NCEA Level 2

—Year 12—

CHEMISTRY
— Workbook —
A write-in workbook with brief revision notes
covering all Achievement Standards for the
NCEA Level 2 Chemistry course.
• Clear, concise revision notes.
• NCEA questions including the 2003 external
exams.
Full answers detailing NCEA grades
(Achieved, Merit, Excellence) for all
externally assessed Achievement Standards.
N E W ,

B I G G E S T

S E L L I N G

S E R I E S ^

Gillian Ward
 AME YEAR 12 NCEA LEVEL 2 WORKBOOKS
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or excellence). The 2004 Editions contain the 2003 externals. You may prefer a Study Guide (see inside back cover).

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AME Year 12 Chemistry Workbook

NCEA Level 2

A write-in w o r k b o o k w i t h brief revision notes covering all

Achievement Standards f o r t h e NCEA Level 2 Chemistry course.

NCEA questions, including t h e 2003 external exams, w i t h full answers

detailing NCEA grades (Achieved, Merit, Excellence) are provided f o r
all externally assessed A c h i e v e m e n t Standards.

Gillian Ward

Z S / t PMicaUom (71%) AU
AME Year 12 Chemistry Workbook
NCEA Level 2
Gillian Ward
ISBN: 1-877291-57-9

This first edition published in New Zealand in 2004 by ESA Publications (NZ) Ltd

© Gillian Ward, 2004

© ESA Publications (NZ) Ltd, 2004
© NZQA in the original questions, 2004

This book is copyright.

Questions in this workbook include the 2003 external exams and NCEA questions.
These are reproduced with the permission of the New Zealand Qualifications Authority, who own the
copyright in the original questions.
The selection and arrangement of the questions, the answers, and assigning of A, M and E grades are entirely
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Infringements will be prosecuted.

Information relating to the Achievement Standards is taken from the NZQA publication, Assessment and
Certification Rules and Procedures for Secondary Schools 2003, and is current at time of publication. ESA
Publications (NZ) Ltd does not take any responsibility for subsequent changes to the Achievement Standards,
exam format or type of examination question. Should a student have any concerns they should:
• Check with a teacher.
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www.nzqa.govt.nz/ncea/

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Contents

Periodic table iv

Achievement Standard 90305 (Chemistry 2.1)

Internally assessed, 2 credits
Carry out qualitative analysis 1

Achievement Standard 90306 (Chemistry 2.2)

Internally assessed, 3 credits
Perform an acid-base volumetric analysis 7

Achievement Standard 90307 (Chemistry 2.3)

Internally assessed, 3 credits
Carry out a gravimetric or colorimetric analysis and solve related problems 15

Achievement Standard 90308 (Chemistry 2.4)

Externally assessed, 4 credits
Describe the nature of structure and bonding in different substances 27

Achievement Standard 90309 (Chemistry 2.5)

Externally assessed, 4 credits
Describe the structural formulae and reactions of compounds containing
selected organic functional groups 49

Achievement Standard 90310 (Chemistry 2.6)

Externally assessed, 4 credits
Describe principles of chemical reactivity 79

Achievement Standard 90311 (Chemistry 2.7)

Externally assessed, 4 credits
Describe oxidation-reduction reactions 105

Answers and explanations

2. 1 125
2. 2 125
2. 3 128
2. 4 134
2. 5 139
2. 6 146
2. 7 153
iv AME Year 12 Chemistry Workbook

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© ESA Publications (NZ) Ltd, Freephone 0800-372266

 NCEA
Achievement
90305 Standard

Carry out qualitative analysis 2.1

Internally assessed
2 credits

Solutions
A solution is formed by dissolving a solute (often a solid) into a solvent (often water). Qualitative
analysis identifies ions in a solution.
When two solutions are mixed, a precipitation reaction is said to occur when an insoluble solid (a
precipitate, abbreviated as ppt) forms; cations (positive ions) from one solution react with anions
(negative ions) from the other solution. (One way to remember the difference between a cation and an
anion is the't' in cations looks like a '+'.)

Ions not involved in the precipitation reaction are called spectator ions.

Solubility rules
Compounds Solubility Exceptions
Nitrates Soluble

Chlorides Soluble Silver chloride, AgCI; lead chloride, PbCl2

Iodides Soluble Silver iodide, Agl; lead iodide, Pbl2
Sulfates Soluble Lead sulfate, PbSC>4; calcium sulfate, CaSC>4; barium sulfate, BaSC>4

Hydroxides Insoluble Barium hydroxide Ba(OH)2 and Group 1 hydroxides (sodium hydroxide,
NaOH; potassium hydroxide, KOH)

Carbonates Insoluble Ammonium carbonate, (NH4)2CC>3 and Group 1 carbonates (sodium

carbonate, Na2C03; potassium carbonate, K2CO3)

Example

Two solutions, iron(ll) sulfate and sodium hydroxide, are mixed. Fe2+ S042-
The solubility rules show all sulfates are soluble and hydroxides are insoluble; Na+ - X
a precipitate of iron(ll) hydroxide forms. OH- • -

Carrying out a procedure to identify ions in solution

The practical part of Achievement Standard 2.1 involves mixing solutions, making observations, identifying
ions and writing ionic equations. You will be given a flowchart and a table of solubility rules, but not a table
of ions or ionic equations.

Mixing solutions
When carrying out a practical activity to determine ions in solution:
• Use (small) test tubes (not boiling tubes or beakers).
• Add small quantities of solution to the test tube (eg 1 mL - about a small finger width).
1
2 Chemistry Achievement Standard 2.3

• After adding different solutions, shake them to mix (ensures a reaction has occurred). This involves
flicking or tapping the base of the test tube gently. Do not place your thumb over the top of the test
tube and shake madly!

Making observations
• Observe whether a precipitate occurs; if it does, note the colour of the precipitate. If it doesn't, state 'no
ppt forms'.
• Observations need to clearly state what you see. Statements such as 'The substances form layers with a
gluggy and fluffy thing on top' are unnecessary and do not state the observations accurately or clearly.

Examples
1. When iron(ll) sulfate and sodium hydroxide are mixed, a dark green precipitate forms.

2. When potassium chloride and sodium hydroxide are mixed, no precipitate forms; a mixture of solutions
remain and these solutions are colourless.

Colourless implies no colour. Do not use the word clear - this means 'able to be seen through'.

Example
A solution of copper sulfate is coloured (blue) but is also clear (you can see through it).

Identifying ions
Testing for Anions

( j J Testing for OH" and CO, 2 " Ions

The formation of C0 2 is difficult to see in solution (the bubbles are quite small) and occurs over a short time - careful
observation is necessary.

(2) Testing for S0 4 2 " ions

Addition of dilute hydrochloric acid (dil HCI) prevents precipitation of carbonate ions (if these were present).
Barium ions are added to an unknown. Either barium chloride or barium nitrate can be added.
Barium ions will form a ppt with any sulfate ions that are present.
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 Carry out qualitative analysis 3

Q Testing for CI" and I" ions

Addition of dilute nitric acid (dil HN0 3 ) prevents precipitation of carbonate ions (if these are present)
as silver carbonate, Ag 2 C0 3 .

Testing for Cations

Pale blue ppt

Confirm by taking fresh Cu2+(aq) + 20H"(aq) -> Cu(OH)2(s)
Blue ppt forms sample and adding a few then dissolves in excess to give a deep blue solution of
Cu2+ present J drops then excess NH3 tetraammine copper(ll) ions
solution
CU(OH) 2 (S) + 4NH 3 (aq) [Cu(NH 3 ) 4 ] 2 + (aq) + 20H"(aq)

Brown ppt forms Confirm by taking fresh

Ag+ present • sample and adding a few
drops then excess NH3
White ppt forms solution Brown ppt
Mg2+, Al3+, Zn2+ or Pb2+ 2Ag+(aq) + 20H"(aq) Ag 2 0(s) + H 2 0
then dissolves in excess to give colourless solution of diammine
silver(l) ions
Mg2+(aq) + 20H~(aq) Mg(OH) 2 (s) Ag20(s) + H 2 0 + 4NH3(aq) 2[Ag(NH3)2 ]+(aq) + 20H"(aq)
Al3+(aq) + 30H-(aq) AI(OH) 3 (s)
Zn2+(aq) + 20H"(aq) Zn(OH) 2 (s)
White ppt dissolves in excess to form a colourless solution
Pb2+(aq) + 2QH~(aq) -> Pb(OH) 2 (s)
Zn present
ppt does not dissolve Zn2+(aq) + 20H"(aq) Zn(OH) 2 (s)
Add excess dil NaOH •
Mg2+ present Zn(OH) 2 (s) + 4NH3(aq) -> [Zn(NH3)4]2+(aq) + 2QH-(aq)
T
ppt dissolves to form colourless solution
Al3+, Zn2+ or Pb 2+ present Take fresh sample and
AI(OH) 3 (s) + OH"(aq) [AI(0H) 4 ]"(aq) add few drops then excess
Zn(OH) 2 (s) + 20H"(aq) ^ [Zn(OH)4]2"(aq) of NH3 solution
Pb(OH) 2 (s) + 2QH~(aq) ^ [Pb(OH) 4 ] 2 '(aq)
White ppt forms
Al3+ or Pb 2+ present
Al3+(aq) + 30H~(aq) - > AI(OH) 3 (s)
Pb2+(aq) + 20H~(aq) - > Pb(OH) 2 (s)

Take fresh sample White ppt forms

and add dil sulfuric Pb 2+ present
acid, H 2 S0 4 Pb2+(aq) + S042~(aq) PbS0 4 (s)

No ppt, colourless
solution forms
Al3+ present

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. 4 Chemistry Achievement Standard 2.4

© Testing for NH4+ ions

If NH4+ is present, a colourless gas, ammonia, NH3, will be given off, which will turn damp red litmus paper (placed
over the top of the test tube) blue.
The litmus paper must be moist, as the NH3 given off needs to dissolve in water to react with the litmus. The litmus
paper must not touch the test tube. The unknown may contain OH" or C032- ions and these will also turn red litmus
blue. You need to test the gas.

(2) Testing for Cu2+ ions

Addition of OH" ions will precipitate Cu(OH)2(s) from a solution containing copper ions:
Cu2+(aq) + 20H"(aq) -> Cu(OH)2(s)
Addition of dilute ammonia solution dil NH3 (aq) will also precipitate Cu(OH)2(s) from a solution containing copper
ions. This is because ammonia solution contains some hydroxide ions (as well as ammonia molecules, large amounts of
water, and some ammonium ions):
NH3(aq) + H 2 0 # NH4+(aq) + OH"(aq)
The reaction of ammonia solution with copper ions is:
Cu2+(aq) + 20H"(aq) -> Cu(OH)2(s)
When excess ammonia solution is added, the precipitate dissolves and a complex ion forms.
Cu2+(aq) + 4NH3(aq) [Cu(NH3)4 ]2+(aq)
deep blue solution
tetraammine copper(ll) ion
Similarly, this occurs for Zn2+ ions:
Zn2+(aq) + 20H'(aq) -> Zn(OH)2(aq)
Zn2+(aq) + 4NH3(aq) -» [Zn(NH3)4]2+(aq)

Writing equations
Equations for precipitation reactions, called i o n i c e q u a t i o n s , show only the ions involved in the reaction.
S p e c t a t o r i o n s are not included.

(aq) indicates an aqueous solution; (s) indicates a solid (ie a precipitate); (I) is a liquid; (g) is a gas.

Example

Copper sulfate solution, CuSC>4(aq), is added to sodium hydroxide solution, NaOH(aq). The reaction occurring is:

Cu2+(aq) + 20H"(aq) -> Cu(OH) 2 (s)

You cannot write ionic equations for reactions that do not occur!

Questions: Solutions
Use the S o l u b i l i t y r u l e s below to help you answer the following questions.

Solubility rules

Compounds Solubility Exceptions

Nitrates Soluble

Chlorides Soluble Silver chloride, AgCI; lead chloride, P b C b

Iodides Soluble Silver iodide, Agl; lead iodide, Pbl2

Sulfates Soluble Lead sulfate, PbSCU; calcium sulfate, CaSC>4; barium sulfate, BaS04

Hydroxides Insoluble Barium hydroxide Ba(OH)2 and Group 1 hydroxides (sodium hydroxide,
N a O H ; potassium hydroxide, K O H )

Carbonates Insoluble A m m o n i u m carbonate, (NH4)2COb and Group 1 carbonates (sodium

carbonate, Na2CC>3; potassium carbonate, K 2 C O 3 )

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 Carry out qualitative analysis 5

1. Will a precipitate form when the following solutions are mixed? If so, name the precipitate.

a. Sodium carbonate and zinc chloride.

b. Sodium sulfate and lead nitrate. _

c. Ammonium nitrate and calcium chloride

d. Silver nitrate and potassium iodide.

e. Sodium hydroxide and iron(ll) chloride.

2. A number of solutions are mixed together. Complete the table by deciding whether a precipitate will
form or not.

Solutions t h a t a r e mixed t o g e t h e r P r e c i p i t a t e f o r m s ? Yes/No

Barium chloride and sodium hydroxide

Sodium sulfate and magnesium nitrate b.

Sodium carbonate and copper chloride

Barium chloride and silver nitrate d.

Sodium chloride and potassium nitrate

3. Complete the following ionic equations.

a. + S042-(aq) PbS0 4 (s)

Cu2+(aq) + b. Cu(OH) 2 (s)

Al3+ (aq) + c. -> AI(OH) 3 (s)

4. Write balanced ionic equations for any reactions occurring when the following solutions are mixed
together:

a. Zinc chloride and sodium hydroxide.

b. Iron(ll) sulfate and potassium hydroxide.

c. Potassium chloride and sodium sulfate.

d. Barium chloride and sodium sulfate.

e. Iron(lll) chloride and sodium hydroxide.

f. Silver nitrate and sodium chloride.

5. Complete the following equations:

a. Cu(OH) 2 (s) + 4NH 3 (aq) -> i. + ii.

b. Zn(OH) 2 (s) + 2 0 H " (aq) -» i.

c. i. + H 2 0 + ii. -> 2[Ag(NH3)2]+(aq) + 20H"(aq)

d. Zn(OH) 2 (s) + 4NH 3 (aq) i. + ii.

e. i. + ii. -» [AI(OH) 4 ]"(aq)

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. 6 Chemistry Achievement Standard 2.4

6. A student takes a sample of solid lead hydroxide and adds excess dilute sodium hydroxide solution.
The solid dissolves to form a colourless solution. Write an ionic equation for the reaction.

7. A student takes a sample of solid aluminium hydroxide and adds excess dilute sodium hydroxide
solution. The solid dissolves to form a colourless solution. Write an ionic equation for the reaction.

