be produced as molten metal.
2Al(s) + Fe2O3(s) → Al2O3(l) + 2Fe(l)
Assume that the values in the table are independent of temperature.

Substance Enthalpy of Molar heat Melting Enthalpy

formation, ΔfHo capacity, Cp point of fusion
kJ mol–1 J K–1 mol–1 o
C kJ mol–1
Al 0 24 660 11
Al2O3 –1676 79 2054 109
Fe 0 25 1535 14
Fe2O3 –824 104 1565 138
 General Chemistry II - Worksheet 2: Entropy and Free Energy
Model 1: Enthalpy (ΔrxnH) and Entropy (ΔrxnS) of Reaction
In week 2, you developed a way of working out the value of enthalpy change for any reaction from the values of
the enthalpies of formation of the reactants and products:
ΔrxnH° = ΔfH° (products) – ΔfH° (reactants) (1)
The change in entropy in a reaction can similarly be calculated as the difference in the entropies of the reactants
and products:
ΔrxnS° = S° (products) – S° (reactants) (2)

Nitrogen dioxide, NO2, is a prominent air pollutant. At low temperatures, it is in equilibrium with its dimer,
N2O4. Starting from NO2, the formation of the dimer can be studied using one of the two equations below:
2NO2(g) N2O4(g) (A)
NO2(g) ½ N2O4(g) (B)
Starting from the dimer, the formation of NO2 can be studied using one of the two equations below:
N2O4(g) 2NO2(g) (C)
½ N2O4(g ) NO2(g) (D)

Critical thinking questions

1. Using the data below, calculate ΔrxnH° and ΔrxnS° for reaction A.
ΔfH°: NO2(g), 33 kJ mol-1, N2O4(g) 9 kJ mol-1. S°: NO2(g), 240 J K-1 mol-1, N2O4(g) 304 J K-1 mol-1

2. Explain in words the origin of the sign of ΔrxnH° and ΔrxnS° in terms of the chemical changes in the
reaction.

3. Calculate ΔrxnH° and ΔrxnS° for reaction B. How are these values related to your answer to Q1?

4. Calculate ΔrxnH° and ΔrxnS° for reaction C and explain in words the origin of the sign of ΔrxnH° and
ΔrxnS° in terms of the chemical changes in the reaction.

5. What are the values of ΔrxnH° and ΔrxnS° for reaction D?

Model 2: Free Energy of Reaction (ΔrxnG)
Reactions can be favoured if the products are more stable than the reactants. This occurs when the enthalpy
decreases: ΔrxnH < 0. Reactions can also be favoured if the entropy increases: ΔrxnS > 0. Depending on the
reaction, these factors can work together or in opposition. They are combined in the definition of the change in
the free energy, ΔrxnG:
ΔrxnG° = ΔrxnH° - TΔrxnS° (3)
Because a favourable reaction may have ΔrxnH < 0 and / or ΔrxnS > 0, a favourable reaction will have ΔrxnG < 0.
Critical thinking questions
1. Is reaction A in Model 1 favourable or unfavourable with respect to the enthalpy factor?

2. Is reaction A in Model 1 favourable or unfavourable with respect to the entropy factor?

3. Is reaction C in Model 1 favourable or unfavourable with respect to the enthalpy factor?

4. Is reaction C in Model 1 favourable or unfavourable with respect to the entropy factor?

5. Given your answers to Q1 – 4 and the equation for ΔrxnG° above, what additional factor needs to be
considered to predict whether reaction A or C is favourable?

6. Calculate ΔrxnG° for reaction A at the two temperatures below and predict whether the reaction is
favourable.
(a) T = 298 K

(b) T = 398 K

7. Calculate ΔrxnG° for reaction C at the two temperatures below and predict whether the reaction is
favourable.
(a) T = 298 K

(b) T = 398 K

8. Using your answer to Q6, predict what happens to an exothermic reaction as the temperature is
increased.

9. Using your answer to Q7, predict what happens to an endothermic reaction as the temperature is
increased.

10. What combination of signs for ΔrxnH and ΔrxnS lead to a reaction that is never favourable?
 General Chemistry II - Worksheet 3: Kinetics and Mechanisms
Model 1: Elementary Steps
The rate law shows us how the rate of a reaction is affected by the concentration of the reactants and you
worked out the rate law from experimental measurements.
Most reactions occur at the molecular level through a sequence of one of more events called elementary steps.
Only two types of elementary step are important:
• a unimolecular step: a bond breaks in a molecule
• a bimolecular step: two molecules collide leading to one or more bonds being broken or made.

Critical thinking questions

1. An example of a unimolecular step is the decomposition of bromine: Br2(g) à Br(g) + Br(g)
(a) If the number of Br2 molecules is doubled, what will happen to the rate?
(b) If [Br2(g)] is doubled, what will happen to the rate?
(c) What is the rate law for this step? (Is the rate proportional to [Br2(g)], [Br2(g)]2 or [Br2(g)]3?)

