THELSON

VCE UNIT 4 CHEMISTRY

SUGGESTED SOLUTIONS
Notes:

The sign (;) means a point which is given a mark.

So long as you state the meaning of what is given in the answers of course with
correct terminology! you should get the mark.

Words that are bolded are essential for the mark.

This exam is not designed to mirror what VCAA might give you. It tests
material inside the course, but in a relatively challenging way, going
back to basic principles. VCAA would be really nasty to give you a
paper like this.

Section A:
 1 2 3 4 5 6 7 8 9 10
C C D D B B C B A C

11 12 13 14 15 16 17 18 19 20
C C A A D C A C D A

Section B:

Question 1

Notes:This question is an application question. It is testing your knowledge of the

principles of acid-base chemistry and seeing if you can apply it to the
given situation. It is unlikely that VCAA will give this kind of question, but I
am again preparing you for the worst case scenario.

a. Answer:

they are equal (;)

Explanation:

By definition, in a neutral solution, the concentration of the protonated

solvent molecule (H3O+ for water on Earth, NH4+ for ammonia on Ecorus) is
equal to that of the deprotonated solvent molecule (OH - for water on
Earth, NH2- for ammonia on Ecorus).

b. Answer:

11(;)

Explanation:

We know that pH = log10[NH4+] as defined in the question only. Hence

we need to find [NH4+].

We know Kam = [NH4+][NH2-] = 1.0 x 10-22 and [NH4+]=[NH2-].

Hence, Kam = [NH4+]2 = 1.0 x 10-22 [NH4+] = 1.0 x 10-11 pH = 11.

c.
Answer:

Both of (for 1 mark):

Ammonia accepts a proton from water in dissolving in
water/ammonia acts as a base when dissolved in water AND
this is the same as water donating its proton to ammonia in Ecorus
(;)

Explanation: Self-explanatory.

d. Answer:
 Either:

H2O(s) + NH3(l) OH- (am) + NH4+ (am) OR

H2O(am) + NH3(l) OH- (am) + NH4+ (am)

*equation with equilibrium arrows (;)

*correct states (;)

Explanation:

This is a typical acid-base reaction, with water acting as an acid. Both the
(s) and (am) states were accepted for water, as one could consider the
reaction of water already dissolved in ammonia reacting with ammonia, or
the water being dissolved in ammonia then reacting with it.

e. Answer:

[NH4+][OH-]/ [H2O] (;) no mark if [H+] was used

Explanation:

This is like any equilibrium constant. Normally in solution on Earth, the

concentrations of the aqueous species are in the constant. In this case
though, the concentrations of the species dissolved in ammonia is in the
constant.

f. Answer/explanation:

n(H2O)initial = 4.25/18.0 = 0.236 mol

[H2O]initial = n(H2O)initial /0.4750 = 0.497 M

Let x = [NH4+]eq, [OH-]eq = x and [H2O]eq = 0.497 x. (;)

Because ionisation is very slight, we can assume that x < < 0.497
[H2O]eq = 0.497 M

Solve the equation Ka = x2/0.497 = 1.8 x 10-5 (;)

x = [NH4+]eq = 3.0 x 10-3 pH = 2.52 (;)

g. Answers (sample):

*0.5 marks rounded down for each assumption or justification to a

total of 3 marks

Assumption Justification
[H2O]initial = H2O is a weak acid, and so ionisation is very slight and
[H2O]eq will not change [H2O] much.

If we didnt make the assumption, and solved the

equation x2/(0.497-x) = 1.8 x 10-5 we would still get x =
3.0 x 10-3.
 [NH4+]initial = 0 M The amount of NH4+ produced from the ionisation of
water is much higher than the amount of NH 4+ produced
from autodissociation of ammonia.

If we didnt make the assumption, then we would say

[NH4+]eq = 10-11 + x (if we let [OH-]eq = x) and we would
form the equation:

x(x + 10-11)/(0.497-x) = 1.8 x 10-5

which would be very tedious and unnecessary to solve.

Qam = Kam after The amount of NH4+ required to bring the NH4+/NH2-
the H2O/OH- system into equilibrium is negligible because [NH 4+] >>
system is at [NH2-].
equilibrium

If we did not make the assumption, then we would have

to solve simultaneous equations. That is...bad.

