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ANSWERS TO PART A OF THE

NATIONAL HIGH S CHOOL C HEMISTR Y EXAMINATION 2001 continued


Ques tions 21 to 25 an d Appe ndix
This question requires the calculation of entropy, which is not on the Pan-Canadian
protocol, although students considering taking Part C (Olympiad section) of the
National High School Chemistry Exam should be able to do this. Other students should be able to
recognize that the evaporation of water involves an increase in entropy (disorder) i.e. the entropy
change is positive. Keys A, B and C cannot therefore be correct.
21.

The equation required for the calculation is:

G = H - T S

Where G is the Gibbs free energy change for the reaction in kJ"
mol-1
H is the enthalpy change for the reaction in kJ"
mol
T is the t emperature at which the reaction is taking place, in K
and S is the entropy change for the reaction in J"
mol-1"
K-1

The chemical equation for the evaporation of water is:


H2O(l) ----> H2O(g)
Now, as in question 20, Hr = " Hf (products) - " Hf (reactants)
And similarly,

Gr = " Gf (products) - " Gf (reactants)

This means that, for the evaporation of water:

H = H"f,298(H2O(g)) - H"f,298(H2O(l))
= (-241.8) - (-285.8) kJ "
mol-1
= + 44.0 kJ"
mol-1
(Note that the positive sign indicates that the process is endothermic, this agrees with evaporation
being a bond-breaking process.)
Likewise:

G = G"f,298(H2O(g)) - G"f,298(H2O(l))
= (-228.6) - (-237.2) kJ "
mol-1
= + 8.6 kJ"
mol-1
Rearranging the equation: G = H - T S, gives the entropy change, thus:

S = ( H - G) T
= (44.0 - 8.6) kJ"
mol-1 298 K
-1
= 0.1188 kJ"
mol K-1
= 118.8 ~ 120 J"
mol-1 K-1

Answers to NHSCE 2001 Part A


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So the correct answer is E. (Note how very important the units are in this question.)

22.

This question tests a similar concept to Question 16 in Part A of the 2000 exam, namely
that absorption of energy is required to break bonds.

The 2001 question goes a little further. The absorption of energy initiates a chain reaction by
causing the homolytic fission of a covalent bond to form two free radicals. So the correct answer
is D. (The sequence in which other reactions in the chain occur are not as easily predicted.)
If you are not familiar with the terminology, then here are some definitions:
A chain reaction is a reaction in which intermediates (chain carriers) can initiate further
reactions. In chemical chain reactions these intermediates are often free radicals or atoms,
whereas in nuclear reactions they are neutrons.
A free radical is an atom or group of atoms with unpaired electrons. Some of these may be quite
stable, e.g. NO molecules, but most radicals are very short lived. The unpaired electron on a
radical is often marked with a dot, thus chlorine atoms are represented as Cl"
when they are
behaving as free radicals in the chain reaction shown in this question. Note, however, that the
oxygen atoms are only shown as O in this question although they can behave as free radicals: they
actually have two unpaired electrons. (An oxygen atom has six valency electrons, four of which
are paired to form two electron pairs, and two are unpaired.)
Homolytic fission occurs when a covalent bond is broken in such a way that one electron from
the bonding pair goes to each of the fragments formed at either end of the broken bond. This
results in the fragments beco ming free radicals. Compare this with heterolytic fission which
occurs when a covalent bond is bro ken in such a way that both t he electrons in the bond go to one
of the fragments, which then becomes a negative ion: the remaining fragment is electron deficient,
so it becomes a positive ion. The greater the polarity of a covalent bond the more likely it is to
undergo heterolytic fission rather than homolytic fission, but external factors such as solvents can
also affect the nature of the fission.
Chemical chain reactions are initiated by the formation of radicals by the action of heat or light on
a normal molecule, so in the example given in the question the chain initiation step is:
D. CF2Cl2 !
"
CF2Cl + Cl"
Once the free radicals have been formed, the chain is propagated by a reaction involving a
molecule producing a product molecule and another radical, which can continue the chain.
Examples of chain propagation steps are:

Answers to NHSCE 2001 Part A


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and

B. ClO"
+ O !
Cl"
+ O2
C. Cl"
+ O3 !
ClO"
+ O2

Inhibition occurs when a free radical attacks the (desired) product of the reaction There is no
example of an inhibition step given in this series of reactions.
The chain terminates when two free radicals combine. An example of a termination reaction is:
E.