2. An example of a bimolecular step is the reaction between H and Br2: H(g) + Br2(g) à HBr(g) + Br(g)
(a) If the number of Br2 molecules is doubled, what will happen to the number of collisions that
occur between H and Br2?
(b) If the number of H atoms is doubled, what will happen to the number of collision that occur
between H and Br2?
(c) If the rate is proportional to the number of collisions, what is the rate law for this step?

3. An example of a bimolecular step is the reaction of NO with itself: NO(g) + NO(g) à N2O2(g)
(a) If the number of NO molecules is doubled, what will happen to the number of collisions that
occur between NO molecules?
(b) If the rate is proportional to the number of collisions, what is the rate law for this step?

Model 2: A Multi-Step Mechanism

Because each step in a mechanism is either a unimolecular or bimolecular step, you can write the rate law down
as you did in Model 1:
• a unimolecular step involves only one molecule so the rate is proportional to its concentration:
rate = k1[Br2(g)]
• a bimolecular step involves two molecules colliding so the rate is proportional to the concentration of
each:
rate = k2[H(g)][Br2(g)]
rate = k3[NO(g)][NO(g)] = k3[NO(g)]2
Each rate constant is different: some elementary steps have high values of k and are fast and some elementary
steps have low values of k and are slow. For a reaction involving more than one step, the overall rate is
determined by the slowest or rate determining step.
We cannot see how the molecules react. When trying to work out the mechanism of a reaction, the process is to
(i) propose what it might look like, (ii) work out by the rate law for this guess and (iii) compare this rate law
with that determined experimentally. The experimental rate law will only involve the concentration of
chemicals that can be varied experimentally, so will only involve reactants. No intermediates should appear
in the rate law.
Critical thinking questions
1. The reaction between NO2 and O3 is proposed to proceed through 3 steps:
NO2 + O3 à NO3 + O2 k1; slow
NO3 + O2 à NO2 + O3 k2; fast
NO3 + NO2 à N2O5 k3; fast
(a) Which is the rate determining step?
(b) What is the rate law for the reaction?

2. The conversion of ozone to molecular oxygen in the upper atmosphere is proposed to proceed via 2 steps:
O3 O2 + O fast equilibrium
O + O3 à 2O2 k2; slow
(a) Which is the rate determining step?
(b) What is the rate law for this step?

(c) If the first step is very fast compared to the second, it will have time to reach equilibrium. What
is the equilibrium constant in terms of [O3], [O2] and [O]?

equilibrium constant = K =

(d) Using your answer to (c), what is [O]?

(e) Substitute your answer to (d) into your rate law from (b) to obtain a rate law that does not involve
any intermediates.

(f) If the first step is at equilibrium, what are the relative rates of the forward and backward reaction?

(g) By first writing down the rate laws for the forward and backward reactions in the first step, find a
relationship between the rate constants k1 and k-1 and the equilibrium constant K.

3. The reaction between NO and O2 gives NO2. By varying [NO] and [O2], the rate law has been found to be:
rate = k[NO]2[O2]
It is proposed that the reaction proceeds through 2 steps:
NO(g) + NO(g) N2 O 2 fast equilibrium
N2O2(g) + O2 à 2NO2(g) k2; slow
Is this mechanism consistent with the experimental rate law?
 General Chemistry II - Worksheet 4: Equilibrium
Model 1: The Equilibrium Constant
Many chemical reactions lead to a mixture of reactants and products. You will end up with a mixture of both
NO2(g) and N2O4(g) whether you start with pure NO2(g) or pure N2O4(g). Such reactions are said to reach an
equilibrium in which the amount of each substance does not change.
Consider a reaction such as that below which has been left long enough to reach equilibrium.
wW(g) + xX(g) yY(g) + zZ(g)
The equilibrium constant in terms of concentrations, Kc, is a constant at a given temperature that defines how
much of each substance there will be at equilibrium:

Kc =

If Kc > 1, the mixture will contain more of the substances on the right hand side (Y and Z) of the equation.
If Kc < 1, the mixture will contain more of the substances on the left hand side (W and Z) of the equation.

In worksheets 2 and 3, you studied the thermodynamics of the equilibrium between NO2 and its dimer N2O4.
Starting from NO2, the formation of the dimer can be studied using one of the two equations below:
2NO2(g) N2O4(g) (A)
NO2(g) ½ N2O4(g) (B)
Starting from the dimer, the formation of NO2 can be studied using one of the two equations below:
N2O4(g) 2NO2(g) (C)
½ N2O4(g ) NO2(g) (D)
Critical thinking questions
1. Write down the expression for Kc for reactions A, B, C and D in Model 1.

Kc (A) = Kc (B) = Kc (C) = Kc (D) =

2. Looking at the equations in Q1, what is the mathematical relationship between the different forms of Kc?

(a) Kc (A) and Kc (B) (b) Kc (A) and Kc (C)

3. At equilibrium at room temperature, [NO2(g)] = 1.60 M and [N2O4] = 0.20 M. Calculate the values of
Kc(A) and Kc(B) and Kc(C) and hence confirm your analysis in Q2.