8. Complete the following flow chart.

White ppt
of silver
chloride

*
Add dilute
NH3(aq)

1
White ppt dissolves. Equation is:

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 NCEA
Achievement
90306 Standard
Perform an acid-base volumetric
2.2
analysis Internally assessed
3 credits

Quantitative chemistry
Solutions and concentration
A solution formed from dissolving a solid in water is called an aqueous solution. The concentration of a
solution is the amount of dissolved solute in a given volume of solution. The unit for concentration is moles
per litre (mol L"1).

Example
The mass of 1 mol of sodium carbonate is 106 g. A 1 mol L" 1 solution of sodium carbonate contains 106 g in
one litre, a 2 mol L _ 1 solution of sodium carbonate contains 212 g (2 mol) in one litre.

Calculating concentration

c= y c— concentration (mol L -1 )
n = n u m ber of moles of d issolved sol ute (mol)
V = volume of solution (L)

Volume must be in litres. To convert millilitres to litres, divide by 1 000 (eg 100 mL is = 0.1 L).
1 000
The formula can be rearranged as n = cxV:V= — : c= —.
c y
Example
The concentration of a solution of NaOH in which there is 0.014 mole in 25.5 mL of solution is calculated
from:

©
When doing calculations:

©
Write the formula.
0.0140
0.0255
© ©
©
Substitute the values. (If
necessary, change mL into L.)
= 0.550 mol L
Write the answer with a suitable
Calculate the amount present, in moles, in number of significant figures (sf)
25 mL of 0.1 mol L"1 solution of NaOH. and include the unit(s). For
n= cxV 0 numbers less than 1, put a zero
in front of the number (eg 0.014
= 0.10x0.025
©
®
not .014)

= 2.5 x 10~3 mol

Significant figures
In practical work there will always be errors through imprecise equipment or inaccuracies with
measurement. Consequently, any measurement recorded or any calculations completed need to indicate
the uncertainty of the result and are therefore written to an appropriate number of significant figures (sf).
The significant figure includes all digits known with certainty, plus a last digit that is estimated.
. 8 Chemistry Achievement Standard 2.4

Significant figures in calculations

Answers to calculations should be rounded to the appropriate number of significant figures. This will be
determined by the number of significant figures in the least accurate number. When doing calculations,
keep the numbers in the calculator until you write down the final answer. Do not round during the
calculation.

Determining the number of significant figures

• All non-zero digits are significant (eg 5.26 g is written to 3 sf, 1.4 g is written to 2 sf).
• Zeros present between non-zero digits are significant (eg 5.403 g is written to 4 sf, 2.04 mol is written
to 3 sf).
• Zeros at the end of an answer and right of the decimal point are significant (eg 25.50 mL is written to
4 sf, 1.20 g is written to 3 sf, 40.10 g is written to 4 sf).
• Zeros at the beginning of an answer are not counted as significant (eg 0.0042 g is written to 2 sf,
0.03 g is written to 1 sf).

Questions: Significant figures

You would not be asked questions such as this for NCEA Level 2 Chemistry. To gain 'Excellence', answers
to calculations must be to an appropriate number of significant figures.

Round off each of the following measurements to three significant figures:

1. 1.232 x 10"4 mol 2. 26.23 mL 3. 0.07430 g
4. 1.3479 mol L"1 5. 2.453 x 10"3 mol L"1

Volumetric analysis
Volumetric analysis involves a titration. In a titration, a solution, of unknown concentration, is typically
titrated (added) from a burette into a flask. The flask typically contains a known amount of solution. If
the number of moles of one of the solutions is known, the number of moles of the other substance can be
found using the stoichiometry of the balanced reaction equation.
A standard solution has an accurately known concentration. Standard solutions are made in a
volumetric flask.
Primary standards - the concentration is determined by directly weighing a reactant and dissolving the
reactant to give a solution of known volume.
A suitable primary standard must:
• Be readily available in a pure form.
• Resist absorbing water from the air.
• Be unreactive when stored.
• Have a high molar mass so weighing errors are less significant.
Secondary standards - the concentration is determined in a previous experiment where the solution is
standardised by titrating against a primary standard.

Example
Sodium carbonate makes a good primary standard, but sodium hydroxide does not, as it absorbs water.

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 Perform an acid-base volumetric analysis 9

Preparing a primary standard solution

spatula
and solute ,
Step one small beaker
• -s
Accurately weigh the required solute (ie primary standard reagent)
into a clean, dry, glass container, eg a small beaker. Record the
amount of solute used.
I
««

lu ' ' 11 3 0
electronic balance readout gives mass
reads zero after tare of solute
button pressed
Step two

Transfer the solute to a volumetric flask using a funnel

and wash-bottle. Take care to transfer all the solute to
the volumetric flask. Use deionised water if available.

solute is a wash-bottle is <r>

added used to ensure
transfer of solute
is complete
Step three

Partially fill the volumetric flask with deionised water,

stopper and shake to dissolve the solute.
stopper flask shake to
dissolve solute
Step four
O
Remove stopper and let any solution run down from the top of
- volume the neck of the volumetric flask. Add deionised water to fill the
mark volumetric flask up to the volume mark. Ensure the bottom of the
meniscus sits on the volume mark. Stopper flask and label it, stating
the name and concentration of the solution
volumetric
flask

In practice it is hard to w e i g h exactly the required mass, so a mass close to that required, but accurately
known, is w e i g h e d out.

Preparing a secondary standard solution

The solution is m a d e up to the approximate concentration required. A titration is then carried out to find
the exact concentration. This procedure is called s t a n d a r d i s i n g the solution.

Sodium hydroxide a n d hydrochloric acid can be prepared as secondary standards.

Equipment used in a titration

Burette 0 the volume
The standard solution usually goes in a burette. of the burette
10 is read from
The burette must be clean and rinsed out with a small amount of the solution that will go 20 the bottom of
into it. The volume of the solution in the burette is read from the bottom of the meniscus. the meniscus
30
The volume of solution delivered by the burette is called a titre.
40
• Clamp the burette firm and straight. 50
• If using a funnel to fill the burette, do not leave it in the burette during
60
the titration, as it may drip and lead to inaccuracies.
70
• Use a white background (eg white paper) to help with the reading.
80
• To clean, rinse thoroughly with cold water.
• Record the burette reading to 2 decimal places (eg 21.20 mL), otherwise accuracy is «T?0
reduced.
. 10 Chemistry Achievement Standard 2.4

pipette Pipette
0 filler
A pipette is calibrated to provide an exact volume of solution. It usually dispenses the
solution whose concentration is to be determined. The pipette must be clean and can be

&
volume rinsed out with a small amount of the solution to be pipetted (preventing dilution of the
mark
solution). A pipette filler is used to fill and dispense the solution. The fixed volume of
solution dispensed by the pipette is called an aliquot.
pipette
• Allow the solution to run from the pipette and touch the pipette gently against the
side of the flask.
• Do not blow out of the pipette.
• Do not shake or bang the pipette on the side of the flask.
• To clean, rinse thoroughly with cold water.

Flasks
The reaction is carried out in conical flasks. Each flask is first rinsed out with distilled water (tap water may contain chemicals that
interfere with the titration) - this does not alter the amount (ie number of moles) of dissolved solute.

Usually a pilot titration is completed first - a titration done quickly to give a rough idea of where the
end point (the point at which the solution just changes colour) would be. (This first flask can be used as
a reference colour for further titrations.) Titrations are repeated until three concordant results are achieved
(ie titres are within 0.2 mL of each other).

Acid-base titrations
An acid-base titration involves a neutralisation reaction between an acidic solution and a basic
solution. The concentration of one of the solutions is known - the aim of the titration is to determine the
concentration of the other solution.
Indicator
An indicator is a dye that changes colour with a change in pH. The indicator will change colour at the end
point.

Indicator Colour in acid Colour in base

Phenolphthalein Colourless Bright pink

Methyl orange Red Orange

• To check what colour an indicator turns, add it to a sample of acid and a sample of base.
• Use small amounts of indicator in a titration.
• Ensure the titration stops at the point where one drop of reactant causes the indicator to change colour.

The titration
A solution is pipetted into a conical flask. A few drops of indicator are added. The solution from the
burette is added with one hand while the flask is swirled with the other. A w a s h bottle is used to wash
splashes from the sides of the flask and drops at the end of the burette into the conical flask solution.
The titration is complete when the indicator just changes colour. This is the end point, the point at which:
• All the solution in the flask has reacted with the solution added from the burette.
• The solutions have reacted according to the stoichiometry of the reaction equation.
The volume of solution from the burette should be recorded in a table.
• Record the initial and final values.
• It is not good practice to begin a titration at 0.00 mL.
• You do not need to fill the burette up each time you carry out a titration.
• Record your results to two decimal places.

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 Perform an acid-base volumetric analysis 11

Example
Table of results

Titration

One Two Three Four

Initial reading (mL) 2.00 21.65 3.20 21.65

Final reading (mL) 21.65 40.05 21.65 40.00

Volume of solution from burette 19.65 18.40 18.45 18.35

The average titre value is calculated by averaging the concordant results (for 'Excellence' these must be within
0.2 mL). For the above results, you would average titrations Two, Three and Four.

Checklist of good practice techniques to ensure accuracy

Use this checklist when practising titrations. You and a lab partner could test each other.

Check
Equipment Technique
/ orX

Flask Before starting, rinse the flask with distilled water.

Put a piece of white paper or a white tile under the flask so that a colour change can be seen easily.

Swirl the flask with one hand and add solution from the burette at the same time with the other
hand.

Pipette Before starting, rinse out with the solution you are going to pipette.

Make sure when measuring the volume of solution the bottom of the meniscus sits 'on the mark' on
the pipette.

Allow the solution to run from the pipette and touch the pipette gently against the side of the flask.

Do not blow residual material out of the pipette.

Do not shake or bang the pipette on the side of the flask.

To clean, rinse thoroughly with cold water.

Burette Before starting, rinse out with the solution you are going to put in the burette.

Clamp the burette firmly and ensure it is straight up and down.

If using a funnel to fill the burette, do not leave it in the burette during the titration, as it may drip
and lead to inaccuracies.

When reading a burette, read the volume at the bottom of the meniscus. Use a white background
(eg white paper) to help with the reading.

Three concordant results (± 0.2 mL) should be achieved.

To clean, rinse thoroughly with cold water.

W a s h b o t t l e The wash bottle is not used as a washing up tool.

Use it to wash any drops off the end of the burette and to wash off drops around the flask into the
reacting mixture.

Indicator Use small amounts of indicator.

Ensure the titration stops at the point where the indicator just changes colour.

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. 12 Chemistry Achievement Standard 2.4

Steps in determining t h e concentration of an u n k n o w n solution

Example
Determining t h e c o n c e n t r a t i o n of a hydrochloric acid solution

15.0 mL of 0.200 mol L"1 sodium hydroxide solution, NaOH, is pipetted into a flask. A few drops of
phenolphthalein is added. Hydrochloric acid, HCI, is added to the burette. Five titrations were completed before
three concordant results were achieved. The concentration of the HCI solution is determined.
start of titration end of titration

pipette

bright pink solution colourless solution

1. The equation for the reaction is:

HCI + NaOH -> NaCI + H 2 0

Results

Titration Initial reading (mL) Final reading (mL) Titre (mL)

1 (pilot) 1.00 16.76 15.76

2 15.76 35.86 20.10

3 2.38 22.38 20.00

4 22.38 43.10 20.72

5 1.50 21.40 19.90

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 Perform an acid-base volumetric analysis 13

2. Concordant results (within a range of 0.2 mL for 'Excellence') are achieved from titrations 2, 3 and 5.

/ , (20.10 + 20.00 + 19.90) „ „ ,

Average titre (volume of HCI) is - = 20.00 mL

3. Number of moles of standard solution (NaOH) is:

r?(NaOH) =cxl/
= 0.200x0.0150 Volume is expressed in litres; 15,0 m L = 0.0150 L
1000
= 0.00300 mole
4. From the equation, 1 mole of NaOH reacts with 1 mole of HCI, so, 0.003 mole of NaOH reacts with
0.003 mole of HCI.
5. Concentratiosn of the unknown solution, HCI, is:
n

~V

_ 0.00300 Always convert mL into L (divide the mL value by 1 000); ie average titre of 20.0 mL
~ 0.0200 divided by 1 000.

= 0.150 mol L' 1 Include units and give answer to 3 significant figures; round figures only at the end of
the calculation.

Questions: Volumetric analysis

1. 20.0 mL aliquots of standardised 0.100 Titration Volume of HCI used in titration (mL)
mol L"1 sodium hydroxide, NaOH, were 1 23.50
titrated with hydrochloric acid, HCI, using
2 21.00
phenolphthalein as an indicator. The
equation for the reaction is: 3 21.50

HCI + NaOH -> NaCI + H 2 0 4 21.50

The results obtained are shown in the 5 20.00

table. Calculate the concentration of
the HCI solution. Give your answer to three significant figures.

2. A standard solution of 0.210 mol L 1 sodium carbonate, Na2C03, was titrated with hydrochloric acid
solution, HCI. 10.0 mL samples of sodium carbonate were pipetted into four flasks.

The volumes 18.10 mL, 14.80 mL, 14.90 mL and 14.70 mL of HCI were used in each titration.

The equation for the reaction is: Na2C03 + 2HCI -» 2NaCI + H2O + C O 2

Determine the concentration of the HCI solution. Give your answer to three significant figures.

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. 14 Chemistry Achievement Standard 2.4

3. A standard solution of 0.350 mol L 1 sodium hydroxide, NaOH, was titrated against 10.0 mL samples
of ethanoic acid, CH 3 COOH.

The equation is: NaOH + CH 3 COOH CH 3 COONa + H 2 0

The volumes of NaOH used for each titration were 23.00 mL, 20.48 mL, 20.45 mL, 19.50 mL
and 20.40 mL. Calculate the concentration of the ethanoic acid.

4. A standard solution of 0.150 mol L _1 Titration Volume of HCI used in titration (mL)
hydrochloric acid, HCI, was titrated against
1 28.00
20.0 mL samples of sodium hydroxide
2 26.26
solution, NaOH. The table shows the results
of the titration. 3 26.18

The equation for the reaction is: 4 26.21

HCI + NaOH NaCI + H 2 0

Calculate the concentration of the unknown solution to three significant figures.

5. Four 20.0 mL aliquots of sodium carbonate solution, Na 2 C03, were pipetted into conical flasks. Four
titrations were carried out with a standard solution of 0.230 mol L"1 of hydrochloric acid solution, HCI.
The four titre values were 22.00 mL, 20.56 mL, 20.50 mL and 20.48 mL.

The equation for the reaction is: Na 2 C0 3 + 2HCI -> 2NaCI + H 2 0 + C 0 2

Calculate the concentration of the sodium carbonate solution. Give your answer to three significant figures.