Eq 1. [NH4+][OH-]/ [H2O] = 1.8 x 10-5

Eq 2. [NH4+][NH2-] = 1.0 x 10-22
Eq 3. [H2O] + [OH-] = 0.497
Eq 4. [NH4+] = [NH2-] + [OH-]

You can solve this using a few tricks (i.e. iteration) and
you get [NH4+] = 3.0 x 10-3 M (2.982) and pH = 2.53
(yes, not 2.52, but thats because of rounding)

Very tedious and unnecessary.

The italicised stuff did not have to be included, it is just there for
understanding.
Question 2

This is another application question of a type you of equilibrium that you are
unlikely to have seen before. Again, the point of this question is to allow you to
use the principles of equilibrium you have learned to answer this question.

a. Answer/explanation:

The solubility is [AgCl]max.

We know that [AgCl]max = [Ag+]eq = [Cl-]eq.
Ksp = [Ag+ ]eq [Cl-]eq = [Ag+ ]eq 2 = 1.6 x 10-10 (;)
[AgCl]max = [Ag+ ]eq = 1.6 x 10-10 = 1.3 x 10-5 M (;)

b. Answer/explanation:

Cl- is being added into solution (so [Cl-] increases initially) (;)
by LCP the system attempts to partially oppose the increase in
[Cl-]/Qsp needs to decrease to bring the system back to
equilibrium/the frequency of successful collisions between Ag+ and
Cl- decreases, decreasing rate of back reaction it shifts the
position of equilibrium back, so more AgCl is formed (;)

This is an application of Le Chateliers principle with addition of

product. If you can either use a LCP argument or a Q sp > Ksp
argument then you get the second mark.

c. Answer/explanation:

This is a very difficult question that requires innovation. You are

unlikely to get this in a VCAA exam, but again think worst case
scenario. Firstly let us assume that AgCl and Cl - is added into water,
so we have the initial conditions:

[Ag+]initial = 0 M
[Cl-]initial = 1.00 x 10-2 M

Now, we know by looking at Qsp that some Ag+ goes into solution in
order to increase Qsp to equal Ksp. So let us set up the equation,
letting [Ag+]eq = x.

[Cl-]eq = 1.00 x 10-2 + x

Ksp = [Ag+]eq [Cl-]eq = x(1.00 x 10-2 + x) = 1.6 x 10-10. (;)

So now we have set up our equation. We could go ahead and solve

the quadratic, or we could see that because AgCl is quite insoluble
in water, [Cl-]initial = [Cl-]eq as [Cl-]initial is very large (i.e. x << 1.00 x
10-2) (;)
x(1.00 x 10-2 + x) = x(1.00 x 10-2) = 1.6 x 10-10
x = 1.6 x 10-8 (if you were to solve the quadratic you get x =
1.5999974 x 10-8) (;)
[Ag+]eq = 1.6 x 10-8 M
n(AgCl)dissociate = n(Ag+)solution = 1.6 x 10-8 x 0.1000 = 1.6 x 10-9 mol
(;)
 This is the amount of AgCl that has gone into solution. Now to work
out how much is left:

m(AgCl)dissociate = 1.6 x 10-9 x (107.9 + 35.5) = 2.29 x 10-7 g

m(AgCl)remaining = 1.00 x 10-5 - 2.29 x 10-7 = 9.8 x 10-6 g (;)
d. Answer/explanation:

the reaction is endothermic/H is positive so an increase in

temperature implies an increase of Ksp (;)
+
concentration (mol L-1 ) an increase of Ksp means an increase in [Ag ]eq = [AgCl]max and
since the solubility is equal to [AgCl]max it increases (;)

OR

increase (;)
when the temperature is increased, the system shifts as to
partially oppose the increase in temperature (it acts to decrease
the temperature), and so favours the endothermic reaction AgCl
going into solution, so [AgCl]max increases (;)

Question 3

This is a straightforward question, yet tests the knowledge of the principles

involved with equilibrium.

time (min) 2 10
10
a. Answer/Explanation

This question was a little bit vague, so a variety of answers will be accepted
here.