Model 2: The Reaction Quotient

The reaction quotient, Qc, for a reaction wW(g) + xX(g) yY(g) + zZ(g), is defined as follows:

Qc =

It looks similar to the equilibrium constant expression. The difference is that Qc can be calculated at any time
during a reaction or if a reaction is disturbed. It is used to predict the direction in which a reaction will move.
Critical thinking questions
Consider the reaction 2NO2(g) N2O4(g) to be at equilibrium with [NO2(g)] = 1.60 M, [N2O4] = 0.20 M
and Kc = 0.078.
1. Predict qualitatively what will happen to this reaction if more NO2 is added so that [NO2(g)] = 2.00 M?

2. Predict qualitatively what will happen to this reaction if instead NO2 is removed so that [NO2(g)] = 1.00 M?

3. Calculate the values for Qc for these two experiments.

(a) [NO2(g)] = 2.00 M and [N2O4] = 0.20 M: Qc =

(b) [NO2(g)] = 1.00 M and [N2O4] = 0.20 M: Qc =

4. Using your answers to Q1 - 3, what in general happens to a reaction if

(a) Qc < Kc

(b) Qc > Kc

Model 3: Equilibrium calculations

Model 2 gives you the tools to predict the direction in which a reaction will move if it is not at equilibrium. The
concentrations that will be obtained when equilibrium is finally reached can be calculated using an ICE table:
initial-change-equilibrium.
Consider the starting mixture in Q1 of Model 2: [NO2(g)] = 2.00 M and [N2O4(g)] = 0.20 M. These are the
initial concentrations and are written in the first row of the reaction table below. You know from Model 2 that
this reaction will shift so that some NO2(g) reacts to make N2O4(g). We do not know how much will react but
we can calculate it:
2NO2(g) N2O4(g)
initial 2.00 0.20
change +x
equilibrium 0.20 + x

Critical thinking questions

1. From the chemical equation: every time one N2O4 molecule is formed, two NO2 molecules are lost. If
[N2O4(g)] increases by x to reach equilibrium, what will the change in [NO2(g)] be? Add this change to
the second row of the table. (Hint: is the change positive or negative.
2. Complete the third row of the table.
3. Substitute the equilibrium concentrations from the third row into your expression for Kc(A) from Q1 in
Model 1.

4. You now have a mathematical expression to solve for x. Using Kc = 0.078. solve for x and hence work
out the equilibrium values of [NO2(g)] and [N2O4(g)].
Exam type questions
Marks
The CO(g) in water gas can be reacted further with H2O(g) in the so-called “water-gas shift”
4
reaction:
CO(g) + H2O(g) CO2(g) + H2(g)
At 900 K, Kc = 1.56 for this reaction. A sample of water gas flowing over coal at
900 K contains a 1:1 mole ratio of CO(g) and H2(g), as well as 0.250 mol L–1 H2O(g). This
sample is placed in a sealed container at 900 K and allowed to come to equilibrium, at which
point it contains 0.070 mol L–1 CO2(g). What was the initial concentration of CO(g) and H2(g) in
the sample?

[CO] = [H2] =

If the walls of the container are chilled to below 100 ºC, what will be the effect on the
concentration of CO2(g)?

Marks
• At 700 °C, hydrogen and iodine react according to the following equation. 10
H2(g) + I2(g) 2HI(g) Kc = 49.0
Hydrogen also reacts with sulfur at 700 °C:
2H2(g) + S2(g) 2H2S(g) Kc = 1.075 × 108
Determine Kc for the following overall equilibrium reaction at 700 °C.
2I2(g) + 2H2S(g) S2(g) + 4HI(g)
 Kc

If 0.250 mol of HI(g) is introduced into a 2.00 L flask at 700 °C, what will be the concentration of
I2(g) at equilibrium?

Answer:

If 0.274 g of H2S were now introduced into the same flask, what would be the concentration of
S2(g) at equilibrium?

Answer:
 General Chemistry II - Worksheet 5: Osmotic Pressure
Model 1: The origin of osmotic pressure
The cell membrane is a semi-permeable barrier to the passage of many (but not all) molecules and ions. Water
can diffuse through it but many charged and large molecules cannot.
To maximise entropy, the concentration of the solutions on either side of a membrane tend to equalise. If the
membrane is impermeable to the solute, only the solvent (water) can flow across the membrane to achieve this.
The schemes below show 3 cells with solute particles shown as black dots. The first picture represents a cell
which has higher levels of solute relative to the medium it is in. The second represents a cell which has the
same levels of solute as the medium. The third represents a cell which has lower levels of solute than the
medium.