"
CF2Cl + "
CF2Cl !
C2F4Cl2

The termination reaction is often the reverse of the initiation reaction, which in this case would be
the reverse of D, thus:

"
CF2Cl + Cl"
!CF2Cl2 (this is not shown as an option in the question)
The reaction given in key A is an interesting one:
O + O3 !
2O2
This shows how the oxygen atoms generated in reaction B can react with ozone to make oxygen.
It is an example of how ozone can be destroyed by the reactions originating with a
chlorofluorocarbon. It is true that the reverse reaction can also occur, generating oxygen atoms,
but these oxygen atoms can then be used in reaction B, creating chlorine radicals which can then
attack ozone in reaction C. Either way, the ozone layer will be reduced.

23.

There are a number of ways in which redox reactions can be recognized. For simple
inorganic reactions such as these the best method is probably to look at oxidation
numbers.

Redox reactions are characterized by a change of oxidation numbers. (The rules for
assigning oxidation numbers are given in the Appendix.) If the redox is considered in two parts,
reduction and oxidation, then the oxidation number goes down in the reduction part and up in the
oxidation part.
One important point to realise is that any reaction that involves an element (as either reactant
and pro duct) must involve a change in oxidation number (to or from zero) and is therefore redox.
This eliminates keys A, B and D.
If you think of the oxidation number rule about oxygen and peroxides, you can immediately see
that key C refers to a redox reaction. This leaves E as the correct answer.

Answers to NHSCE 2001 Part A


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Some of the reactions suggested as options in this question are of interest for a number of
reasons, which are considered below.
A. Br2 + H2O !HBr + HBrO
This reaction is interesting because it is an example of a disproportionation reaction. In this
kind of reaction the same element is both oxidized and reduced. Here elemental bromine
(oxidation state zero) is reduced to oxidation state -1 (in hydrogen bromide) and oxidized to
oxidation state +1 (bromic(I) acid - also known as hypobromous acid).
B. I2 + 2Na2S2O3 !2NaI + Na2S4O6
In this reaction iodine is reduced from oxidation state zero (in the elemental state) to -1 (in
sodium iodide), whilst sulfur is oxidized from oxidation state +2 (in sodium thiosulfate) to +2.5
(in sodium tetrathionate). The tetrathionate ion is a good example of a species containing a
partial oxidation number (see also question 4 from Part A of the 2000 exam). A partial
oxidation number is, in fact, an indication that the element is present in two different oxidation
states in the same compound, or that some of the atoms of the element are linked t o atoms of the
same element. In fact sulfur is linked to ot her atoms of sulfur in both t he thiosulfate ion and in the
tetrathionate ion (as well as being linked to oxygen atoms). This can be seen if you draw o ut the
structural formulae of the ions. Note that this does not preclude the use of the oxidation number
method for balancing the equation (check here that the total oxidation number change up equals
the total oxidation number change down ).
In reactions containing more co mplex systems than those represented in this question, the
oxidation number method of identifying redox reactions, and of balancing them, becomes difficult,
and other methods are more practicable. In organic chemistry, for example, it is often easier to
see whether oxygen is being added to a compound (oxidation), or whether hydrogen is being
added (reduction).
C. Na3AsO3 + H2O2 !H2O + Na3AsO4
In this reaction arsenic is being oxidized from oxidation state +3 to oxidation state +5, whilst
oxygen is being reduced from -1 in hydrogen peroxide to -2. Note that one of the product
oxygens is in water whilst the other is in sodium arsenate(V). Also see how that there is a greater
proportion of oxygen in Na3AsO4 than in Na3AsO3, indicating that the arsenic is in a higher
oxidation state. A comparison of the proportions of oxygen in the corresponding acids also
signals that H3AsO4 is more strongly acidic than H 3AsO3 (cf Question 14).
D. 3I2 + 6NaOH !NaIO3 + 5NaI + 3H2O
This is another disproportionation reaction in which elemental iodine (oxidation state zero) is

Answers to NHSCE 2001 Part A


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oxidized to iodate(V) (with iodine in oxidation state +5) and reduced to iodide (oxidation state
-1). Note how the stoichiometry works in order to balance the oxidation number changes.
E. 2K2CrO4 + H2SO4 !K2Cr2O7 + K2SO4 + H2O
This is NOT a redox reaction, even though pot assium dichromate is often used as an oxidizing
agent. Some teachers recommend that students learn the names and formulae of common
oxidizing and reducing agents, just so that they can recognize redox reactions - but you can get
caught out by this approach!
This reaction is, in fact, a condensation (addition-elimination) reaction. Potassium ions and
sulphate ions are spectators , and the essential reaction is that two chromate ions add together
and water is eliminated, as shown in the following ionic equation:
2CrO42- + 2H+ !Cr2O72- + H2O
The chromium ions remain in the +6 oxidation state. Note that this is a good example of an
equilibrium system that can be manipulated by changing the pH. Addition of acid swings the
equilibrium to the dichromate side of the reaction, and, in fact, dichromate ions are only found to
any appreciable extent in acid media. On the other hand, chromate ions require to be in an
alkaline environment.