Rate of reaction graph:

o Axes must be labelled. The horizontal axis must be labelled with
time with unit minutes whilst the vertical axis must be labelled
reaction rate (OWTTE). Given that VCE does not (I think) stipulate
 that you must know the units of the reaction rate, it is not
necessary to put in units here. However, FYI the units are mol L -1 s-1
or mol s-1 or gs-1 or any acceptable measure of
amount/concentration against any form of time. (;)
o The back and forward reaction lines must be labelled. They must be
equal to one another up to 10 minutes, and increase (technically
they should initially double, but it wont be penalised as you are not
required to know the differential rate law) at 2 minutes. The back
reaction rate must increase initially at 10 minutes and subsequently
decrease. The forward reaction rate must slowly increase at 10
minutes. The two reaction rates must be equal. (;)

Concentration-time graph
o Axes must be labelled. The horizontal axis must be labelled with
time with unit minutes whilst the vertical axis must be labelled
concentration with units of mol L-1 or M or g L-1 or mol dm-3 any
acceptable measure of amount or mass against volume . (;)
o The [HI], [H2] and [I2] can start anywhere, given that the K value
was not given. At 2 minutes, the concentrations of each reagent
initially double and remain constant subsequently, given that the
number of particles at each side of the equation is the same. At 10
minutes, the changes must be as shown on the graph above. (;)

b. Answer/Explanation

1 mark for each of:

Initial change (all of):

o [HI] initially increases (whilst the concentration of the other
species remains the same).
o Thus, the number of collisions per unit time (and thus
successful collisions per unit time) between HI molecules
increases
o back reaction rate increases, whilst the forward reaction rate
does not initially change. (;)
Over time (all of):
o [HI] subsequently decreases (as the back reaction is initially
faster), hence frequency of successful collisions decreases,
hence rate of back reaction decreases.
o Similarly, [H2] and [I2] subsequently increases, hence
frequency of successful collisions increases, hence rate of
forward reaction increases.
o This occurs until the rate of the back and forward reactions
are equal. (;)

Of course, not all of the words need be used here, but the stuff that is bolded
MUST be included to get full marks.
Question 4

a. Answer/Explanation

This question is assessing the ability to synthesise information and to

explain the principles behind industrial chemistry. One point for one mark;
each point must make a reference to either:

KINETIC: increased reaction rate implying a faster rate of

chemical production
EQUILIBRIUM: position of equilibrium facing the right implying a
higher yield

One mark should be deducted if a reference to the bolded text above was
not made for both dot points.

At least one kinetic and one equilibrium factor must be made. If the two
conflict, then a reference to a compromise must be made. A mention of
cost could also be made in reference to why a particular reaction
condition was not utilised, even though it is kinetically and/or
thermodynamically favourable.

Mark allocation:

one equilibrium factor (;)

one kinetic factor (;)
four other factors (;) (;) (;) (;)
-1 if a reference was not made to both of the two dot points

b. Answer/Explanation

This question assesses the LINK between the properties of the chemical
and its uses.

Mark allocation

two uses (;) (;)

the correlating properties (;) (;)

Correlating properties mean the properties that make the chemical

suitable for the particular use.

Examples (these are only a few of many uses):

Sulfuric Acid
 Use Property
production of superphosphate acid, protonates the PO43- ion to
fertiliser H2PO4-
production of ammonium fertiliser acid, donates a proton to NH3 to
form the soluble NH4+ (in the form
(NH4)2SO4)
pickling of iron to remove surface acid, protonates O2- to H2O to
oxide dissolve the Fe2O3
production of TNT acid, protonates HNO3 to form
H2NO3+ NO2+ + H2O
removal of organic sulphides from oxidant, oxidises the sulphides
petrol
drying agent high affinity for water; H2SO4 (l)
H2SO4 (aq) is highly exothermic