(i) Hypotonic medium (ii) Isotonic medium (iii) Hypertonic medium

Critical thinking questions

1. In an isotonic medium, water flows in and out at the same rate. Draw arrows on the other two pictures to
indicate the direction in which water flows.
2. Describe what you think will happen to the size of the cell in each of the mediums.
(i)

(ii)

(iii)

3. Animal cells do not have cell walls. Using your answer to Q2, describe what might occur if pure water is
accidentally injected into a blood vessel.

4. (a) Animals continually expend energy by pumping Na+ ions out of their cells. By considering the
effect this has on the solute concentration in the cell, suggest why this action is vital for the
health of the cell.

(b) In some blood disorders, such as sphero- and elliptocytosis, the membrane of the red blood cells
is so permeable to Na+ ions that they diffuse back in more rapidly than the pump can cope with.
What effect will this have on the flow of water and hence on the shape of the cell?
(Hint: consider the names of these disorders.)
Model 2: Osmotic pressure
The pressure that must be applied to the solution to stop the processes described in Model 1 is called the
osmotic pressure, π. For dilute solutions, it is given by:
π = cRT where R = 8.314 J K-1 mol-1
c is the concentration of all impermeable species in solution. As salts dissociate into ions in solution, the
concentrations of all of the ions must be added together.

Critical thinking questions

1. If 0.35 mol of NaCl and 0.15 mol of KCl are added to 1.00 L of water, calculate:

(i) [Na+(aq)]

(ii) [K+(aq)]

(iii) [Cl-(aq)]

2. What is the overall concentration of ions in this solution? Convert this value into mol m-3.
(Hint: there are 1000 litres in a m3).

3. Calculate the osmotic pressure for this solution at 298 K.

4. Explain why the osmotic pressure depends on the concentration of particles but not their identity. (Hint:
re-read Model 1 on the origin of osmotic pressure).

5. Suppose a compartment separated from an extracellular medium by a semipermeable membrane. The

membrane allows movement of water but not solute particles. For each of the initial compositions shown
below, does the compartment (a) swell, (b) stay the same size or (c) shrink?
compartment medium

(i) 0.1 M sucrose 0.1 M glucose

(a) (b) (c)
(C12H22O11) (C6H12O6)

(ii) 0.1 M sucrose 0.05 M sucrose (a) (b) (c)

(iii) 0.10 M sucrose 0.05 M NaCl (a) (b) (c)

(iv) 0.10 M sucrose 0.050 M MgCl2 (a) (b) (c)

Exam type questions
• The freezing point of a sample of seawater is measured as –2.15 °C at 1 atm pressure. Assuming Marks
that the concentrations of other solutes are negligible, determine the molality (in mol kg–1) of NaCl 3
in this sample. The molal freezing point depression constant for H2O is 1.86 °C kg mol–1.

Answer:

Marks
• An aqueous solution with a volume of 10.0 mL contains 0.025 g of a purified protein of
3
unknown molecular weight. The osmotic pressure of the solution was measured in an osmometer to
be 0.0036 atm at 20.0 °C. Assuming ideal behaviour and no dissociation of the protein, estimate its
molar mass in g mol–1.

Answer:
• At 21.0 °C, a solution of 18.26 g of a non-volatile, non-polar compound in 33.25 g of bromoethane, Marks
CH3CH2Br, has a vapour pressure of 4.42 × 104 Pa. The vapour pressure of pure bromoethane at 4
this temperature is 5.26 × 104 Pa. What is the molar mass of the compound?

Answer:

Marks
• Assuming ideal behaviour, calculate the mass of MgCl2·6H2O that should be dissolved in 1.0 L
4
of water at 37 oC to obtain a solution with an osmotic pressure of 6.0 atm, the same as that of cell
cytoplasm.

Answer:
• Lysozyme is an enzyme that breaks down bacterial cell walls. A solution containing 0.150 g of this Marks
enzyme in 210 mL of solution has an osmotic pressure of 0.00125 atm at 25 oC. What is the molar 3
mass of lysozyme?

Answer:

Marks
• What mass of ethylene glycol, HOCH2CH2OH, is required to lower the freezing 3 point of 1.00
3
L of water to –10.0 oC? The freezing point depression constant of water
is 1.86 oC kg mol–1.
Assume the density of water is 1.00 g mL–1 at 0 oC.

Answer:
 General Chemistry II - Worksheet 6: Acids and Bases

Model 1: Strong and Weak Acids

A strong acid is one that is essentially 100% dissociated in water: if 1.0 mole of the acid is added to enough
water to make a 1.0 L solution, the solution will have [H3O+(aq)] = 1.0 M and will be pH = 1.

A weak acid is one that is significantly less than 100% dissociated in water: if 1.0 mole of the acid is added to
enough water to make a 1.0 L solution, the solution will have [H3O+(aq)] < 1.0 M and will be pH > 1.