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 NCEA
Achievement
90307 Standard
Carry out a gravimetric
analysis and solve related
or colorimetric
problems
2.3
Internally assessed
3 credits

Moles and stoichiometry

Amounts in chemistry are measured in

moles (abbreviation mol, symbol n).
n(H2) means the 'amount of hydrogen 58.5 g sodium chloride
in moles'. 18 g water
A mole always contains 6.02 x 1023
particles (rounded to 6 x 1023 in this 1 mole
book). This number has been given the 6 x 1023 particles

name Avogadro's number (symbol

N a ). A mole of different substances
always contains 6 x 1023 particles, but 4 g helium
197 g gold
can be a different mass.

Molar mass
Molar mass (symbol M, units 'gram per mole' or g moM) is the mass of one mole of an element,
compound or ion.

Example
1. Molar mass of C 0 2
44
M ( C 0 2 ) = M(C) + [2 x /W(0)] A carbon dioxide molecule is y j times heavier than
= 12.0+ (2x16.0) an atom of carbon-12.

= 44.0 g mol-1
The masses of ions are very similar to the masses of
2. Molar mass of CaS0 4
the atoms they are derived from; the molar mass of
M(CaS0 4 ) = M(Ca) + M(S) + [4 x M(O)] an ionic substance (eg CaS0 4 ) is regarded as being
= 40.1 + 32.0+ (4 x 16.0) made up of calcium atoms, sulfur atoms and oxygen
atoms.
= 1 36.2 g moh 1

Mole calculations
n is measured in moles (mol)
m(mass of substance)
/7(amount of substance) = m is measured in grams (g)
M(molar mass of substance)
M is measured in grams per mol (g moH).

The equation can be arranged as follows:

m = nM and M =
n
16 Chemistry Achievement Standard 2.3

Example
1. The mass of 2 mol of oxygen gas is:

m = nM
= 2 mol x 32.0 g mol" 1 M { 0 2 ) = 2 x 16.0 = 32 gmol" 1
= 64.0 g

2. The amount of sodium in 2.00 kg of sodium chloride is:

n =-^- M(NaCI) = 23 + 35.5 = 58.5 gmol"

2000 g
= 58.5 g mol"— m is in grams, so convert kg to g by x 1 000.

= 34.2 mol The answer 34.2 mol is written to 3 significant figures.

Chemical equations
A chemical equation is a way of summarising what happens in a reaction.

Reactants —> Products

Substances that mix together and Can be read as 'to form' Substances produced in the reaction
react - written on left of the equation ~w r i t t e n o n t h e ri9ht o f t h e equation
Example
Magnesium + oxygen —> magnesium oxide

can be read as:

The reactants, magnesium and oxygen, react together to form the product, magnesium oxide.

The correct formulae must be shown and the equation must be balanced (ie there is the same number of
each kind of atom on each side of the equation and the total charge is the same on each side). States (or
phases) are sometimes shown.
2HCI(aq) + Na 2 C0 3 (s) -> 2NaCI(aq) + H 2 0(l) + C0 2 (g)
(aq) = aqueous solution (s) = solid (I) = liquid (g) = gas

Using mole calculations and balanced equations

Mole calculations and balanced equations are used to calculate amounts of products and reactants for
chemical reactions, using the following steps:
1. Find the amount (in moles) of the known substance.
2. Use the ratio of moles in the equation to work out the number of moles of unknown substance.
3. Work out the mass of the unknown substance.
Example
What is the mass of sulfuric acid formed when 4 kilograms of sulfur trioxide dissolves in water?

M ( S 0 3 ) = 80.0 g mol" 1 and M(H2S04) = 98.0 g mol" 1

The equation for the reaction is: S 0 3 + H 2 0 —> H 2 S 0 4

Answer:

1. n(sulfur trioxide) =
M

4000
Convert 4 kg into g (4 x 1 000).
80.0
= 50.0 mol

2. From the equation, 1 mol of sulfur trioxide reacts to form 1 mol of sulfuric acid -

so, 50.0 mol of sulfur trioxide reacts to form 50.0 mol of sulfuric acid.

3. m(sulfuric acid) = r) x M
= 50 x 98
= 4900 g
= 4.90 kg
 Carry out a gravimetric or colorimetric analysis and solve related problems 1/

Questions: Moles and stoichiometry

Molar masses (g mol"1)

H = 1.00 C = 12.0 N = 14.0 O = 16.0 Na = 23.0 Mg = 24.3 S = 32.1
CI = 35.5 K = 39.1 Ca = 40.1 Fe = 55.9 Cu = 63.5 Zn = 65.4

3ive answers to all questions to 3 significant figures where appropriate.

1. Calculate the molar mass of:

a. CuS

b. CaC0 3

c. CaS0 4 .2H 2 0

2. Calculate the mass, in grams, for each of the following (show all working):

a. 5 mol 0 2

b. 2 mol NaOH

c. 0.241 mol Na 2 S0 4

3. Calculate the amount of substance, in moles, for each of the following:

a. 60.0 g MgCI 2

b. 12.0 g KOH

c. 2.0 kg C 6 H 1 2 0 6

4. Magnesium burns in air to form magnesium oxide. The balanced equation is:

2Mg + 0 2 -> 2MgO

What mass of magnesium has completely burned in oxygen to form 2.60 g magnesium oxide?
. 18 Chemistry Achievement Standard 2.4

5. Chlorine gas reacts with excess sodium iodide to produce sodium chloride and iodine, according to
the following equation:

Cl2 + 2Nal -> 2NaCI + l 2

If 12.8 g of chlorine gas is reacted with excess sodium iodide, how many grams of sodium chloride are
produced?

Percentage composition
The mass of the different elements within a compound can be expressed as a percentage of the total mass
(percentage composition) - this can be used to identify a compound.

Example
Find the percentage composition of ethane, C 2 H 6

1. 1 mole of C 2 H 6 contains 2 mol of C and 6 mol of H.

2. The mass of C present is 2 x 12.0 = 24.0 g

The mass of H present is 6 x 1.0 = 6.0 g

3. The mass of 1 mole of C 2 H 6 is 30.0 g, so the percentage composition

24.0
o f C i s — — x 100 = 80.0%
30.0 6Q
The percentage composition of H is x 100 = 20.0%.

4. 8 0 % C + 2 0 % H = 1 0 0 % (Checked.)

Empirical formula
An empirical formula can be calculated from the percentage composition. It is the simplest whole
number ratio of the atoms in a compound.

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 Carry out a gravimetric or colorimetric analysis and solve related problems1/

Example
Analysis of a compound showed that it contained 14.29% H and 85.71% carbon.
^ ^ In 100 g of compound there is:
14.29 g of H
85.71 g of C

^ ^ In 100 g of compound there is:

i y ? = 14.29 mol H [since M ( H ) = 1 g mol"1]

^ = 7.14 mol C [since M (C) = 12 g moP1]

0 Moles of H Moles of C
7.14
^=2.001 •= 1
7.14 7.14

@ Moles of H Moles of C

2.001 = 2 1

The empirical formula of the

compound is CH2.

Molecular formula
The molecular formula can be determined from the empirical formula and molar mass. It gives the
actual number of atoms present.

Example
The empirical formula of a compound was found to be CH 2 0.
If the molar mass is 60.0 g moh1, find the molecular formula.
molar mass
x =
molar mass of empirical formula
60.0
~ 30.0
= 2

Molecular formula = (CH 2 0) x

= (CH 2 0) 2

The molecular formula is C 2 H 4 0 2

Gravimetric analysis
In some substances, water is part of the crystal, and is known as the w a t e r of crystallisation - eg
CUS04.5H20 is the formula for copper sulfate that contains 5 moles of water for every mole of CuS0 4 .
CuS0 4 .5H 2 0 is known as a hydrated solid or a hydrous solid. Sometimes, heating the compound can
drive off the water of crystallisation. A compound without the water of crystallisation is known as an
anhydrous solid.
Gravimetric analysis can be used to determine the water of crystallisation in a substance.
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. 20 Chemistry Achievement Standard 2.4

Finding the water of crystallisation of a substance

In A c h i e v e m e n t S t a n d a r d 2.3 y o u will be g i v e n the p r o c e d u r e that y o u n e e d to carry out a n d y o u will need
to c o m p l e t e the practical e x p e r i m e n t a n d d o the calculations to find o u t t h e w a t e r of crystallisation in t h e
substance that has b e e n g i v e n to y o u .

W h e n carrying o u t a g r a v i m e t r i c analysis:

• A l w a y s m a k e sure t h e crucible is clean a n d dry. You d o not w a n t o t h e r substances to be present that

w o u l d reduce t h e a c c u r a c y of t h e w e i g h i n g .

• T h e crucible s h o u l d b e w e i g h e d as soon as it is c o o l e d to p r e v e n t t h e a n h y d r o u s solid f r o m regaining

w a t e r of crystallisation.

• If possible, repeat h e a t i n g to ensure all t h e w a t e r of crystallisation is driven off ( r e m o v e d ) .

Example

Finding the formula of hydrated magnesium sulfate M g S 0 4 . x H 2 0 .

heating

MgS04.xH20 >• MgS0 4 (s) + H 2 0 ( g )

Method

Record all your results in a s y s t e m a t i c f o r m a t

1. Weigh a clean, dry crucible and lid. Record the mass.

2. Add about 1 g of magnesium sulfate crystals to the crucible and reweigh.

3. Heat the crucible with the lid on, gently at first and then strongly for 5 minutes.
Remove the lid and continue to heat strongly for a further 5 minutes.

4. Allow to cool, reweigh and record mass.

5. Repeat heating, cooling and reweighing until two masses are within 0.05 g.

Results

mass of crucible + lid 30.14 g

mass of crucible + lid + M g S 0 4 . x H 2 0 31.30 g
First weighing
mass of crucible + lid + contents
Second weighing
mass of crucible + lid + contents
Third weighing
mass of crucible + lid + contents
Average weighing
mass of crucible + lid + contents

Calculations

Data M ( M g S 0 4 ) = 120 g mol" 1 ; M ( H 2 0 ) = 18.0 g mol" 1 .

1. Mass of the anhydrous magnesium sulfate This is at an 'Achieved' (A) level of complexity.

30.71 - 30.14 = 0.57 g of anhydrous magnesium sulfate.

2. Amount, in moles, of anhydrous magnesium sulfate This is at a 'Merit' (/W) level of complexity.
m of anhydrous MgS0 4
n =
M of anhydrous MgS0 4
0.57
120
: 4.75 x 10" 3 mol

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 Carry out a gravimetric or colorimetric analysis and solve related problems 27

3. Mass of water driven off This is at an 'Achieved' (A) level of complexity.

31.30 - 30.71 = 0.59 g of water driven off.

Could also calculate by:

M g S 0 4 . x H 2 0 weighed - mass of anhydrous M g S 0 4

1.16 - 0 . 5 7 = 0.59 g

4. Amount, In moles, of water driven off This is at a 'Merit' ( M ) level of complexity.

m of water driven off
n =
M of water
0.59
~ 18.0

= 0.0328 mol
This offers 'Merit' (Af) and 'Excellence' (£) levels of complexity.
5. Mole ratio to 3 sf

Mole ratio n ( M g S 0 4 ) : n ( H 2 0 )

4.75 x 10-3 : 0.0328

1.00 : 6.90

Using mole ratio value to determine the formula of the hydrated salt
Formula of the hydrated salt is M g S 0 4 . 7 H 2 0
\

Questions: Percentage composition and gravimetric analysis

M o l a r masses ( g m o H )

H = 1.00 B = 10.8 C = 12.0 N = 14.0

O = 16.0 N a = 23.0 CI = 35.5 Fe = 55.9

G i v e answers to 3 significant figures w h e r e appropriate.

1. Find t h e p e r c e n t a g e c o m p o s i t i o n of e a c h of t h e elements w i t h i n t h e f o l l o w i n g c o m p o u n d s :

a. CH3NH2

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. 22 Chemistry Achievement Standard 2.4

b. NH 4 CI0 4

2. Borax, Na 2 B 4 0 7/ is used as a cockroach and ant poison. What is the percentage of boron in borax?

3. Urea is used as a fertiliser because it is an important source of nitrogen. The formula for urea is
CO(NH 2 )2- What is the percentage of N in urea?

4. What is the empirical formula of a compound that contains 52.1 7 % carbon, 1 3.04% hydrogen and
34.78% oxygen?

5. A compound contains 30.43% nitrogen and 69.57% oxygen.

What is the empirical formula of the compound?

If the molar mass of the compound is 92.0 g moH, what is the molecular formula?

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 Carry out a gravimetric or colorimetric analysis and solve related problems 29

6. Find the empirical formula for the compound that contains 40.0% carbon, 6.67% hydrogen and
53.33% oxygen.

If the molar mass of the compound is 180 g mol"1, what is the molecular formula?

Concentration
Prior knowledge of concentration from Achievement Standard 2.2 is assumed.

Calculating the mass of solid needed to make up a solution

Mass is related to number of moles and molar mass by:
m = nx M m = mass (g)

n = number of moles

M = molar mass (g mol" 1 )

Examples
1. Calculate the mass of NaCI required to make up a 0.500 mol L"1 solution of NaCI in a 250.0 mL volumetric
flask. M(Na) =23.0 g mol"1 M(CI) =35.5 g mol"1
The molar mass of NaCI and both formulae are needed.
M(NaCI) = 58.5 g mol"1
n(NaCI) = cV
= 0.500 x 0.250
= 0.125 mol
m(NaCI) =nx M
= 0.125 x 58.5
= 7.31 g
7.31 g of NaCI would be weighed out on a balance and then added to some water in a 250 mL volumetric
flask, shaken and then made up with water to the 250 mL mark.

2. 2.20 g of NaOH is dissolved in 500 mL of water. What is the concentration of the solution?
M(NaOH) = 40.0 g mol"'.
m 2.20
n(NaOH) =— = = 0.0550 mol
v ' M 40.0
n 0.0550
c(NaOH) =— = = 0.110 mol L"'
V 0.500

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. 24 Chemistry Achievement Standard 2.4

Diluting solutions
Aqueous solutions can be diluted by adding water.
Original solution contains Dilute solution contains
0.02 mol of solid 0.02 mol of solid

add 90 mL 100 mL
water

•10 mL

The solution contains The solution is diluted by

0.02 mol of solute in 10 mL adding 90 mL of water; the
of solution amount of solute is the
same; the volume is now
100 mL
n 0.02 _ ..1 n 0.02 n _ ..,
C =— = = 2 mol L 1 c=— = = 0.2 mol L 1
V 0.01 V 0.1
Increasing the volume of water 10 times decreases the concentration by 10 times.