Nitric acid

Use
production of TNT
production of ammonium fertiliser
production of nitrate salts
production of laughing gas
Property
nitic acid can be protonated, and
the product decomposing to form
NO2+
acid, donates a proton to NH3 to
form the soluble NH4+ (in the form
NH4NO3)
the conjugate base of HNO3 is
NO3-/nitric acid is a strong acid, so
dissolution in water yields nitrate
anion
acid; nitric acid can produce
NH4NO3, which decomposes to
form N2O (laughing gas)

Ethene

Use Property
production of polyethene ethene has a C=C double-bond,
making it possible for it to
polymerise via addition
polymerisation
ripening fruit ethene acts as a plant growth
regulator/plant hormone, and
accelerates ripening of fruit

Ammonia

Use
production of superphosphate
fertiliser
production of urea fertiliser
Property
acid, protonates the PO43- ion to
H2PO4-
base/contains lone pair of
electrons/Lewis base/nucleophile,
can attack the C atom on CO2
which has a positive polarity.
 production of nitric acid ammonia can be oxidised to NO
pharmaceuticals sulphonamides: ammonia is a
base/contains lone pair of
electrons/Lewis base/nucleophile,
and can attack the partially
positively charged sulphur atom in
the sulfonyl group
nitration of benzene ring (this is a
precursor to LOTS of drugs):
ammonia can be used to produce
nitric acid, which can form NO2+

As I was writing these solutions, I realised that this question was actually
somewhat unfair its much easier for the people doing sulphuric acid than for
those doing ethene and ammonia! VCAA should not ask this question, given
that its a doddle for those doing sulphuric acid.

Question 5

This question is a typical and straightforward calorimetry question.

a. Answer/explanation:

All of:
endothermic
temperature decrease means removal of heat
energy from water
hence heat energy is absorbed in the reaction (;)

This is a straightforward question. The marking criteria may be somewhat

harsh here, but remember, it is essential that you explain all relevant logical
steps; never assume the examiner will infer. If you know something, show it!

b. Answer/explanation:

If assuming c(solution) = c(water) = 4.18 J K -1 g-1,

q = mcT = (0.243 + 200.0) x 4.18 x (296.41 296.14) = 226 J

(225.99) (;)

n(NH4NO3) = 0.243/80.0 = 3.04 x 10-3 mol (3.0375)

qm = 225.99/n(NH4NO3) = 7.44 x 104 J mol-1 = 74.4 kJ mol-1 (;)

If assuming amount of ammonium nitrate is so small that its

contribution to absorbing heat is negligible,

q = mcT = 200.0x 4.18 x (296.41 296.14) = 226 J (225.72) (;)

 n(NH4NO3) = 0.243/80.0 = 3.04 x 10-3 mol (3.0375)
qm = 225.72/n(NH4NO3) = 7.43 x 104 J mol-1 = 74.3 kJ mol-1 (;)

Either of these two approaches is acceptable. Within the scope of the year 12
course, it is very difficult to find a very accurate value of the molar heat of
dissolution we would have to consider the specific heat capacities of all the
species in solution and that would have not been nice.

Also, the question should have specified to make the assumption that the
specific heat capacity of the solution is equal to that of water. Given that I did
not state this assumption, either of the two answers should be marked correct.
In the VCAA exam they will specify what assumptions you should make.

c. Answer/explanation:

So, we need to work out the amount of energy required to heat the
calorimeter by one Kelvin. Let us work out the total amount of energy
delivered to the calorimeter.

E = VIt = 6.00 x 3.10 x 30.0 = 558 J

Cf = E/T = 558/(296.41-294.32) = 267 J K-1 (266.99) (;)

q (released by calorimeter) = Cf x T = 267 x (296.41 296.14) = 72.1
J (72.086)
q (absorbed in reaction) = 72.1 J (72.086) (;)
qm = 0.0721/(0.243/80.0) = 23.7 kJ mol-1 (;)

This is again a regulation question.

d. Answer/explanation:

Both of:
value calculated in part c
the value quoted in part b assumed that water was the
only entity releasing heat energy, which is not the case
the calorimeter itself releases heat energy (;)

This question tests your practical analytical skills to determine sources of error in
practical work associated with this course.

e. Answer:

-23.7 kJ mol-1 (consequential marks may be awarded here) (;)

 Explanation:

We have worked out that the more accurate molar heat of dissolution (i.e.
the reaction NH4NO3 (s) NH4NO3 (aq)) is +23.7 kJ mol-1.