When an acid HA is placed in water, H3O+(aq) ions are produced according to the reaction:

HA(aq) + H2O(l) H3O+(aq) + A(aq)

Ka =

Critical thinking questions

1. What are the major species present in a solution of a strong acid like HCl?

2. What are the major species present in a solution of a weak acid like CH3COOH?

3. Under what pH conditions would CH3COO-(aq) be the dominant species in a solution of CH3COOH?

4. Write down the equilibrium expression, Ka, for CH3COOH.

5. What are the major species present in a solution of a weak base like CH3NH2?

6. Under what pH conditions would CH3NH3+(aq) be the dominant species?

7. The extent of ionization of a drug helps determine how it is distributed in the body because ions are less
likely to cross cell membranes than uncharged molecules. Are the two drugs below likely to be absorbed
in (i) the acid environment of the stomach or (ii) the basic environment of the intestine?

Model 2: A Solution Containing a Weak Acid

 Acids and Bases
+
As a strong acid is one that is essentially 100% dissociated in water: pH = -log10[H3O (aq)] = -log[HA]initial
As a weak acid is significantly less than 100% dissociated in water, an equilibrium must be considered:
HA(aq) + H2O(l) H3O+(aq) + A(aq)
Ka =

Calculating the pH requires that the equilibrium value of [H3O+(aq)] be first calculated. To do this, the ‘ICE’
approach covered in Model 3 of Worksheet 4 can be followed. Consider a 2.0 M solution of CH3COOH:

CH3COOH (aq) H2O(l) CH3COO(aq) H3O+(aq)

initial 2.00 large 0 0
change -x -x +x +x
equilibrium 2.00 - x large +x +x

As hardly any weak acid dissociates, x is very small and so 2.00 – x ≈ 2.00. Using this approximation, the
equilibrium constant can then be written down as:

Ka = = ≈ and so x = [H3O+(aq)] =

After working out [H3O+(aq)], the pH and percentage dissociation of the weak acid can be calculated:

pH = -log[H3O+(aq)] and % dissociation = × 100%

Critical thinking questions

1. What are the initial and final concentrations of CH3COOH in the ICE table above? How are they related
when the small x approximation is used?

2. Using your answer to Q1, write down a formula for x for any dilute weak acid.

3. Calculate the pH and percentage dissociation of the acetic acid as it is diluted (Ka = 10-4.76).
(a) 2.00 M pH = (c) 0.500 M pH =

% dissociation = % dissociation =

(b) 1.00 M pH = (d) 0.250 M pH =

% dissociation = % dissociation =

4. Complete the graph below showing how the percentage dissociation changes with the initial concentration.
 Acids and Bases

5. Carefully explain in words what happens to the amount of dissociation of a weak acid as it is diluted.

6. What are the major species present in a 1.00 M solution of acetic acid?

Model 3: Addition of Strong Base to a Solution of a Weak Acid

Model 2 describes the pH and extent of dissociation of a solution of a weak acid. If a strong base, such as
NaOH, is added to this solution, it will react with the weak acid.
HA(aq) + OH(aq)  A(aq) + H2O(aq) Ka =

As long as the amount of OH-(aq) added is less than the amount of CH3COOH(aq) present, the solution will
contain both CH3COO-(aq) and left over CH3COOH(aq). A solution like this containing both a weak acid and
its conjugate base will have a pH given by the Henderson-Hasselbalch equation:

pH = pKa + log = pKa + log

Critical thinking questions

1. If 0.100 mol of NaOH(s) is added to a 1.00 L solution of 0.500 M CH3COOH, it will react to form a
solution which is 0.100 M in CH3COO-(aq) and 0.400 M CH3COOH(aq). What is the pH of this
solution? (pKa (CH3COOH) = 4.76).

2. Complete the table below showing the concentrations of CH3COOH(aq) and CH3COO-(aq) and the pH of
the solution as more NaOH(s) is added to this solution. (Hint: see Model 2 for the first column)

Amount of NaOH(s) added (mol) 0.000 0.100 0.200 0.300 0.400 0.500
[CH3COOH(aq)] (M) 0.500 0.400
[CH3COO-(aq)] (M) 0.000 0.100
pH
 Acids and Bases
3. To react completely with the original CH3COOH, 0.500 mol of NaOH must be added. What is the pH of
the solution when exactly half this amount is added?

4. Using the data from Q2, complete the graph below showing how the percentage of CH3COOH(aq) and
CH3COO-(aq) changes with pH. This is called a speciation plot.

Model 4: Neutralizing a Weak Acid

Model 3 describes the pH changes as a strong base is added to a solution containing a weak acid. The strong
base reacts with the weak acid leading to a solution containing the conjugate base of the weak acid and any left
over acid. The equivalence point occurs when enough base has been added so that there is no acid left. At this
point, the solution contains only the conjugate base.
The pH of the solution of the conjugate base of a weak acid can be calculated by considering the equilibrium it is
involved in. The calculation is very similar to that in Model 2.
A(aq) + H2O(l) HA(aq) + OH(aq)
Kb =

From the chemical equation, at equilibrium:

[HA(aq)] = [OH(aq)] and [A(aq)] = [A(aq)]initial – [HA(aq)]
As hardly any base reacts, [A(aq)]initial – [HA(aq)] ≈ [A(aq)]initial and so:

Kb = and [OH-(aq)] =

After working out [OH-(aq)], the pOH can be calculated using pOH = -log[OH-(aq)]. Finally, the pH can then
be calculated using pH = 14.00 – pOH.