Calculating dilutions
The concentration of an aqueous solution after dilution can be calculated using the formula:

c,!/, = c2V2
Example
Calculate the concentration of 20.0 mL of a 0.100 KOH solution after it has been diluted to 100 mL.

c, V, = c2V2

c2 = c. Rearranging equation.
^2
c(KOH) = 0.100 X 0.020 = 0.0200 mol L"1
0.100

Mass concentration
Mass concentration can be used to express concentration where the mass of the solute is used. The unit is
grams per litre, g L_1.
m
c = 7
Example
0.200 g of KOH is dissolved in 100.0 mL of water. What is the concentration in grams per litre, g L"1?
m 0.200 , .
c—— = = 2.00a g L-1
V 0.100

Interconversion of g L1 and mol L1

Grams per litre can be changed into moles per litre and vice versa if the molar mass of the solute is known.

To convert grams per litre into moles per litre

Divide the value in grams per litre by the molar mass.

Example
The molar mass of KOH is 56.0 g mol-1. To convert a mass concentration of 2.00 g L*1 into mol L~1:
2.00 g L"1
3 = n0.0357
r i mol1 L"
I
56.0 g L"1

To convert moles per litre into grams per litre

Multiply the molar mass by the value in moles per litre.

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 Carry out a gravimetric or colorimetric analysis and solve related problems 25

Example
The molar mass of KOH is 56.0 g mol"1. To convert 0.0620 mol L' 1 of KOH into g L"1:

c= 56.0 g moh1 x 0.0620 mol L"'= 3.47 g L"1

Colorimetric analysis
Colorimetry can be used to find the concentration of a coloured solution by comparing the intensity of the
coloured solution with the colours of different concentrations of that solution, using:
• The eyes - ie looking at and comparing the coloured solutions.
• A colorimeter - a simple spectrophotometer.

Colorimetry by eye
This involves making up a range of diluted solutions, called standard solutions, of the same compound.
The unknown is compared to the range of standards and the concentration estimated.
• The range of standards should represent narrow intervals so the estimate of the concentration of the
unknown can be as accurate as possible.
• The set of standards should be such that the unknown does not lie near the outer concentration of the
range of standards.
• Look at the colours against a white background.
• Look down the tubes from above when comparing colours.

Questions: Concentration

Molar masses (g mol-1)

NaOH = 40.0 Na 2 S0 4 = 142 KCI = 74.5 Na 2 C0 3 = 106

NaCI = 58.5 CuS0 4 .5H 2 0 = 249.5 HCI = 36.5

1. Find the concentration of the following solutions in mol L"1.

a. 0.0102 mol Na 2 S0 4 in 35.0 mL of solution.

b. 0.00100 mol KCI in 5.00 mL of solution.

2. Determine the amount of substance present, in moles, in each of the following solutions:
a. 500.0 mL of a 0.0200 mol L~1 CuS0 4 .5H 2 0 solution.

b. 10.0 mL of a 0.100 mol L"1 NaCI solution.

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. 26 Chemistry Achievement Standard 2.4

3. Calculate the concentration, in mol Lr1 of the following solutions:

a. 2.12 g Na 2 SQ 4 in 250.0 mL of solution.

b. 0.0220 g NaCI in 20.0 mL of solution

4. Determine the mass, in grams, of NaOH solid needed to prepare 250 mL of a 0.100 mol L _1 solution.

5. What mass of solid is needed to prepare 250 mL of a 0.100 mol L~1 CuS0 4 .5H 2 0 solution?

6. Calculate the concentration of the following solutions after dilution:

a. 20.0 mL of a 0.500 mol L"1 Na 2 CQ 3 solution is diluted to 100 mL.

b. 1.00 mL of a 0.100 mol L"1 solution of HCI is diluted by adding 9 mL of water.

7. Calculate the concentration of the following solutions after dilution,

a. 0.100 mol NaCI in 250 mL of solution is diluted to 500 mL.

b. 0.0500 mol HCI in 25.0 mL of solution is diluted to 100.0 mL.

8. Convert a 0.0333 mol L~1 solution of NaCI into g L"1.

9. Convert a 0.379 g L~1 solution of Na 2 C0 3 into mol L_1.

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 NCEA
90308 Achievement
Standard
Describe the nature of structure and
bonding in different substances
Externally assessed
4 credits

Chemical bonding and Lewis Structures

This chapter assumes knowledge of atomic structure.

Chemical bonding and Lewis structures

Helium, neon and argon exist as separate and isolated atoms. Each of these atoms has a stable outer
energy level.

Most elements contain more than one atom; the atoms are held together by chemical bonds.
Atoms can achieve a stable outer shell by either losing electrons, gaining electrons from another atom, or
sharing electrons with another atom.

Types of bonding

Ionic bonding
Electrons are transferred from atoms that lose electrons to form positive ions (cations) to atoms that gain
these electrons to form negative ions (anions). The positive and negative ions attract one another. This
electrostatic attraction is known as an ionic bond.

Example
In the reaction between sodium metal and chlorine gas, a new substance is formed, called sodium chloride.

S o d i u m - metal, on left-hand side of periodic table; atomic number = 11; electron arrangement 2, 8, 1.

Each sodium atom in the sodium metal loses one electron to gain a stable outer energy level:

Na 2,8, 1 loses one electron -> Na+ 2,8

Chlorine - non-metal, on right-hand side of periodic table; atomic number = 1 7; electron arrangement 2, 8, 7.

Each chlorine atom in chlorine gas gains an electron from a sodium atom to gain a stable outer shell:

CI 2, 8, 7 gains one electron -> CI" 2,8,8

33
. 28 Chemistry Achievement Standard 2.4

Covalent bonding
The sharing of electrons (to achieve stability) forms a covalent bond. These bonding electrons 'belong' to
both atoms at the same time. Covalent bonds form between non-metals.

Example
Chlorine has the electron arrangement 2, 8, 7. The gain of one electron would make it stable (2, 8, 8). By
sharing an electron with another chlorine atom, stability is achieved.
Two atoms of chlorine Two atoms of chlorine
covalently bonded together

valence bonding
electrons

nucleus (inner-shell Outer shells overlap and a pair of

electrons not shown) electrons are shared. Each atom
now has a stable valence shell of
eight electrons at any one time.

Lewis structures
Lewis structures (also called electron dot diagrams) can be used to represent the formation of the
covalent bond.
non-bonding electron

covalent •• •• •• ••
SCI* .CI J SCI Sci S sci
•• — ••
ci:
bonding

bonding electron

The shared electrons are called bonding electrons. The electrons not involved in bonding are called non-
bonding electrons or lone pairs of electrons.

Shared electrons are often represented by a line; eg chlorine is CI—CI.

Example

H • + •CIS -*- H sci: H —CIS or H —CI

A hydrogen atom and chlorine atom share electrons to gain stable outer energy levels. Hydrogen achieves a full
outer shell of two electrons. A hydrogen chloride molecule, H-CI, is formed.

Atoms that share more than one pair of electrons, as double or triple bonds, form a multiple covalent
bond.

Examples
1. The oxygen molecule, 0 2 , is bonded together
lo
• s s o•: or J o• = O*
•
by a d o u b l e b o n d .

2. The nitrogen molecule, N 2 , is bonded

together by a t r i p l e b o n d .
SIM •• N S or I N = NS

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 Describe the nature of structure and bonding in different substances 29

Drawing complex Lewis structures

Follow the procedure outlined below for water and carbon dioxide.

Example

© Water, H 2 0 Carbon dioxide, C0 2

•• •• ••
•H «H o: c :o o:

© Oxygen, 0, is the
central atom. Two
Carbon, C, is the
central atom. Two
hydrogen atoms, H oxygen atoms, 0 and
and H, are the outer 0, are the outer
atoms. atoms.

H* o: *H SO 0!

© Share an electron
from each H atom
Share an electron
from each 0 atom
with an electron from with an electron from
the 0 atom. the C atom.
•• * ••
HSOSH •o:c:o#

Each H atom has a Each 0 atom has only

full valence shell. No seven valence
additional bonds are electrons. Share
necessary. another electron each
to form double bonds.

:o::c::d:

© Eight electrons Eight electrons

around the 0 atom - around the C atom -
the Lewis structure is the Lewis structure is
complete. complete.

Non-polar covalent bonds

A non-polar covalent bond forms when a shared electron pair is attracted to the nuclei of both atoms
equally. The shared electrons are found half-way between the atoms. This kind of bond is formed between
non-metal atoms that are identical.

Polar covalent bonds

A polar covalent bond forms when electrons are shared unequally between atoms. The shared electrons are
attracted to (and thus found closer to) one atom more than the other. Polar covalent bonds are formed
between non-metal atoms from different elements.
The atom that attracts the bonding pair(s) more is said to be more electronegative than the other
atom. Electronegativity describes how strongly bonding electrons are attracted to the nucleus of an atom.
Elements on the right-hand side of the periodic table are the most electronegative.
• Electrons are found closer to the more electronegative atom - this atom will have a slightly negative
charge (shown by 5-).

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. 30 Chemistry Achievement Standard 2.4

• The less electronegative atom will have the electrons drawn away from it - this atom will have a slightly
positive charge (shown by 8+).
Charge separation is called a dipole. A polar bond has a bond dipole.

Example
Hydrogen chloride

valence electron cloud shows that

the electrons spend most of their
5+ 8- time orbiting the chlorine atom

The electron cloud shows that the electrons are closer to the chlorine atom most of the time. The chlorine atom
is slightly negative and the hydrogen atom is slightly positive.

The polar bond may be represented in a variety of ways.

Example
Hydrogen chloride g+ §_
H H — • CI or H —CI

Shapes of molecules
Electron pairs repel each other. The shape of a molecule can be predicted by using the valence shell
electron pair repulsion theory (VSEPR) - 'molecules are stable when the repulsive forces are at a
minimum'; this occurs when electrons (bonding and non-bonding pairs or lone pairs) around the central
atom are as far apart as possible.
• If there are four pairs of electrons around the central atom, the electrons repel each other to form a
tetrahedral shape.
• For diatomic molecules (molecules with 2 atoms) the shape is linear (eg nitrogen, N 2 ; oxygen, 0 2 ;
hydrogen, H 2 ; chlorine, Cl2).

To determine the shape of a molecule

Step 1: Draw the Lewis structure of the molecule.
Step 2: Determine the number of pairs around the central atom.
Step 3: Determine the number of bonded pairs and non-bonded pairs.
The number of bonded pairs and non-bonded pairs is used to determine the overall shape.

Number of electrons Number of bonded Number of non-

around the central pairs around the bonded pairs around Shape
atom central atom the central atom

1 3 Linear

2 2 Bent
4
3 1 Trigonal pyramidal

4 0 Tetrahedral

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 Describe the nature of structure and bonding in different substances 31

Example
The shape of a molecule of water.
Step 1: Lewis structure of water.
, non-bonded pair

*0*
/ \ bonded pair
H H

Step 2: There are four pairs of electrons around the oxygen atom - suggested shape is tetrahedral, '
as the electrons repel each other as far as possible. / \
H ' H
Step 3: There are 2 bonded pairs and 2 non-bonded pairs - actual shape is bent.
• •
•o'
/ \
H H

Polar Molecules

Polar molecules contain polar bonds. Polar molecules have an uneven charge distribution over the whole
molecule ( w h e n it is considered three-dimensionally). This occurs w h e n the symmetry of the molecule
means the dipoles do not cancel each other out. Part of the molecule is slightly negative, part is slightly
positive - a m o l e c u l a r d i p o l e exists.

Example
Water contains polar bonds, with oxygen being more electronegative than hydrogen. When the molecule is
considered three-dimensionally, it has an uneven charge distribution. Therefore, the molecule is polar.
• •
•o'
/ \
H H

Non-polar molecules

W h e n the charge distribution over the whole molecule is even, the molecule is non-polar.

Example
1. The bond between the chlorine atoms in chlorine, Cl2, is non-polar - t h e charge distribution over the whole
molecule is even, so the molecule is non-polar.
2. Tetrachloromethane, CCI4, contains polar bonds (each C-CI bond is polar), but when the whole molecule
is considered in three dimensions, the charge distribution is even - the polar bonds cancel each other. The
molecule is therefore non-polar. This occurs because the symmetry of the molecule means the dipoles cancel
each other out.
Other non-polar molecules are: oxygen, 0 2 ; cyclohexane, C 6 H 12 ; hexane, C 8 H 18 ; nitrogen, N 2 ; hydrogen, H2.

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. 32 Chemistry Achievement Standard 2.4

Questions: Chemical bonding and Lewis structures

1. When volcanoes erupt, a number of gases may be released. These include sulfur dioxide (S0 2 ), carbon
dioxide (C0 2 ), hydrogen sulfide (H 2 S) and water vapour (H 2 0). At the surface, sulfur dioxide may also
oxidise to form sulfur trioxide (S0 3 ).

Complete the table below by:

a. drawing a Lewis structure (electron dot diagram) for EACH of the formulae

b. naming the shape for C0 2 , H 2 S and S0 3 .

Formula of molecule a. Lewis structure b. Name of shape

S0 2 bent or V-shaped

C02

H2S

H2O bent or V-shaped

S03

c. State whether EACH of the following molecules is polar or non-polar. Explain your answers
(You may use Lewis diagrams in your explanation.)

i. C02

li. H2S

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 Describe the nature of structure and bonding in different substances 33

iii. Explanation:

d. The shapes of S0 2 and H 2 0 molecules are both described as bent or V-shaped. The molecules are
drawn below, with approximate bond angles shown.

120° 109°

Explain why the bond angles in these two molecules are different.

e. Following an eruption, lakes and streams become more acidic due to S0 2 dissolving in the water
and reacting with it.
Use the structure and bonding in H 2 0 and S0 2 to explain why S0 2 is soluble in H 2 0.

2. Write down the type of bond (covalent or ionic) formed between the following atoms:

a. Oxygen and oxygen.

b. Oxygen and hydrogen.

c. Copper and chlorine.

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. 34 Chemistry Achievement Standard 2.4

3. a. Use Lewis structures to explain how methane, CH4, is formed from a carbon atom and hydrogen
atoms.

b. Name the type of bond that is formed.

4. Draw Lewis structures for the following molecules:

a. NH3 b. 0 2 c. CH3OH d. HOCI (where 0 is

the central atom)

5. Draw Lewis structures for the compounds below:

a. C 3 H 8 b. C2H4 c. PCI3 d. Cl 2 0 (where O is

the central atom)

6. Explain the difference between a polar molecule and a polar bond. Give an example to illustrate your answer.

7. Trichloromethane, CHCI 3 , is commonly called chloroform. It was once used as an anaesthetic,

a. Draw the Lewis structure for trichloromethane.

b. Predict the shape of the molecule.

c. Is the molecule polar or non-polar? Justify your answer.

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 Describe the nature of structure and bonding in different substances 35

8. Complete the following table by:

a. Drawing the Lewis structure.
b. Identifying the shape of the molecule.
c. Stating whether the molecule is polar.