Note that reaction kinetics are not on the Pan-Canadian protocol, however a question on
rates will be included in Part A of the National High School Chemistry Exam, because
of the importance of this topic, particularly to chemical engineers. Questions will be restricted to
testing knowledge of the meaning of rate of reaction, methods of measuring rates of reaction, and
the fact ors affecting rates. Students will be expected to know the meaning of act ivation energy,
but the rate expression and t he Arrhenius equation will no longer be included on Part A of the
exam (but they may appear on Part C).
24.

Question 24 tests t he student s understanding of the way in which the st oichiometry of the
reaction can influence the measured rate, and of the different ways in which rates can be measured
experimentally. Generally the rate of reaction is defined as the change of concentration of a
particular reactant in unit time, which would give units of mol"
L-1"
min-1 (mol"
L-1"
s-1, mol"
L-1"
h-1
etc. would also be possible). The rate may, however, be monitored in a variety of ways apart from
measuring concentration changes. Any quantity that changes in proportion to concentration may
form an acceptable basis for rate measurement, for example the volume of gas at constant
temperature and pressure could be used.
Note that, in this question, the rate is taken as positive, irrespect ive of whether it applies to the
decrease in concentration of a reactant, or to the increase of concentration of a product. Some

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authors consider the rate to be negative if it refers to a decrease in concentration with time.
This question refers to the reaction between mercury(II) chloride and ethanedioate (oxalate) ions,
which is represented by the following equation:
2Cl-(aq) + 2CO 2(g) + Hg2Cl2(s)
2HgCl2(aq) + C2O42-(aq) !
It is (presumably) possible to measure the rate of reaction at a particular stage of the reaction in
terms of the mercury(II) chloride concentration (or, more likely, the Hg2+ ion concentration). Let
us consider what happens to the other components of the mixture at this point.
The rate of reaction in terms of the ethanedioate (oxalate) ion, C2O42- will be half that of the rate
in terms of HgCl2, because according to the equation, 2 moles of HgCl2 are required to react with
each mole of C2O42-, so the HgCl2 will be used up twice as fast. Thus, if the rate of reaction is
min-1, then the rate of reaction in terms of C2O42- will be 2.50
L-1"
terms of HgCl2 is 5.00 x 10-5 mol"
x 10-5 mol"
L-1"
min-1, so key A cannot be correct.
The equation shows, however, that 2 moles of HgCl2 produce 2 moles of aqueous chloride ions,
Cl-, so that the rate in terms of Cl- will be the same as that for HgCl2, and key B is correct.
If you have time you could cont inue to consider the other keys, all of which require assumptions
that are not really valid.
The rate of reaction in terms of carbon dioxide gas could be measured by measuring the loss of
mass to the system if the reaction were performed in an open container. The rate in terms of
min-1 would be the same for CO2, as for HgCl2, because the equation shows that 2 moles
mol"
L-1"
of HgCl2 produce 2 moles of CO2. Supposing that we have one litre of reaction mixture, and that
5.00 x 10-5 mol of CO2 are produced from this in a minute, then the mass produced in the same
time would be 2.20 x 10-3 g (= 5.00 x 10-5 mol x 44.0 g"
mol-1 ) not 1.14 x 10-6 g (= 5.00 x 10-5
44.0), so that key C cannot be correct.
Another method of measuring the carbon dioxide gas, would be to trap it and measure its volume.
Again supposing that we have one litre of reaction mixture, and that 5.00 x 10-5 mol of CO2 are
produced from this in a minute, and supposing that the volume of gas is measured at standard
ambient temperature and pressure, then the volume of gas produced in a minute would be 1.21 x
10-3 L (= 5.00 x 10-5 mol x 24.2 L"
mol-1), so key D cannot be correct.
The rate of reaction could also be measured by filtering off the solid mercury(I) chloride, drying
it, then measuring its mass. The equation tells us that one mole of Hg2Cl2 is formed from 2 moles
of HgCl2, so that the if we start with 5.00 x 10-5 mol of HgCl2 we would expect to obtain 2.50 x
10-5 mol of Hg2Cl2. (Again we would have to suppose that we start with one litre of reaction
mixture.) 2.50 x 10 -5 mol of Hg2Cl2 corresponds to a mass of 1.18 x 10-2 g (= 2.50 x 10-5 mol x
472.1 g"
mol-1) not 1.05 x 10-7g (= 5.00 472.1), so key E cannot be correct.