Critical thinking questions

1. To react completely with the original CH3COOH in Q5, 0.500 mol of NaOH must be added. What will
be [CH3COO-(aq)] when this occurs?

2. Calculate the pH of the solution in Q1. Correct your entry in the final column of the table in Model 3 if
required! (Hint: remember that pKa + pKb = 14.00 or Ka × Kb = 10-14.00)
 Acids and Bases
Model 5: Solubility and pH
Metal hydroxides dissolve to give metal ions and hydroxide ions. For example,

Fe(OH)3(s) Fe3+(aq) + 3OH-(aq)

The position of the equilibrium (i.e. the solubility) is very sensitive to pH since this controls [OH-(aq)].
All forms of life depend on iron and the concentration of iron in the oceans and elsewhere is one of the primary
factors limiting the growth rates of the most basic life forms. One reason for the low availability of iron(III) is
the insolubility of Fe(OH)3 which has a Ksp of only 1 x 10--39.
Critical thinking questions
1. Write down the expression for the solubility product, Ksp, for Fe(OH)3.

2. The pH of the oceans is currently 8.179. Use this to work out [OH-(aq)].

3. If x moles of Fe(OH)3 dissolve in 1.00 L of water, [Fe3+(aq)] = x mol L-1. Use your answers to Q1 and
Q2 to work out x in the ocean.

4. If the amount of CO2 in the atmospheres increases, the pH of the oceans will decrease due to the
equilibrium below. What will happen to [Fe3+(aq)]?
CO2(g) + H2O(l) HCO3- + H3O+(aq)

5. The concentration of Fe3+ in our blood is about 10-6 M. Assuming a typical blood pH of 7.4, calculate
the concentration of free Fe3+ in our blood and account for any difference with the actual concentration.

Model 6: To dissolve or not to dissolve?

The solubility product gives the maximum values of the ion concentrations that are allowed. If
their concentrations are such that their product is less than Ksp, then more solid can dissolve. If
[Mg2+(aq)][OH-(aq)]2 < Ksp then more solid can dissolve
If their concentrations are such that their product is more than Ksp then the concentrations must reduce:
precipitation must occur.
If [Mg 2+(aq)][OH-(aq)]2 > Ksp then precipitation must occur
The value of the product can thus be used to predict whether dissolution or precipitation can occur. Because of
its importance, it is called the ‘ionic product‘ and given the symbol Qsp:
Qsp = [Mg 2+(aq)][OH-(aq)]2
 Acids and Bases
If Qsp < Ksp then dissolution will occur. If Qsp > Ksp then precipitation will occur.

Critical thinking questions

1. A solution is made by mixing 500.0 mL of 0.12 M NaOH solution with 500.0 mL of 0.10 M
Mg(NO3)2.
Ksp is 1.8 × 10-11
(a) Assuming that no reaction occurs, what will [Mg2+(aq)] and [OH-(aq)] be after mixing?

(b) Write down the value of the ionic product, Qsp.

(c) Does a precipitate form?

2. For each of the following experiments, predict whether or not a precipitate of MgF2 will form. Ksp
MgF2(s) = 6.4 × 10-9

(a) 500.0 mL of 0.050 M Mg(NO3)2 is mixed with 500.0 mL of 0.010 M NaF

(b) 500.0 mL of 0.050 M Mg(NO3)2 is mixed with 500.0 mL of 0.0010 M NaF.

Model 7: The Stability of Complexes

Complexes contain a metal ion bonded to ligands. Most transition metal ions exist in aqueous solution as aqua
complexes [M(OH2)m]n+ The stability of a complex can be measured using the stability constant or Kstab. This is
just an equilibrium constant, like the others you have met, and represents the formation of the complex from the
aquo ion and the ligands. For example,

Ag+(aq) + 2CN−(aq) [Ag(CN)2]−(aq)

Critical thinking questions

1. The Kstab values for [Zn(NH3)4]2+ and [Cu(NH3)4]2+ are 1 × 109 and 1 x 1013 respectively.

(a) Which complex ion is more stable?

(b) Excess NH3 is added to a solution containing equal amounts of Zn2+(aq) and Cu2+(aq). Does
the resulting solution contain more uncomplexed Zn2+(aq) or Cu2+(aq)?

2. The ligand EDTA4– forms very stable complexes with metal ions such as Ca2+. It is administered as
the complex [Ca(EDTA)]2– to treat lead poisoning.
(a) Is Kstab larger for [Ca(EDTA)]2– or [Pb(EDTA)]2–?
 Acids and Bases
2–
(b) Why do you think it is administered as [Ca(EDTA)] ?