Is it a polar molecule?
Molecule Lewis structure Shape
(Yes/No)

CCI4

co2

SCI2

H2

Types of substances

Molecular substances
Attractive forces within a molecule are called intramolecular forces; forces between molecules are
intermolecular forces.

Molecular substances are made up of atoms (eg Ne) or discrete molecules (eg l2, S8, H 2 0, NH3,
C 60 (buckminsterfullerene)).
In the molecules, the intramolecular forces are strong covalent bonds; the intermolecular forces between
adjacent molecules are weak forces.

Example

strong covalent bonds exist

within (ie intramolecular
forces) each molecule

weak intermolecular forces act

between molecules, attracting
one molecule to another

molecule of C 0 2

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. 36 Chemistry Achievement Standard 2.4

Non-polar molecules
Electrons in molecules are continually moving. At any one moment, a small instantaneous dipole exists
due to the unsymmetrical distribution of moving electrons. This sets up an attractive force between adjacent
molecules.

Polar molecules
In a polar molecule (eg water, ethanol or ammonia), the electrons are not spread evenly throughout the
molecule. One part of the molecule is slightly negative relative to another part that is slightly positive.
Attractive forces exist between the opposite dipoles of different molecules, known as permanent dipoles.
These intermolecular forces are stronger than those between non-polar substances.

intramolecular force
(covalent bond)

intermolecular force

Properties
Melting and boiling points
Molecular substances have low melting and boiling points - the forces between molecules require little energy
to break so are broken at low temperatures.

Iodine and carbon dioxide sublime (change from a solid to a gas without going through the liquid phase).

Conduction of electricity
For a substance to conduct electricity, it must contain charged particles and these particles must be free to
move. Molecular substances do not conduct electricity as they do not consist of charged particles.

Solubility
Substances dissolve in solvents if the forces between the solute particles and the solvent particles are
stronger than:
• the forces between the solute particles and other solute particles; and
• the forces between the solvent particles and other solvent particles.
Non-polar molecular substances do not dissolve in polar solvents (such as water and ethanol).

Example
I o d i n e d o e s n o t dissolve i n w a t e r

The forces between the water molecules are relatively strong. Attractive forces between the water molecules and
the non-polar molecular iodine are insufficient to overcome the bonding between the water molecules (ie the
forces between the water molecules do not break apart to allow the molecular substance to move in between
the water molecules).

Polar molecular substances do dissolve in polar solvents.

Example
A m m o n i a g a s dissolves i n w a t e r

The attractive forces between the polar molecule, ammonia, NH 3 , and the polar solvent molecule water, H 2 0 ,
are the same as the intermolecular forces between the molecules of the ammonia and the intermolecular forces
between the molecules of water, so the ammonia dissolves.

Non-polar molecular substances dissolve in non-polar solvents (such as cyclonexane and hexane).

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 Describe the nature of structure and bonding in different substances 37

Example
Iodine dissolves in c y d o h e x a n e

Intermolecular forces between the molecules of a non-polar solvent (eg cyclohexane) are weak forces. The
attractive forces between a non-polar substance (eg iodine) and cyclohexane is the same as the intermolecular
forces between the iodine molecules and the intermolecular forces between cyclohexane - the non-polar
molecular substance thus dissolves in cyclohexane.

Polar molecular substances do not dissolve in non-polar solvents.

Example
A m m o n i a gas does not dissolve in cyclohexane

Forces between polar ammonia molecules (solute-solute force) are strong compared with forces between the
ammonia and cyclohexane - forces between the polar molecules do not break (ie the ammonia and cyclohexane
do not mix).

Extended networks
Extended networks are substances made up of particles in which the pattern of particles is repeated many
times. Types of extended networks include ionic, giant covalent and metallic substances.

Ionic substances
Ionic substances (eg KCI, NaCI, MgO, MgCI 2 ) are made up of positive and negative ions in fixed positions
in a three-dimensional arrangement in a regular repeating pattern known as a lattice. The electrostatic
attraction between the oppositely charged ions (ionic bond) is strong.

Properties
Melting and boiling points
The melting and boiling points of ionic substances are high because the positive and negative ions strongly
attract one another - considerable energy is required to separate the ions to melt or vaporise an ionic
substance.

Conduction of electricity
Ions are charged particles. In the solid state, ions are held in fixed positions in the lattice and are unable to
move - the solid will not conduct electricity. When an ionic solid is melted or dissolved, the ions separate
and are free to move and will conduct electricity.

water molecules the molten state

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38 Chemistry Achievement Standard 2.3

Solubility in polar solvents

Ionic solids dissolve in polar solvents.

Example
S o d i u m c h l o r i d e dissolves in w a t e r

Ions are 'pulled out' of a sodium chloride lattice when attraction between water (a polar solvent) and the sodium
chloride solid (solute) is stronger than the attraction between the ions and the attraction between the water
(solvent) molecules. The negative end of a water molecule is attracted to the positive (Na + ) ion; the positive end
of the water molecule is attracted to the negative (Cl~) ion. Consequently, the ions separate and the substance
dissolves.

Solubility in non-polar solvents

Ionic solids do not dissolve in non-polar solvents.

Example
S o d i u m c h l o r i d e d o e s n o t dissolve in c y c l o h e x a n e

The forces between the ions in an ionic solid such as sodium chloride are stronger than the forces between those
in cyclohexane molecules - the solvent molecules are too weak to attract the ions and separate them from each
other.

Covalent network solids

These are substances that contain an extended network of covalently bonded atoms.

Linear chains
A long one-dimensional chain of covalently bonded atoms, eg polythene, plastic sulfur, rubber.

2-dimensional layers stronK cova,ent

Graphite is a soft and greasy solid made of layers bond

of carbon atoms covalently bonded to three other

layer of carbon
carbon atoms. The remaining valence electron atoms
(one per carbon atom) is delocalised (free to move
through the structure) between the layers. Atoms weak forces
in each layer are held together by strong covalent
bonds. The layers are held together by weak forces
- they are easily broken, so the layers slide over one layer of carbon
atoms
another (graphite is used as a 'dry' lubricant and in
pencil 'leads').

3-dimensional networks
All the atoms are held together by strong covalent bonds. The 3-dimensional structure formed is very rigid
and strong, eg diamond - each carbon atom is covalently bonded to four other carbon atoms; silicon
dioxide (silica) - each silicon atom is covalently bonded to four oxygen atoms and each oxygen atom is
covalently bonded to two silicon atoms.

Properties
Melting and boiling points
Large amounts of energy are needed to melt or vaporise covalent networks, as covalent bonds must be
broken; melting and boiling points are high.
Linear chain solids may melt or soften more easily because the covalent bonding occurs in only one
dimension. The longer the molecule, the higher the melting point (more sites exist for intermolecular
attractions between chains).
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 Describe the nature of structure and bonding in different substances 39

Conduction of electricity
Covalent network solids do not consist of any free-moving charged particles so do not conduct electricity
(exception - graphite). In graphite, three valence electrons are involved in covalent bonding - the fourth
valence electron is free to move between the layers, so graphite will conduct electricity.

Solubility
Covalent network solids are insoluble in polar and non-polar solvents.

Metallic substances
Metallic substances are three-dimensional networks in which positive ions (nucleus plus full inner electron
shells) are packed closely together in a fixed position. Valence electrons are loosely held and are attracted
to the nucleus of all the atoms around them - the 'sea' of delocalised electrons surround positive ions
- the strong attraction of electrostatic forces is called metallic bonding. The attractive forces have no set
direction.
2-D picture of a 3-D picture of a
metallic lattice metallic lattice
•c
00:00
O t O T O ^ delocalised
electrons

o o o o positive ions
~ in fixed ""
positions

Properties
Melting and boiling points
Most metals have high melting and boiling points - metallic bonding is strong. The positive ions in the
lattice must be separated when metals are melted, so large amounts of energy are needed to overcome the
attractive forces between the positive ions and delocalised valence electrons.

Conduction of electricity
Metals are good conductors of electricity because of the free movement of valence electrons through the
lattice of positive ions.

Malleability and ductility

Metals are malleable (can be beaten into shapes).

Metals are ductile (can be drawn out into thin wires).

Positive ions in the metal are arranged in ordered layers and held together by strong attractive forces with
the delocalised electrons. When a force is applied, the layers can be made to slide over one another - the
non-directional metallic bonding allows this to occur without breaking up the structure.

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. 40 Chemistry Achievement Standard 2.4

Answering NCEA questions

For questions involving 'explaining properties in terms of structure and bonding', the answer must be
structured carefully.

Step 1: State what type of solid the substance is.

Step 2: State how the solid is structured. (What type of particle is it made of? How are the particles arranged?)
Step 3: Link the structure to the property (a property is its 'use' or 'characteristic').
Step 4: Refer back to the property.

Example

Questions: Types of substances

1. Complete the table below by:

a. identifying the type of particle in EACH solid as atoms or ions or molecules

b. naming the attractive force that is broken when EACH solid melts
c. stating whether the relative melting point of EACH solid is high or low.

Name of solid Type of solid a. Type of particle in b. Attractive force broken c. Relative
solid - atoms or ions or when solid melts melting
molecules point - high
or low

ice
molecular
(H20)

silicon dioxide covalent

(Si0 2 ) network

iron
metallic
(Fe)

potassium
chloride ionic
(KCI)

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 Describe the nature of structure and bonding in different substances 41

2. a. The table below shows three properties of iodine crystals (l2).

Explain, in terms of the structure a n d bonding within the solid, w h y the solid has EACH of the
properties stated.

Property Explanation in terms of structure and bonding within the solid

Iodine crystals will readily

sublime (change from
a solid to a gas) when
heated gently over a
bunsen burner.

Iodine crystals are more

soluble in cyclohexane
than they are in water.

Iodine crystals do not

conduct electricity.

b. Magnesium chloride (MgCI 2 ) and sulfur dichloride (SCI 2 ) are both chlorides of Row 3 elements.
Describe the type of bonding present in solid samples of EACH of these chlorides.

3. Diamond and graphite are allotropes of carbon. This means that they are both made only of carbon
atoms but the atoms are arranged differently, which results in different physical forms of the same
element. Some uses of diamond and graphite are shown below.

Allotrope Use(s)

Diamond • Used to make saws to cut marble

Graphite • Used as a solid lubricant in machinery

• Used to make electrodes

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. 42 Chemistry Achievement Standard 2.4

Discuss the structure and bonding within diamond and graphite, and relate this to the uses shown
in the table above.

4. Complete the table by classifying each of the substances as molecular, ionic, metallic or covalent
network.

Substance Type of substance

Oxygen a.

Polythene b.

Copper carbonate c.

Zinc d.

Potassium bromide e.

Silicon dioxide f.

5. Complete the following table.

Melting point Type of solid (metallic, molecular, ionic or

Substance Conducts electricity?
(°C) covalent network)?

A -130 No a.

B 3 550 No b.

Only in the molten state

C 825 c.
or in aqueous solution

D 651 Yes d.

6. Key substance list: Ammonia, copper carbonate, wax, potassium chloride.

From the key list above, write down the substance(s) which:

a. Conducts electricity strongly in aqueous solution

b. Has a low melting point and does not dissolve in ethanol

c. Do not dissolve in water.

d. Has the lowest melting point.

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 Describe the nature of structure and bonding in different substances 43

7. You have been given two unknown solid samples. You know one is silicon dioxide and the other is
sodium chloride. Describe a test you would use to distinguish between the two substances.

8. a. Hydrogen sulfide has a low melting point, whereas copper sulfide has a high melting point. Explain
the differences in properties of these two substances, referring to their structure and bonding.

b. Sodium sulfate dissolves in water, whereas sulfur does not dissolve in water. Explain the difference
in properties of these two substances, by comparing and contrasting their structure and bonding.

9. Explain the following properties in terms of structure and bonding,

a. Carbon dioxide sublimes at low temperatures.

b. Iodine dissolves in hexane.

c. Aluminium is a very good conductor of electricity.

d. Calcium has a high melting point.

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. 44 Chemistry Achievement Standard 2.4

e. Diamond has a high melting point.

f. Graphite conducts electricity.

The Periodic Table

An example of a periodic table has been provided at the front of this book (p. iv).

The groups (1-18) are the columns in the periodic table. Elements in the same group have similar
chemical properties.

Example
Group 1 7, the halogens, have similar chemical properties. This is due to the fact they all have 7 valence
electrons.

Rows run across the periodic table. Elements in a row are in the same energy level.

Example

The third row (Na to CI) elements have their valence electrons in the third energy level.

Metals are found on the left-hand side of the periodic table; non-metals are found on the right-hand side.

Sources of elements
Only a few elements are found naturally as pure elements - unreactive metals (eg gold and silver) and
unreactive gases (eg those in Group 18); stable molecules (eg oxygen, sulfur, nitrogen); various forms of
carbon (eg diamond).

Most elements are found as part of compounds and need to be extracted to be used in their pure state.

Example
Chlorine is not found in its elemental state as it is too reactive. It is found in seawater as magnesium chloride,
MgCI2, and can be extracted by electrolysis.

Period trends
Across a period there is:
• A change from metallic behaviour to non-metallic behaviour.
• An increase in the nuclear charge (the number of protons increases).
• A decrease in the size of the atoms.
As the nuclear charge increases, electrons are pulled closer to the nucleus and atoms are thus smaller (eg
chlorine is smaller than sodium).
• An increase in ionisation energy (energy needed to remove an electron).
As the nuclear charge increases, the attraction to the electrons is greater and it is more difficult to remove
an electron from the outer shell.
The first ionisation energy is the energy required to remove one electron from one mole of atoms of a
particular element in the gas state.
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 Describe the nature of structure and bonding in different substances 45

Croup trends
Moving down a group:
• lonisation energy decreases - valence electrons are further from the nucleus and therefore less energy is
required to remove an electron.
• Size of atoms increases - number of energy levels increases; electrons are further from the nucleus and
less tightly held.

Example
F 2,7 two energy levels.

CI 2, 8, 7 three energy levels. Hence, CI is larger than F.

Group 17 - The halogens

The halogens form group 1 7. They all have 7 valence electrons and form -1 ions and have similar chemical
properties.

Halogens table

Element Fluorine Chlorine Bromine Iodine

Symbol F CI Br 1

Formula F2 Cl2 Br 2 L2
Appearance at room
Pale yellow gas Yellow-green gas Dark orange/red liquid Purple-black solid
temperature (25°C)

Melting point (°C) -220 -101 -7 114

Boiling point (°C) -188 -35 59 184

Type of solid Molecular Molecular Molecular Molecular

Halogens exist as diatomic molecules (eg Cl2, l 2 ). They are molecular substances and therefore have low
melting and boiling points.

Third row ha Iides, eg chlorides

Moving across the third-row chlorides, the following trends exist:
• A change from ionic bonding to covalent bonding.
• A change from high melting points to low melting points.
• A change from neutral properties to acid properties. Acidic compounds usually involve covalent
bonding.