Hence, given that NH4NO3 (aq) NH4NO3 (s) is the reverse reaction, we
change the sign of the heat value, so the answer is - 23.7 kJ mol -1.

However, the mark should be given depending on the answers to parts b, c

and d. If you calculate values for parts b and c, and quote one of them in
part d, and change the sign of the answer quoted in d, you should get the
mark.

This is a regulation question testing your knowledge on thermochemical

equations.

Question 6

This question tests your understanding of redox chemistry. Up to part d, this

question is routine. However, parts e-g test your ability to grapple with new and
unseen information and use your understanding of the material to make sense of
what is going on. Part g is particularly difficult; this question requires you to think
somewhat laterally.

a. Answer:

V
-
NO3 K+
(aq) (aq)

Ni
Pb

Ni2+ Pb2+ (aq)

(aq)

ANODE (-) CATHODE (+)

1 mark for each of:

 correct species in each electrode Ni 2+ in one cell with a Ni
electrode and Pb2+ in the other cell with a Pb electrode AND
indication of KNO3 on salt bridge (;)
correct labelling of cathode and anode (cathode is the Pb electrode,
anode the Ni electrode) AND correct polarities (anode is ve,
cathode +ve) (;)
electron flow from anode to cathode (;)
NO3- flow towards anode, K+ towards cathode (;)

Explanation:

The electrochemical series shows that Ni is a more reactive metal, so the

electrons would flow from Ni to Pb2+. Anode is the site of oxidation, so Ni
will be the anode as it is being oxidised, and the cathode is the site of
reduction, and since Pb2+ is reduced, the Pb electrode will be the cathode
(AN OIL RIG CAT).

Since electrons are flowing from Ni half-cell to Pb half-cell, the anions in

salt bridge need to balance this charge, so anion flows towards Ni half-cell
to replace the lost electrons, whilst the cations flow towards the Pb half-
cell.

b. i. Answer:

Ni (s) + Pb2+ (aq) Ni2+ (aq) + Pb (s) (;)

States MUST be included for the mark.

Explanation:

Writing the half-equations is redundant, as inspection shows that two

electrons are being transferred. Ni is more reactive, so it is oxidised.

ii. Answer:

0.10 V (;)

Explanation:

A quick inspection of the electrochemical series shows that the reduction

potentials of the two half-cells are -0.13 V and -0.23 V. Given that this is a
spontaneous reaction, we take the absolute difference between the two,
which is 0.13 + 0.23 = 0.10 V.

c. Answer:

BOTH of:
Yes/they are equal
 The half-cells are in standard conditions 298 K, 1 M solutions (and
solids in pure state, but it can be assumed) (;)

The values for the standard conditions must be specified for the mark
(apart from the pure solid condition).

Explanation:

It was given that the cells had 1M solutions and were at 298 K; these
constitute standard conditions. The actual potential difference between
the half-cells ECELL1 is the same as the potential difference under standard
conditions when the half-cells are under standard conditions.

d. Answer:

BOTH of:
No/they are not equal
The half-cells are not at standard conditions 304 K not 298 K,
0.100 and 2.00 M not 1 M solutions (;)

A comparison between standard conditions and actual conditions needed

to be made for the mark.

Explanation:

The potential difference between half-cells will not be equal to the

standard potential difference between the half-cells, as temperature and
the concentration of aqueous species (and pressure of gaseous species)
determines the standard potential difference and the temperature and
concentration of aqueous species were not the same as for standard
conditions. Im being a little harsh in saying that a comparison had to be
made, but you want to try and show the examiner that you know your
stuff and you are not randomly guessing the answer.

e. Answer:

8.31304 2.00
ECELL = 0.10 log e (;)
2 96500 0.100

= 0.06 V (;)
 Explanation:

This is simply application of knowledge given in the question. The

concentrations of each species were given in the stem of the question.

f. Answer/Explanation:

2+

Ni

2+

Pb
ECELL = ECELL



RT
log e
2F

As given in the stem of the question, the system is at equilibrium when

ECELL is 0 V. We also know that:

2+


2+
Pb



K c =

Thus,

8.31304
0 = 0.10 log e K c (;) Kc = 2.1 x 103 (2079) (;)
2 96500

This is again an application question that required you to recognise the

expression for the equilibrium constant in the Nernst equation and to
comprehend the information in the question stem.

g. Answer/Explanation:

This is a relatively difficult problem requiring a little algebra.