We are often interested in working out exactly how much of a metal ion is not complexed. Consider a
solution prepared by mixing 0.0200 M silver nitrate (10.0 mL) with 1.00 M sodium cyanide (10.0 mL).
3. Without performing a calculation, how much free Ag+ would you expect to be present in this
solution once complexation has occurred? (Hint: remember that Kstab = 1 x 1020 and CN- is present
in excess)

4. After mixing, what are the initial concentrations of Ag+ and CN-?

[Ag+]init = [CN-]init =

5. From the chemical equation, each mole of Ag+ reacts with two moles of CN-. What is the
equilibrium concentration of CN- ?

[CN-]equilibrium =

6. Virtually all of the Ag+ initially present reacts to form the complex [Ag(CN)2-], so

[Ag(CN)2-] equilibrium ≈ [Ag+]init =

7. Finally, substitute your values from Q5 and Q6 into the expression for Kstab and solve to work out
[Ag+].

8. What do you predict will happen if 1 mL of 1.00 M NH3 is added to this solution? (Kstab = 1 × 107
for [Ag(NH3)2]+.)

9. What is the concentration of copper(II) ion in a solution made by dissolving copper(II) sulfate
(0.100 mole) and ammonia (2.00 mole) in water and making up to 500 mL? (Kstab = 1 × 1013 for
[Cu(NH3)4]2+.)
 General Chemistry II - Worksheet 7: Electrochemistry
Model 1: Reduction Potentials
The standard reduction potential, E0red has units of volts (V) and is a measure of a species ability to attract
electrons. The more positive the reduction potential, the stronger is the attraction for electrons. Put another way,
the more positive the reduction potential, the easier the reduction occurs. Some standard reduction potentials are
given below.
Reduction reaction E0red (V)
(1) Ag + (aq) + e− Ag(s) +0.80
2+ −
(2) Cu (aq) + 2e Cu(s) +0.34
2+ −
(3) Sn (aq) + 2e Sn(s) -0.14
(4) Zn2+ (aq) + 2e− Zn(s) -0.76
Critical thinking questions
1. Which is a stronger oxidising agent: Ag+ or Cu2+? Explain how you can tell in terms of the reduction
potentials.

2. If reactions (1) and (2) are added together as a redox reaction which do you think will proceed as a
reduction and which as an oxidation? (Hint: which one will reverse?)

3. Apply the same logic to reactions (3) and (4). Does it matter that they both have negative reduction
potentials?

Model 2: Galvanic Cells

We can harness the electrical energy in a redox reaction, to make
a battery, by setting up a Galvanic cell. To do this, two half
reactions are separated into compartments and electrodes are used
to facilitate the electron transfer. The potentials for the two
reactions are:
Sn2+ (aq) + 2e− Sn(s) E0red = -0.14 V
Zn(s)  Zn2+ (aq) + 2e− E0ox = +0.76 V
This gives an overall voltmeter reading of:
E0cell = E0ox + E0red = +0.62 V.
Critical thinking questions
1. Explain why the Zn half reaction is proceeding as an oxidation and why +0.76 V is used as the potential
for its half cell instead of -0.76 V as in the table in Model 1?

2. Which electrode (Zn or Sn) will lose mass and which one will gain mass?

3. Does oxidation or reduction occur at the cathode?

4. Which of the following statements are correct?
(a) Electrons flow through the wire, towards the zinc electrode.
(b) Electrons flow through the wire, towards the tin electrode.
(c) Electrons flow through the salt bridge, towards the zinc electrode.
(d) Electrons flow through the salt bridge, towards the tin electrode.
5. Electrons flow from the negative electrode to the positive electrode. Which is positive, the anode or the
cathode?

6. The salt bridge contains Na+(aq) and SO42-(aq). Do these ions move when the cell is operating and, if so,
in which direction(s)?

7. If an electrochemical cell with Ag and Cu electrodes was setup, what would be the two half reactions,
which would be the cathode and which would be the anode, and what would be the standard cell potential?
(Hint: use the standard reduction potentials in Model 1.)

8. If an electrochemical cell with Sn and Cu electrodes was setup, what would be the two half reactions,
which would be the cathode and which would be the anode, and what would be the standard cell potential?

9. If an electrochemical cell with Sn and Zn electrodes was setup, what would be the two half reactions,
which would be the cathode and which would be the anode, and what would be the standard cell potential?