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. 46 Chemistry Achievement Standard 2.4

Chlorides

Group 1 2 13 14 15 16 17 18

Element Na Mg Al Si P s CI Ar

Formula(e) of
chloride(s)
NaCI MgCI 2 AICI3 SiCI4 PCI3 SCI 2 Cl2 -

ionic
(<180°C); pure
Bonding ionic ionic polar covalent -
covalent covalent
(>180°C)

Melting point sublimes at

801 712 -70 -91 -80 -101 -
(°C) 180

yellow/
white white colourless colourless pale green
Appearance white solid orange -
solid solid liquid liquid gas
liquid

conducts in aqueous conducts

non-conductor (conduct to some extent in aqueous solution
Conductivity solution and in molten in aqueous
because HCI acid forms)
state solution

Melting point of 193 under

801 712 -70 -91 -80 -101 -
chloride (°C) pressure

Boiling point of Sublimes

1 465 1 418 57 74 59 -35 -
chloride (°C) at 180

Sodium chloride, NaCI, and magnesium chloride, MgCI2

White solids, at room temperature (25°C). Properties:
• High melting points.
• Do not conduct electricity as solids. Conduct when molten or in aqueous solutions.
• Soluble in polar solvents (eg water).
Properties suggest the type of bonding is ionic.

Aluminium chloride, AICI3

A solid that sublimes at temperatures below 180°C. When heated under pressure it melts. Covalently
bonded aluminium chloride is formed during the change from solid to liquid.

Silicon chloride, SiCI4

Colourless liquid at room temperature (25°C). Properties:
• Low melting point.
• Non-conductor of electricity (no ions or electrons that are free to move).

Properties suggest molecules are covalently bonded with weak forces between molecules.

Phosphorus(lli) chloride, PCI3

Colourless liquid at room temperature (25°C). Properties:
• Low melting point.
• Non-conductor (no ions or electrons that are free to move).
Properties suggest molecules are covalently bonded with weak forces between molecules.

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 Describe the nature of structure and bonding in different substances 47

Sulfur dichloride, SCI2

Yellow/orange liquid at room temperature (25°C). Properties:
• Low melting point.
• Non-conductor.

Properties suggest molecules are covalently bonded with weak forces between molecules.

Questions: The Periodic Table

1. Third-row chlorides
Use the data in the table below to answer the questions about the chlorides of the third row.

Element Na Mg Al Si P S CI

Formula NaCI X AlClj Y PCI 3 SCI 2 Cl2

Melting point of 193 under

801 712 -70 -91 -80 -101
chloride (°C) pressure

Boiling point of Sublimes

1 465 1 418 57 74 59 -35
chloride (°C) at 180

a. What is the formula of the chlorides X and Y in the table?

i. X = ii. Y =

b. What is the state, at room temperature (25°C), of AICI3? Using information from the table above,
explain your answer.

c. Classify the type of solid (ionic, molecular, covalent network or metallic) for the following
substances:

i. NaCI

ii. Cl2
d. The nature of bonding in sodium chloride, NaCI, is quite different from that of phosphorus
trichloride, PCI3. Use the information in the table to compare and contrast the differences in
structure and bonding between the two substances.

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. 48 Chemistry Achievement Standard 2.4

2. The halogens

Halogens table

Element Fluorine Chlorine Bromine Iodine

Symbol F CI Br 1

Formula F2 Cl2 Br 2 l2

Melting point (°C) -220 -101 -7 114

Boiling point (°C) -188 -35 59 184

a. What is the state of bromine at room temperature (25°C)? Justify your answer using data from the
table above.

b. What type of bonding exists in chlorine gas? Justify your answer using information from the table.

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 NCEA
90309 Achievement
Standard
Describe the structural formulae and
reactions of compounds containing 2.5
selected organic functional groups Externally assessed
4 credits

Physical properties of hydrocarbons

Compounds that contain carbon are called organic (except carbonates, hydrogen carbonates, carbon
monoxide and carbon dioxide). Hydrocarbons are organic compounds that contain only carbon and
hydrogen.

Alkanes, alkenes and alkynes are all hydrocarbons. They each form a homologous series (a 'family' where
members of the series are represented by the same general formula, have the same functional group, and
show a gradual change in physical properties).

Alkanes Alkenes Alkynes

General formula CnH2n+2 CnH2n CnH2n-2

Saturated hydrocarbon? Yes No No

Functional group - Double bond Triple bond

H H
H H
H—C—C—H \ /
Example C = C
1 1 / \
H H H H H— C= C— H
Ethane Ethene Ethyne

S a t u r a t e d hydrocarbons contain single bonds. Unsaturated hydrocarbons contain a double or triple

bond, and more atoms or groups can be added into the hydrocarbon.
A functional group is an atom or group of atoms within the organic molecule that determines the
characteristic chemical properties of the particular family of organic compounds.

Examples and uses of hydrocarbons

Alkanes such as methane can be used as fuels and in the production of methanol from natural gas.

Methane is a molecular substance. The melting point and boiling point are low due to weak forces
between the molecules. There is a strong covalent bond between the carbon and hydrogen atoms within
the molecule. Methane is tetrahedral in shape.

| 109°
c J

H
Alkenes are used to make polymers and are the starting materials for other substances such as ethanol,
antifreeze and cosmetics.

Ethyne is commonly called acetylene. It is used in welding torches. Ethyne has a linear shape.
. 50 Chemistry Achievement Standard 2.4

H—C=C—H
Ethyne is made by adding water to calcium carbide. Ethyne is collected by the downward displacement
of water.

CaC2(s) + 2H20(I) -> C 2 H 2 (g) + Ca(OH) 2 (aq)

Physical properties of hydrocarbons

Physical property Alkanes, alkenes and alkynes

Colour Colourless
Polarity Non-polar

Solubility in water Insoluble*

Electrical conductivity Do not conduct

Conductivity of heat Poor

Density Less dense than water

*Ethyne is very slightly soluble.

Melting points and boiling points gradually increase as molar mass increases.

Naming alkanes
Straight-chain alkanes
Ending (suffix) is -ane.
Beginning of name (prefix) depends on the number of carbons.

Number of carbons Prefix Alkane name

1 meth- methane
2 eth- ethane
3 prop- propane
4 but- butane
5 pent- pentane

6 hex- hexane
7 hept- heptane
8 oct- octane

The molecular formula shows the kind and number of atoms in the substance (eg molecular formula for
propane is C 3 H 8 ).
The structural formula (also known as constitutional formula) represents how the atoms in a
molecule are bonded together, eg propane is:
H H H
I I I
H—C—C—C—H
I I I
H H H

The 'stick' between the carbon and the hydrogen represents a shared pair of electrons (ie a single covalent bond).
Sometimes the condensed structural formula is used, eg CH 3 CH 2 CH 3 .

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 Characteristics and physical properties of hydrocarbons 51

Branched chain alkanes

Branched chains are called alkyl groups.
Methyl CH3- Ethyl CH3CH2-
Other alkyl groups are named accordingly - propyl, butyl, etc, and a hyphen is placed between a number
and a word.
Example
H H H H H
I© I© I® I® I®
H—C—C—C—C—C—H

l_l l_l The methyl group (methyl) is attached to carbon number 2 (2-methyl) of
H
the 5-C chain (pentane).
H —C —H

H
2-methylpentane

For identical branches:

• -di if there are 2 branches the same.
• -tri if there are 3 branches the same.
• -tetra if there are 4 branches the same.
A comma is placed between numbers.
Example
H H H H H
I ® I© I ® I ® I ®
H—C—C—C—C—C—H
There are two (di) methyl groups attached at positions 2 and 4
(2,4-dimethyl) of the 5-C chain (pentane).
H— C-HH-C-H
I I
H H
2,4-dimethyl pentane

Naming alkenes
Ending (suffix) is -ene.
Beginning of name (prefix) depends on the number of carbons (as for alkanes); eg
H H
\ /
C= C is ethene (also known as ethylene).
/ \
H H
If there are 4 or more carbon atoms in the chain, the position of the double bond must be stated.
Number the carbon atoms from the end closest to the double bond and choose the lower of the two
carbons joined by the double bond to identify the double bond.
h H H H H H H H H H
\ © I® I® I® I ® I ® I© I ® I ® I ®
C=C—C—C—C—H H—C—C=C—C—C—H
/ I I I I I I I
H H H H H H H
pent-1-ene pent-2-ene
The double bond is between the 1st The double bond is between the 2 nd and 3rd carbon
and 2 nd carbon (ie not pent-3-ene)
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. 52 Chemistry Achievement Standard 2.4

Branched alkenes
Position of the double bond is identified by numbering the chain from the © ) CH2CH3
CH3CH=CCH © ©
2
end that gives the double bond the lowest number; the branch is then
© © I
identified. CH3
3-methylhex-2-ene

Naming alkynes
Ending (suffix) is -yne.

Beginning of name (prefix) depends on the number of carbons (as for alkanes); eg
H — C = C — His ethyne (commonly called acetylene).

Branched alkynes - as for alkenes

H H H
I© © ® I© I©
H—C—C=C—C—C—H
I I I
H H-C-HH
I
H

4-methylpent-2-yne

Questions: Characteristics and physical properties of hydrocarbons

1. a. Name the functional group circled. (^^^CH2CH2CHCH3

CH3
b. Give the systematic name of the compound.

2. For each of the following organic compounds, draw the structural formula,
a. 2,2-dimethylhexane. b. 3-methylheptane.

c. Propyne. d. 3-methylbut-l-yne.

e. 4-methylpent-2-ene.

3. Name the following organic compounds:

a. CH 3 CH 2 CH 2 CH 3

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 Characteristics and physical properties of hydrocarbons 53

b. CH 3 CHCH 2 CH 2 CH 2 CH 3

CH 3

c. CH 3 CHCH 2 CHCH 3
I I
CH 3 CH 3

d. CH 2 =CHCH 2 CH 3

e. CH 3 CH 2 CH 2 CH 2 CH 3

f. CH 3 CH 2 CHCH 3
I
CH 3

Chemical properties of hydrocarbons

Alkanes are less reactive than alkenes and alkynes, as alkanes do not have a double or triple bond. All
hydrocarbons are useful as fuels, as they all burn readily.

Combustion reactions
Complete combustion

Occurs in a plentiful supply of oxygen. Products are water and carbon dioxide; the flame is hot and blue.
Alkane C 3 H 8 + 50 2 3C0 2 + 4H 2 0
Alkene C 3 H 6 + 4-J0 2 -> 3C0 2 + 3H 2 0
Alkyne C 3 H 4 + 40 2 -> 3C0 2 + 2H 2 0

Incomplete combustion
Occurs in a limited supply of oxygen. Products are water and carbon monoxide or water and carbon (soot);
the flame is yellow.
Alkane C 3 H 8 + 3^0 2 3CO + 4H 2 0 limited supply
Alkane C 3 H 8 + 20 2 3C + 4H 2 0 very limited supply

Substitution reactions
A substitution reaction is one in which an atom (or group of atoms) attached to a carbon in an organic
compound is/are replaced by a different atom (or group of atoms).
Alkanes undergo substitution reactions:
UV from sunlight , , , , , . ,
ethane + bromine > bromoethane + hydrogen bromide
UV from sunlight „
CH3CH3 + Br2 —> CH 3 CH 2 Br + HBr

Bromoethane can react further, because the other hydrogen atoms can be replaced - dibromoethane,
tribromoethane and tetrabromoethane will also be produced.
UV from sunlight is the catalyst for the reaction.

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. 54 Chemistry Achievement Standard 2.4

The hydrogen bromide will turn moist blue litmus paper red.
Chlorine will react with alkanes in a similar way.
Bromoethane is an example of a haloalkane - an alkane in which one or more of the H atoms has been
replaced with a halogen (ie a CI, F or I atom).

Naming haloalkanes
As for alkanes, plus prefix for halogen atom (CI - chloro, Br - bromo, I - iodo).

Classification of haloalkanes
Haloalkanes can be classified as primary, secondary or tertiary according to the position of the halogen
atom.
Examples

P r i m a r y haloalkanes Secondary haloalkanes Tertiary haloalkanes

The halogen is attached to a The halogen is attached to a The halogen is attached to a

carbon that is attached to one carbon that is attached to two carbon that is attached to three
other carbon. other carbons. other carbons
H H H H H H (CI) H

c — c— c—H H — C- -C — C — H C —H

H H H H H H H
1-chloropropane 2-chloropropane H -C- H

H
2-chloromethylpropane

Addition reactions
An addition reaction is one in which the double (or triple) bond breaks and other atoms are introduced
into the organic molecule. The molecule becomes saturated. Alkenes and alkynes undergo addition
reactions because they are unsaturated compounds.

Addition reactions of alkenes

Addition of bromine or chlorine (halogenation)
H H ^r Br
\ / 1 1
C= C + Br-Br H—C — C — H
7 X I I
H H H H
ethene + Br2 1,2-dibromoethane

\ 7 T ? ? T
C= C— C— H + CI — C I -> H — C — C — H — H

JH H H
1 1 1
H
propene + Cl2 1,2-dichloropropane
In addition reactions, the double bond breaks. The substance added is placed on the C atoms either side of
the double bond (for propene + Cl2, 1,2-dichloropropane is produced, not 1,1-dichloropropane).

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 Characteristics and physical properties of hydrocarbons 55

Addition of hydrogen (hydrogenation)

H H ^ H
\ / Pt 1 1
C= C + H—H > H—C — C — H
7 X I I
H H 1 1
H H
Pt
ethene + H 2 (g) > ethane
(A platinum catalyst is used - there are other methods of hydrogenating ethene.)

Addition of hydrogen chloride (hydrohalogenation)

H H V ?
\ / 1

C= C + H —CI -> H —C —C —H
/ \ | |
H H 1 1

H H
ethene + HCI -» chloroethane

Addition of water (hydration)

Ethene reacts with steam at 330°C and at a pressure of 60 atmospheres in the presence of an acid catalyst
(H+) to form ethanol:
i_i
H Li
H H I OH
,
\ / H+
C= C + H— O — H >H — C — C — H
7 X I I
H H 1 1
H H
H+
ethene + H20 » ethanol

Addition of hydrogen chloride to unsymmetrical alkenes

If an alkene is unsymmetrical, there are two possible products from addition of hydrogen chloride. The
major product has the hydrogen attached to that carbon that has the greater number of hydrogen atoms
attached to it.
H H H CI H CI H H
H x I I I I I I I I
C = C—C — C — H + HCI H—C — C — C —H or H—C — C — C —H
/ 1 1 I I I I I I
" H H H H H H H H
H attaches to C with greater
number of H's

propene + HCI —> 2-chloropropane + 1 -chloropropane

major product minor product

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. 56 Chemistry Achievement Standard 2.4

Addition reactions of alkynes

Reactions are similar to alkenes, but further addition occurs until the molecule is fully saturated.
Br Br
\ /
H — C = C — H + Br — B r C= C
/ \
H H
ethyne Br2 1,2-dibromoethene
H H Br Br
\ / I I
C =C + Br — B r H—C — C — H
/ \ I I
H H
Br Br
1,2-dibromoethene + Br2 —> 1,1,2,2-tetrabromoethane

Using addition reactions to identify alkenes

Identification with bromine water

Bromine is a reddish colour but when added to water forms bromine water, Br2(aq), which is orange. When
added to an alkene, bromine water decolourises rapidly.
H
T \ /Br
H \ / C W H H \ / C \ / B r

c c c c
H^l I + Br-Br ^ I |XH
H\l l/H H\l l/H
c c c c
/ c \ / \
H H H H
cyclohexene + Br2(aq) 1,2-dibromocyclohexane
(colourless) (orange) (colourless)
If an alkane, such as cyclohexane, had bromine water added to it, the bromine water would remain orange.