But first, lets work out what is going on. We know that Ni is being oxidised
in the reaction, so we know that [Ni 2+] increases and [Pb2+] decreases. So
we can set up the equations:

[Ni2+]eq = [Ni2+]i + x = 2.000 + x

[Pb2+]eq = [Pb2+]i - x = 0.100 x
 2+



2+
Pb (;)



K c =

We did work out Kc in part f, but given that we may get rounding errors, its
best if we find x in terms of Kc first:

(0.100 x) Kc = 2.000 + x
x = (0.100 Kc 2)/(Kc + 1) = 0.099
[Ni2+]eq = 2.000 + x = 2.099 M
[Pb2+]eq = 0.100 - x = 0.001 M (;) [both concentrations for
answer mark]

As you can see the reaction is pretty much complete, but not 100%.

Question 7

a. Answer:

impure copper sample, pure copper sample, cathode

anode (+) (-)
 Cu2
+

1 mark for each of:

anode and cathode correctly labelled (;)

o anode must be on the LHS because electron flow direction
was given!
correct polarities labelled (to the anode and cathode) (;)
correct labelling of the composition of each electrode (;)
Cu2+ present in solution (;) you could also put in H+ (aq) from
autodissociation of water if you want to be a smart alec but you
wouldnt lose a mark for that, and you could also put in other metal
ions and that would be fine.

Explanation:

After electrolysis occurs, the copper from the impure copper sample is
deposited onto the pure sheet. The wording is not great actually given
that its not the same copper atoms that get oxidised that end up on the
sheet, but this shows that we are removing copper from the impure copper
sample, hence we are oxidising it. So the impure copper sample is the
anode, and it is +ve because we are manually ripping electrons from this
electrode, making it positively charged. The anode is the electrode on the
left, because the direction of electron flow is away from the anode.

The other electrode with the pure copper sample is the cathode, and it has
a ve polarity as electrons are being forced into it.

Cu2+ must initially be in solution so it can accept electrons at the cathode

to become reduced to Cu. Other ions MAY be in solution during
electrolysis, and you would not REALLY be penalised for putting other ions
in your diagram, so long as you include Cu 2+ as well.

b. Answer: Ni, Fe, Pb, Co, Sn, Zn (;) ALL of these for the mark.
If Ag or Au circled, 0 marks.
 Explanation:

A quick inspection of the electrochemical series on the RHS (where the

reductants are) show that only Ag and Au are above Cu, and the further
down you go, the more reactive the metal is.

c. Answer: they are oxidised (and go into solution)

Explanation:

These metals are more reactive, and therefore donate their electrons in
preference to copper. Hence they are oxidised and become aqueous
species.

d. Answer: they remain in their metal form (and fall to bottom beaker as
anode mud)

OR

they are also oxidised accept this answer ONLY if the

answer also states something to do with a very high
potential difference applied between the electrodes.*

Explanation:

These metals are less reactive than copper; they do not donate their
electrons in preference to copper. Hence they are not oxidised

*It is possible for these metals to be oxidised as well IF the potential

difference exerted across the electrodes is high enough.

e. Answer/Explanation:

Lets work out first how many electrons were transferred onto the impure
copper sample (which is now the cathode because the technician has no
idea):

Q = It = 3.00 x 2.00 x 60 = 360 C (;)

n(e-) = 360/96500 = 3.73 x 10-3 mol using Faradays constant of 96500

(;)

Given that one Cu2+ ion requires 2 electrons to be reduced,

n(Cu) = n(e-)/2 = 1.87 x 10-3 mol

m(Cu)deposit = n(Cu) x 63.6 = 0.119 g

m(Cu)final = 1.00 + 0.119 = 1.12 g (;)

This is a straightforward application of Faradays law.