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This equation co uld be solved using the Nernst equation. This is not, however, on the
Pan-Canadian protocol, although it is something that students taking Part C (Olympiad
section) of the exam should know. The Nernst equation would give an exact numerical value for
the overall cell pot ential under non-standard conditions, but this is not in fact required. The
question as it stands can be solved by applying Le Chtelier s principle to the redox equilibria.

25.

Let us first consider the reduction potentials that are given, namely:
Zn(s); E "= - 0.76V
Zn2+(aq) + 2e- !
Ni2+(aq) + 2e- !
Ni(s); E "= - 0.25V
These are bot h standard reduction pot entials, meaning that they refer to standard ambient
temperature (298 K), 1 atmosphere (101.3 kPa) pressure, and solution concentrations of 1.0
mol"
L-1 . They are also determined with reference to the standard hydrogen electrode, which may
be written as:
H2 (g); E "= 0.00V
2H+(aq) + 2e- !
The reduction potentials of zinc and nickel half-cells are negative because in both cases the metals
are more likely to dissolve when placed in a solution of their own ions than hydrogen gas is when
it is placed in a solution of hydrogen ions. When these metals dissolve they tend to be oxidized
rather than reduced, so the equilibrium reactions are reversed and electrons are produced, thus
Zn(s) !
Zn2+(aq) + 2eNi(s) !
Ni2+(aq) + 2eIf the concentration of a metal ion solution is lowered, then it can be predict ed that the
equilibrium will shift so that more metal will dissolve in order to replace the ions, making the
electrode more negative. Co nversely, if the concentrations of the metal ions are increased the
electrode becomes more positive.
Now let us return to the equations originally given for the two half-cells under consideration:
Zn2+(aq) + 2e- !
Zn(s); E "= - 0.76V
Ni2+(aq) + 2e- !
Ni(s); E "= - 0.25V
As the zinc half-cell is more negative than the nickel half-cell, oxidation is more likely to occur at
the zinc electrode, whilst reduction will occur at the nickel electrode. The sign of the standard
electrode potential for zinc must therefore be reversed when calculating the overall cell potential
under standard conditions, thus:

Answers to NHSCE 2001 Part A


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Ecell" = Eredn"(Ni2+/Ni) - Eredn"(Zn2+/Zn)
Ecell" = - 0.25 V - (- 0.76 V) = + 0.51 V
Now, we saw above that if the concentration of the nickel ion solution is increased the standard
reduction potential becomes more positive, i.e. less negative. The overall cell potential will
therefore become more positive than + 0.51 V, and the correct key is A.

Answers to NHSCE 2001 Part A


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APPENDIX
RULES FOR ASSIGNING OXIDATION NUMBERS (OXIDATION STATES)
In simple binary compo unds the oxidation number is equal to the valency of an ion. 1 Valency,
however, is a value that is determined experimentally by looking at the formula of a lot of
compounds containing an element or group of elements. On the other hand oxidation numbers
are theoretical values that assume every element in a compound is present as an ion - even though
it may, in fact, be covalently bonded! Oxidation number is an indication of the number of
electrons that an atom is using for bonding.
The rules for assigning oxidation numbers (also called oxidation states) are mainly common sense,
and are not difficult to learn. They are:
1.

The oxidation number of atoms in uncombined elements = 0.

2.

In neutral compounds the algebraic sum of the oxidation numbers = 0.

3.

In ions, the algebraic sum of the oxidation numbers equals the charge on the ion.

4.

In any substance, t he more electro negative atom has the negative oxidation number, and
the less electronegative atom(s) has the positive oxidation number.
Remember that the elements in a formula are written in order of increasing
electronegativity.

5.

The oxidation number of hydrogen in all its compounds, except metal hydrides, is +1. (In
metal hydrides it is -1.)

6.

The oxidation number of oxygen is always -2 (except in peroxides when it is -1, and in
OF2 when it is +2).

* Remember that for the main groups of the periodic table: all Group I elements have a valency of
+1. All group II elements have a valency of +2. All Group III (or IUPAC 13) elements have a
valency of +3, but thallium also has a valency of +1. Group IV (or IUPAC 14) elements have a
valency of +2 or +4, with +4 being more common at the top of the group, and +2 being more
common at the bottom. The transition metals and most non-metal exhibit variable valencies, but
transition metals will usually have +2 as one of their valencies. The non-metals will have negative
valencies if they are written at the end o f the formula. The negative valency of a non-metal will
equal (simple group number - 8), thus sulfur has a valency of (6 - 8) = -2.

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