(If placed in sunlight, however, the bromine water would decolourise slowly with an alkane - sunlight
catalyses the reaction between alkanes and bromine).

Identification with potassium permanganate solution

(Acidified) potassium permanganate solution, H+/Mn04~, is purple. If added to an alkene, the solution
changes from purple to colourless.
H Hx / OH
H
Hv
1
\ ,<L \ C/ \ C/oh c
C C—H N/ I |\H
u / I I H + /Mn0 4 - H M

\\ \ H ' H \' '/H

\ '/ H c c

H7 ^H H H

cyclohexene + H+/Mn04" 1,2-dihydroxycyclohexane

(colourless) (purple) (colourless)
Alkanes do not react with potassium permanganate. If an alkane, such as cyclohexane, was used, the
potassium permanganate solution would remain purple.

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 Characteristics and physical properties of hydrocarbons 57

Polymers
A polymer is a large molecule made up of many smaller molecules (called monomers).
Polymerisation is the reaction in which the small molecules join together to form the large molecule.
Polythene is a polymer made from the monomer ethene.
The type of polymerisation is called addition polymerisation.
H H H H H H
\ / \ / \ /
C = C + C == C + C = C
/ \ / \ / \
H H H H H H

H H H H H H
| 1 1 1
I I I I
C — C— C -- C — C— C -
I I I I I
1 1 1 1 1
H H H H H H

To write the formula for the molecule, the repeating unit is represented; the symbol 'n' represents the
number of monomer units.
H H \ r H H ~
\ / I

/
C = C J- - - c -- C --
\ 1 1
H CI / L H CI J

or N(C H 2 =CHCI) -£CH2 — CHCLJ"

Monomer Polymer Uses

Ethene Polythene Bottles

H H r H H -
\ / 1 1
C = C - C — C -
/ \ 1 1
H H LH H _ n

Propene Polypropy lene Thermal wear, carpets

H H H — H H
1 1
\ 1 1
— C — C -
C = C — C — H
1 1
— H CH3- n
H H

Chloroethene Polyvinyl :hloride (PVC:) Lino, garden hoses, shower

H CI curtains, artificial leather (eg car
r h czi —I
\ / 1 1 seats), clothing
C = C - c —c -
/ \ 1 1
H H LH H Jn

Tetrafluoroethene PolytetrafI uoroethylen a Non-stick frying pans, gaskets,

F F (also calle d Teflon) (PT bearings
\ /
C = C
- F F -|
/ \
1 1 FE)
- C — C -
F F 1 1
_ F F J

n
. 58 Chemistry Achievement Standard 2.4

Questions: Chemical properties of hydrocarbons

1. CH 3 CH=CHCH 3 CH 3 CH 2 CH 2 CH 3
compound A compound B
Contrast the reactions of compound A and compound B with bromine. Include relevant observations
and equations, and identify the type of reaction that occurs in EACH case.

2. a. Polypropylene is the common name for a polymer used widely in clothing designed for warmth. It
is an addition polymer made from propene (CH 3 CH=CH 2 ).

Draw a section of the polymer showing at least TWO repeating units.

b. Propene can undergo other addition reactions, as given below.

Complete the following equations, showing the structural formulae or the organic products. For
ii., it is necessary to give BOTH of the possible organic products.

i. CH 3 CH=CH 2 h2/Pt»

H 2 O/H +
ii. CH 3 CH=CH 2

and

Mi. Write an asterisk (*) below the product in ii. above that is produced in the larger amount.

3. Describe a test, using a solution of bromine in a non-polar solvent, that could be carried out in the
laboratory to compare the degree of unsaturation of two fats.

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 Characteristics and physical properties of hydrocarbons 59

4. Following is a list of different types of reactions:

addition, substitution, incomplete combustion, complete combustion.

From the list, choose the type of reaction that is indicated by each of the following statements:

a. A reaction in which the products are carbon dioxide and water.

b. The type of reaction that occurs when ethyne reacts with bromine solution.

5. Classify the following haloalkanes as either primary, secondary or tertiary haloalkanes.

H H H H CH 3 H H H CH 3 H H H
I I I I I I I I I I I I
H —C — C — C —H H — C — C — C — C —CI H— C— C— C — C— C
I I I I I I I I I I I I
H CI H H CH 3 H H H CI H H H
A B C

6. Complete the following equations, using structural formulae for the organic products.

7. Write equations for the following reactions. Use structural formulae for the organic reactants and
products.
a. Ethane reacting with bromine water in the presence of sunlight.

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. 60 Chemistry Achievement Standard 2.4

b. Hept-2-ene reacting with hydrogen in the presence of a platinum catalyst.

8. You have been given two unlabelled bottles of colourless liquids; one contains an alkane, the other an
alkene.

Describe a chemical test that could distinguish between the two substances, writing down what you
would see for each test.

9. Teflon is a polymer that is used on non-stick frying pans. Teflon is made by addition polymerisation. A
section of the polymer can be represented by:
F F F F F F
I I I I I I
c —C —C —C —C — c

F F F F F F

Draw the structural formula of the monomer used to make Teflon.

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 Characteristics and physical properties of hydrocarbons 61

Alcohols

The word 'alcohol' is commonly used to describe beverages such as beer and wine. These drinks contain
ethanol that belongs to a family of organic compounds called alcohols.

Alcohols have the general formula of C n H 2n+ iOH (sometimes written as ROH, where R represents an
alkyl group).

The functional group is the hydroxyl group, -OH. (This is not a hydroxide ion as found in, say, sodium
hydroxide, NaOH.)

Alcohols are saturated compounds and form a homologous series.

Naming alcohols
Replace the final 'e' from the corresponding alkane with 'ol':

ethane (C 2 H 6 ) : ethanol (C 2 H 5 OH)

Alcohols with three or more carbons are named by the position of the hydroxyl group.
H H H H H H
I I I J J J
H —3C —2C — t — OH H— C— C— C — H
I I I I I I

H H H H OH H

propan-1-ol propan-2-ol

Branched chain alcohols

The -OH group is given the l o w e s t number when naming.
H CH 3 OH H
I I I I
H — C— C— C — C— H This is named 3-methylbutan-2-ol (not 2-methylbutan-3-ol).
I I I I
H H H H

Classification of alcohols
Alcohols can be classified as primary, secondary or t e r t i a r y alcohols.

Primary alcohol
The -OH group is attached to a carbon that is attached to one other carbon.

Example
CH3CH2CH2OH
propan-1 -ol

Secondary alcohol
The -OH group is attached to a carbon that is attached to two other carbons.

Example
CH3CHCH3

OH
propan-2-ol

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. 62 Chemistry Achievement Standard 2.4

Tertiary alcohol
The -OH group is attached to a carbon that is attached to three other carbons.

Example
OH
I

CH 3 CCH 3

CH3
2-methypropan-2-ol

Physical properties of alcohols

Alcohols are colourless.

Alcohols are polar due to the -OH group. Because of their polarity, small alcohol molecules are soluble in
water. As the length of the carbon chain increases, the length of the non-polar part of the alcohol (ie the
carbon chain) becomes larger - hence large alcohol molecules are insoluble in water.

The boiling points and melting points increase with increasing size, as the forces between the molecules get
stronger. Boiling and melting points are higher than those of the corresponding alkanes because attraction
between molecules is increased through polarity of the molecules.

Straight-chain alcohols have higher boiling points than those of branched chain alcohols.

Chemical properties of alcohols

Combustion reactions
Alcohols undergo complete and incomplete combustion like hydrocarbons. Products of complete
combustion are carbon dioxide and water. Products of incomplete combustion are carbon monoxide (or
carbon, depending on the amount of oxygen) and water.

Oxidation reactions
If an oxidising agent such as acidified potassium dichromate solution, Cr2072~/H+, is added to a primary
alcohol and the mixture warmed, the alcohol will be oxidised to form a carboxylic acid.

Cr2072"/H+
Ethanol » ethanoic acid
(alcohol) warm (carboxylic acid)
The -equation for the oxidation of ethanol is:
CH 3 CH 2 OH(aq) + H 2 0(l) CH 3 COOH(aq) + 4H+(aq) + 4e"
The half-equation for the reduction of the dichromate ions is:
Cr2072-(aq) + 14H+(aq) + 6e" 2Cr3+(aq) + 7H 2 0(I)
The overall balance equation is:
3CH3CH2OH(aq) + 2Cr 2 0 7 2 "(aq) + 16H+(aq) -> 3CH 3 COOH(aq) + 4Cr+(aq) + 11 H 2 0(l)
The orange dichromate ions, Cr 2 0 7 2- , are reduced to green chromium(lll) ions, Cr3+.
Acidified potassium permanganate, Mn04_/H+, is another oxidising agent that can be used to oxidise
alcohols to carboxylic acids; the purple permanganate ions, Mn04~, will be reduced to pale pink
manganese(ll) ions, Mn2+.

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 Characteristics and physical properties of hydrocarbons 63

Alcohol Carboxylic acid f o r m e d o n o x i d a t i o n of alcohol

Methanol Methanoic acid

Ethanol Ethanoic acid

Propan-1-ol Propanoic acid

Questions: Alcohols

1. a. What type of alcohol (primary, secondary or tertiary) is the compound CH3CH2CH2CH2OH?

b. State the type of reaction that will change CH3CH2CH2CH2OH to CH 3 CH 2 CH 2 COH

II
O

2. The structural formula for 3-methylbutan-2-ol is:

H OH CH 3 H
I I I I
H—C—C—C—C—H
I I I I
H H H H

Circle the functional group on this molecule.

3. a. Name the following alcohols:

i. CHJOH

ii. CH3CH 2 CH 2 CH 2 CH20H

H H H H
I I I I
iii. HO — C — C — C — C — H
I I I I
H H H H
H CH 3 H H H
I I I I I
iv. HO — C — C — C — C — C — H

H H H H H
H CH 3 H
I I I
v. H— C— C— C— H
I I I
H OH H
b. Classify the alcohols in a. either primary, secondary or tertiary alcohols:

i.

ii.

iii.

iv
. 64 Chemistry Achievement Standard 2.4

4. Draw the structural formula of the following alcohols:

a. Propan-1-ol

b. Pentan-2-ol

c. 4-methylhexan-3-ol

5. Complete the following table.

Oxidation reactions of alcohols

Alcohol Reagents a n d conditions Observation Carboxylic acid f o r m e d

Propan-1 -ol Cr 2 0 7 2 "/H + and heat a. b

c. d Purple permanganate Methanoic acid

turns colourless

6. Complete the following equations.

a. + H20 CH 3 CH 2 OH
Cr2072-/H+
b. CH 3 CH 2 CH 2 CH 2 OH >
warm
7. A student has been given two bottles, each containing a colourless liquid. One contains a primary
alcohol and the other contains an alkane. Describe a simple chemical test that could distinguish
between the two compounds. Write down what you would do and observe in each case.

Isomers

Isomers are compounds with the same number and type of atoms but in which these are arranged
differently. Although they often look similar, isomers have different physical properties, and sometimes
different chemical properties.

Structural isomerism
Structural isomers have the same molecular formula but their atoms are arranged differently.

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 Characteristics and physical properties of hydrocarbons 65

Example
Some structural isomers differ in the a r r a n g e m e n t of the atoms. Pentane and methylbutane have the same
molecular formula, C 5 H 10 , but the atoms are arranged differently:
H H H H H H CH3 H H

H — C — C — C — C — C — H H — C — C C —H

H H H H H H H

pentane methylbutane

Example
Some structural isomers differ in the position of t h e f u n c t i o n a l group:
OH H H H OH H

H — C — C — C — H H — C — C — C — H

H H H H H H
propan-1-ol propan-2-ol

H CI H H H H CI H H
I I I I i I
2. H — C •C- C — C — C — H C — C — C — C — C — H

H H H H H H H H H H

2-chloropentane 3-chloropentane

Cis-trans isomerism (Geometric isomerism)

C i s - t r a n s i s o m e r s have the same molecular formula but their arrangement of atoms in space is different.
S o m e alkenes exhibit cis-trans isomerism d u e to the non-rotation of the double bond.

Examples
1. The bromine atoms in 1,2-dibromoethene can exist either on the same side as each other or opposite one
another:
Br Br Br H
\ / \ /
c=c c=c
/ \ / \
H H H Br

cis-1,2-dibromoethene trans-1,2-dibromoethene
(bromine atoms on the same side) (bromine atoms opposite one another)

Although these molecules have the same molecular formula, CHBr= CHBr, they cannot be turned into one
another without breaking the double bond. The molecules also have different physical properties (eg different
melting and boiling points).
2. But-2-ene has geometric isomers:
CH3 CH3 CH3 H
\ / \ /
C = C C = C
/ \ / \
H H H CH3

cis but-2-ene trans but-2-ene

Geometric isomerism does not occur with alkanes.

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. 66 Chemistry Achievement Standard 2.4

3. Not all alkenes exhibit geometric isomerism:

Br H
\ /
C = C
/ \
Br H
1,1 -dibromoethene

Questions: Isomers

HCOCH 2 CH 2 CH 3
CH3CH2CH2CH20H CH 3 CH=CHCH3
0
A B c

CH 3 CH 2 CH 2 COH CH3C=CH2
CH3CH2CH2CH3 1
0 CH 3
D E F

1. a. Explain what is meant by the term structural isomer. Use examples from the table above to
illustrate your answer.

b. Compound B has two geometric isomers (c/'s and trans). Draw the TWO isomers in the boxes
below.

trans isomer

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 Characteristics and physical properties of hydrocarbons 67

2. Which pairs of the organic molecules below are structural isomers?

H H H H H H H H H H C I H
I I I I I I I I I I I I
A H—C—C—C—C—C—C—H B H—C—C—C—C—C—C—H

H H H H CI H H H CI H H H

H H H H H H H
1 1 1 1 1 1 i1H j 1
i l l ! 1 1 1
c H —C —C —C —C —H D H—C —
C —
c —C — CI
1 1 1 1 1 1 1
1
H H H OH H CH 3 H H

CH 3 H H H H
1 | |
1
E CH 2 CI — C — C H 3 F CI — C --
|
c - - C1 - - C1 - • H
I 1 1 l l
CH 3 H H H OH

Draw the structural isomers with the molecular formula, C 5 H 12 .