10. Which combination of the half cells in Table 1 would make the highest voltage battery?

11. Nicotine adenine dinucleotide (NAD) is involved in redox chemistry throughout the respiratory system.
The reduced form of NAD is written as NADH and the oxidised form is written as NAD+. The standard
reduction reaction and potential of NAD is given by:
NAD+ + H+ + 2e-  NADH E° = -0.105 V
NAD is combined with each of the following reactions:
(a) CO2 + H+ + 2e-  HCOO- E° = -0.20 V
(b) O2 + 4H+ + 4e-  H2O E° = +0.82 V
Write the overall reaction for each of the cells in the direction of spontaneous change. Is the NAD reduced
or oxidised in these reactions?
 Introduction to Electrochemistry
Model 3: The Nernst Equation
The actual cell potential, 𝐸cell, can be calculated from the standard cell potential using the Nernst equation:

where R is the gas constant (8.314 J K- 1

mol-1), T is the temperature (in Kelvin), n is the number of electrons
transferred in the reaction, F is Faraday’s constant (96485 C mol-1) and Q is the reaction quotient. For the reactions
in Model 2:

Critical thinking questions

1. What is the value of n in these reactions? (Hint: how many electrons in total are required to change the
oxidation number of Zn in (1) and of the two O atoms in O2 in (2)?)

2. In the biochemical literature, the biological standard state is used. This has all concentrations as 1 M,
except [H+] which is taken to be 10-7 as this is closer to its value in the body. Use the Nernst equation to calculate
the biological standard cell potential for the oxidation of NADH by O2 at the typical body temperature of 37 °C.

Model 4: Concentration Cells

A concentration cell is an electrolytic cell that is comprised of two half-cells with the same electrodes, but
differing in concentrations. A concentration cell acts to dilute the more concentrated solution and concentrate the
more dilute solution, creating a voltage as the cell reaches an equilibrium. This is achieved by transferring the
electrons from the cell with the lower concentration to the cell with the higher concentration.

Critical thinking questions

1. A pair of copper(II) sulfate solutions, one concentrated and dark blue and the other dilute and light blue,
are separated by a removable barrier.
(a) What will happen when the barrier is removed?

(b) What will happen to the entropy of the system?

(c) What will happen to the enthalpy of the system?

2. The cell opposite consists of two half cells connected together by a wire and a salt bridge. Each cell is
made from a copper electrode in a solution of Cu2+(aq) ions.
• Cell A has [Cu2+(aq)] = 1.0 M.
• Cell B has [Cu2+(aq)] = 0.1 M.
 (a) Is the system at equilibrium?

(b) If not, what must happen to the

concentrations in each cell to reach equilibrium?
• Cell A:
• Cell B:
(c) Unlike the situation in Q1, equilibrium must
be achieved without Cu2+ ions being able to move.
What redox processes can occur in each cell to change
the concentrations in the required direction to achieve
equilibrium?
• Cell A:
• Cell B:
(d) In which direction must electrons flow for these redox processes to occur?

(e) Label the cathode and anode in the diagram.

(f) What is the standard electrode potential for this cell?

(g) Use the Nernst equation to work out the electrode potential of the cell when the switch is connected at
298 K. (Hint: remember that Ecell > 0 for a spontaneous process.)

Model 5: Electrolytic Cells

The reverse reaction can be made to happen if power from an external source with potential greater than E0cell is
applied.

Critical thinking questions

1. Which electrode (Zn or Sn) will now lose mass and which
one will gain mass?

2. What is the overall reaction that now occurs when the cells
are connected?

3. Oxidation always occurs at the anode. Label the anode and

cathode on the cell.
4. Which way do the electrons flow? Draw an arrow on the
diagram to show this.
5. The power source supplies electrons to the electrode where reduction occurs, so it becomes negative. The
power source removes electrons from the electrode where oxidation occurs, so it becomes positive. Which is
positive, the anode or the cathode? Label the electrodes as positive or negative.

6. The salt bridge contains Na+(aq) and SO42-(aq). In which direction(s) do these ions move?
 Introduction to Electrochemistry
Model 6: Electrolysis of Water
Electrolytic cells can be used to perform many useful tasks. A particular useful one is the electrolysis of water as
this has the potential to convert electricity generated using solar energy into hydrogen gas, a combustible fuel.
The reactions at the cathode and anode are:
Cathode: 2H2O(l) + 2e-  H2(g) + 2OH-(aq) E0red = -0.83 V
Anode: 2H2O(l)  O2(g) + 4H+(aq) + 4e- E0ox = -1.23 V
The amount of a substance produced in an electrolytic cell is directly proportional to the amount of electricity that
passes through the cell. The number of moles of electrons that pass when a current I is applied for a time t is given
by: number of moles of electrons = I × t / F

Critical thinking questions

1. What is the overall reaction for the electrolysis of water?

2. F is Faraday’s constant. It is the charge of one mole of electrons. The charge of one electron is 1.602 ×
-19
10 C. What is the charge of one mole?

3. If a current of 10.0 A is applied for 2.00 hours, how many moles of electrons are supplied? (Hint:
remember to convert t into seconds).

4. How many moles of H2(g) will be generated from this amount? (Hint: look at the stoichiometry of the
reaction at the cathode.)

5. How many moles of O2(g) will be generated from this amount?

6. Water is a poor conductor so a salt is usually added to increase the conductivity. The salt must contain
ions that are harder to reduce or oxidise than water. Using the standard reduction potentials, select a suitable salt.