4. a. Which of the following substances would exhibit cis-trans isomerism?

H H u r\ r\ u
H
11 11
H CI CI
\ / \ /
H— C— C— H B C ==
= CC cC cC == C D CI — C — C — CI
I I // \
\ // \
\ | |
CI H
H CI H
H
H CI H H

b. Draw the cis-trans isomers that you have identified in a.

5. Draw all four structural isomers of the haloalkanes with the molecular formula, C 4 H 9 Br.

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68 Chemistry Achievement Standard 2.7

6. Which of the alcohols below are structural isomers?

OH OH
I I
A CH3CHCH2CH2CH3 B CH3CHCHCH3
I
CH 3

C CH 3 CHCH 2 CH 3 D CH3CH2CH2CH2CH2OH
I
OH

7. a. Explain why the following molecules are not structural isomers.

H H H O H H H H H
I I I II I I I I I
H— C— C— C— C— O— C— H and H— C— O — C— C— C— C— H
I I I I I II I I I
H H H H H O H H H

b. Explain why the following molecule does not exhibit cis-trans isomerism:
CH 3 H
\ /
C = C
/ \
CH 3 H

Carboxylic acids and esters

Carboxylic acids
Carboxylic acids are organic acids. Some are used in cooking (eg tartaric acid, citric acid); one of the
most familiar carboxylic acids is ethanoic acid (commonly called acetic acid). Vinegar contains about 4 %
ethanoic acid.
Carboxylic acids have the general formula RCOOH and form a homologous series.

The functional group is the carboxyl group, -COOH, or — C — OH.

II
O
Naming carboxylic acids
Replace the final 'e' from the corresponding alkane with 'oic'.

ethane (C 2 H 6 ): ethanoic (CH 3 COOH)

Branched chain carboxylic acids

Named in the same way as other branched chain molecules.

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 Characteristics and physical properties of hydrocarbons 69

Physical properties of carboxylic acids

Carboxylic acids are colourless liquids or white solids at room temperature. Pure ethanoic acid is referred to
as glacial acetic acid because it readily freezes below 16°C to resemble ice crystals.

Carboxylic acids are polar due to the -COOH group. The oxygen atoms are highly electronegative.

Small carboxylic acid molecules are soluble in water because of their polarity. As the length of the carbon
chain increases, the length of the non-polar part of the carboxylic acid (ie the carbon chain) becomes larger
- hence the large carboxylic acid molecules are insoluble in water.

The boiling point and melting points increase with increasing size, as there are stronger forces present
between the molecules.
The boiling points and melting points are also higher than the corresponding alkanes, because the polarity
of the carboxylic acid molecule means the attraction between molecules is also increased.

Chemical properties of carboxylic acids

Carboxylic acids are weak acids - eg, ethanoic acid will partially ionise in water:

CH 3 COOH(aq) + H 2 0(l) CH 3 COO"(aq) + H 3 0 + (aq)

Carboxylic acids can be formed from the oxidation of an alcohol.

Solutions of carboxylic acids will:

• Turn blue litmus red.
• Conduct electricity due to ions present in solution that are free to move.
• React slowly (because they are weak acids) with magnesium ribbon to form a salt and hydrogen gas, eg:

2CH 3 COOH + Mg > (CH 3 COO) 2 Mg + H2

ethanoic acid magnesium magnesium ethanoate hydrogen gas

Mg disappears and bubbles of gas are observed.

• React with metal oxides and metal hydroxides to form a salt and water, eg:

CH 3 COOH + NaOH > CH 3 COONa + H20

ethanoic acid sodium hydroxide sodium ethanoate water

• React with metal carbonates and metal hydrogen carbonates (bicarbonates) to form a salt, water and
carbon dioxide, eg:

CH 3 COOH + NaHC0 3 > CH 3 COONa + H20 + C02

ethanoic acid sodium bicarbonate sodium ethanoate water carbon dioxide

2CH 3 COOH + Na 2 C0 3 > 2CH 3 COONa + H20 + C02

ethanoic acid sodium carbonate sodium ethanoate water carbon dioxide

Bubbles of gas are observed.

Esters
Esters are organic compounds with the general formula of RCOOR' (where R and R' represent alkyl groups)
and form a homologous series.

The functional group is — C — O —

O
Esters often have fruity smells.

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70 Chemistry Achievement Standard 2.7

Naming esters

<J>
Split the molecules into two o
parts at the C — O bond. //
CH3CH2Cy
OCH3

<DIdentify the alcohol part. The

r

— OCH3 fr<3m alcohol.

number of carbons attached to Therefore , methyl.
the O forms the first part of the
name, with the ending 'yl'.

(3>
Identify the carboxylic acid part. O
The number of carbons that has //
come from the carboxylic acid CH3CH2C comes from the
forms the second part of the \ acid; 3 carbons,
name, with the ending 'oate'. therefore
'propanoate'.

Note: The words are separate, not

joined as in other organic Methyl propanoate
substances.

Preparation of Esters
Esters can be made by reacting a carboxylic acid with an alcohol using concentrated sulfuric acid as a
catalyst.
General equation:

carboxylic acid + alcohol =^ ester + water

Example
H o
// // H,0
H—C + CH3CH2OH H—C
\ \
OH OCH2CH3
methanoic acid ethanol ethylmethanoate water

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 Characteristics and physical properties of hydrocarbons 71

The process of ester production is called esterification.

In the reaction, the -OH group from the carboxylic acid

is removed, the H from the -OH group of the alcohol is
also removed, and water is formed. The -OH part of the
carboxyl group is replaced by the -OR group of the alcohol. condenser

The reaction does not go to completion unless concentrated

sulfuric acid is used as a catalyst and a dehydrating agent.
The acid removes water (drives equilibrium to the right),
producing more ester. Because the reaction is slow and pear-shaped
incomplete, refluxing is used to produce the ester. flask
The reactants boil and the gases formed condense back
boiling water
down into the flask - this provides maximum product
reaction mixture
formation, as reactants can be heated without the
reactants vapourising away.

The water bath is used rather than heating directly with a

Bunsen, as the Bunsen flame could otherwise cause the
volatile reagents and products to ignite.

Hydrolysis of e s t e r s
Hydrolysis of esters results in the ester being broken up into the alcohol and carboxylic acid, from which
the ester was formed. The reaction is catalysed with either an acid or a base. When a base is used, the
carboxylic acid formed reacts with the base to form a salt.

Example
O O
CH,
//
\ //
CH 3 C
OCH2CH3 \
NaOH CH3CH2OH 0 _ Na +

ethyl ethanoate sodium hydroxide ethanol sodium ethanoate

(salt of ethanoic acid)

When an acid is used, the alcohol and carboxylic acid are formed.

Example
O O
//
CH, CH 3 C
\ \
OCH 2 CH 3 HJO CH 3 CH 2 OH OH

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72 Chemistry Achievement Standard 2.7

Triglycerides and soap

Triglycerides are triesters and are used to make soap.

Triglycerides (triesters) are formed in a similar way to other esters (ie a reaction between an alcohol and
a carboxylic acid). The alcohol is glycerol (propan-1,2,3-triol); the carboxylic acids are acids with long
hydrocarbon chains (called fatty acids). In the reaction, 3 fatty acid molecules join to one glycerol molecule:
ester linkage

g
i + fatty acid
V
c + fatty acid
e
— • - W -
r
0 + fatty acid
1
triglyceride
An example of this reaction is that between glycerol and stearic acid, CH 3 (CH 2 )i6COOH:

H H O

H — C — OH H —C — O — C (CH 2 ) 16 CH 3
O

OH 3CH 3 (CH 2 ) 16 COOH H— C— O— C-(CH2)16CH3

stearic acid O

H OH H C- O - C — (CH 2 ) 16 CH 3

H H
glycerol

Soap manufacture
Triglycerides can be found naturally as oils in seeds and nuts, and fats in animals. Fats are soft solids at room
temperature, oils are liquid at room temperature.

Soap is made by heating fats and oils with sodium hydroxide (ie hydrolysis of the triester). The fat or oil
(triester) is hydrolysed to produce glycerol and the sodium salt of the long chain-carboxylic acid, in a
reaction called saponification.

The sodium salt formed is commonly called soap.

CH 3 (CH 2 ) 1 6 COOCH 2 HO — C H 2

CH 3 (CH 2 ) 1 6 COOCH + 3NaOH 3CH 3 (CH 2 ) 1 6 COONa + HO — C H

CH 3 (CH 2 ) 1 6 COOCH 2 HO — C H 2
sodium stearate glycerol

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 Characteristics and physical properties of hydrocarbons 73

Questions: Carboxylic acids and esters

1. a. Describe what would be observed if CH 3 CH 2 CH 2 COH is added to sodium carbonate.
II
O
h.
CH 3 CH 2 CH 2 CH 2 OH HCOCH 2 CH 2 CH 3 CH 3 CH 2 CH 2 COH
IIII
0 o
A B c

Compounds A, B and C are all colourless liquids. Describe tests that would identify EACH of
these compounds if the labels were left off the bottles. Use the physical a n d chemical properties
of these compounds to select suitable tests. Include any observations that would be made when
carrying out these tests.

c. Complete the table below by writing:

i. the name of EACH functional group circled

ii. the systematic name for EACH compound.

N a m e of Systematic n a m e
Compound
functional group of t h e c o m p o u n d

CH 3 CH,COH\
II

PH 3
II
w

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74 Chemistry Achievement Standard 2.7

2. Compounds X, Y, Z, W , V and V' are involved in a series of reactions as shown by the scheme below.
In this scheme only the organic reaction products are indicated. Molecular formulae for compounds
X and W are given. Additional information about the compounds is listed in the box at right.

Complete the table below by writing the structural formula and name for EACH compound.
(Hint: Begin with compound X, which is a straight-chain molecule.)

Compound Structural formula Name

V'

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 Characteristics and physical properties of hydrocarbons 75

3. Fats and oils are triester molecules. Hydrolysis of a fat can be represented by the equation below.

O
II
CH 2 OC(CH 2 ) 16 CH 3

? + SNaOH • f + C o m P°und
CHOC(CH 2 ) 16 CH 3 3CH 3 (CH 2 ) 16 CONa M

O
II
CH 2 OC(CH 2 ) 16 CH 3

a. Circle ONE of the ester groups in the fat.

b. Write the name of the functional group that would be present in compound M.

Unsaturated fats are usually considered to be healthier than saturated fats,

c. What is meant by the term unsaturated?

4. Draw the structural formula for propanoic acid.

5. Name the following molecule:

H H H H
1 1
I i
C -- C — C — C —
i I i
1 1 1 1
H H H H

6. Write the letter of the organic compound below that is:

a. An ester:

b. A carboxylic acid:
O
//
CH 3 CH 2 CH 2 COOH CH 3 CH 2 CH 2 CH 3 CH 3 CH 2 C CH 3 CH 2 CH 2 CH 2 OH

OCH 3
A B C D

7. Ethyl methanoate is an ester that smells like raspberries. What organic substances would you use to
make this ester?

8. Propyl ethanoate is found in pears.

a. Draw the structural formula of propyl ethanoate.

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76 Chemistry Achievement Standard 2.7

b. Circle the functional group on the structural formula you have drawn.

9. When ethanol, butanoic acid and concentrated sulfuric acid are heated under reflux conditions, a
product that smells like pineapple is formed.

a. What is the purpose of refluxing?

d. What homologous group does the organic product belong to?

e. Write the equation using structural formulae for the formation of the organic product.

10. Write the names of the alcohol and carboxylic acid which could be used to make the following esters:

a. CH 3 CH 2 CH 2 COOCH3

i. Alcohol: ii. Carboxylic acid:

0

b. CH 3 CH 2 CH 2 OCCH 3

i. Alcohol: ii. Carboxylic acid:

11. The following substance is made by the reaction of an alcohol and a carboxylic acid:

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 Characteristics and physical properties of hydrocarbons 77

0
II
C 17 H 35 — C — O — CH 2
0
II
C 17 H 35 — C — O — C H
0
II

C 17 H 35 — C — O — CH 2

a. What organic family does this molecule belong to?

b. What is the name of the alcohol that is used to make this molecule?
c. Soap can be made from this molecule. Write an equation for the formation of the soap from this
molecule.

d. What is the name given to the soap-making reaction?

12. Complete the following equations using structural formulae for the organic products,
a. H H H H O
I I I I II
H — C — OH + H — C — C — C — C — OH

H H H H

methanol + butanoic acid

H

H - C - C
/ H H
I \ I I
A o — C — C — H + NaOH
H I I
H H
sodium hydroxide —>
ethyl ethanoate +
13. Name the following compounds:
O

a. CH 3 CH 2 COCH 2 CH 3 b. CH 3 COCH 3
II
O CH 3
I
c. CH 3 CH 2 CH 2 COOH d. CH 3 CHCOOH

e. CH 3 CH 2 CH 2 CH 2 OCCH 2 CH 3
II
o

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78 Chemistry Achievement Standard 2.7

14. You have been given two unlabelled bottles that contain colourless solutions. One contains a solution
of an ester and the other a solution of a carboxylic acid. You have been provided with some baking
soda, NaHC0 3 , and litmus paper. Using the resources available to you, describe TWO simple tests that
you could carry out to tell the difference between the substances. What observations would you make
in each case?

Test 1:

Observation:

Test 2:

Observation:

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 NCEA
Achievement
90310 Standard
Describe
reactivity
principles of chemical
2.6
Externally assessed
4 credits

Energy changes
Energy changes are involved in chemical reactions. Heat energy changes are common.

Exothermic reactions
Heat energy is produced by exothermic reactions, eg candle burning, zinc reacting with copper sulfate
solution, fireworks going off. The heat production can be detected by an increase in the temperature of the
surroundings (the air, the test tube, etc).

Example
Zinc a d d e d t o hydrochloric a c i d

Thermometer-

Heat energy is released (reaction is exothermic) and warms the

surroundings. As a result, the test tube feels warmer and the
temperature increases.
Heat -HCI
energy

Heat
energy
Zn-

G
Endothermic reactions
Heat energy is absorbed by endothermic reactions, eg water evaporating, dissolving ammonium chloride in
water, photosynthesis. The heat absorbed causes a decrease in the temperature of the surroundings.

Example
A m m o n i u m nitrate added to w a t e r

Ammonium • Thermometer
nitrate n

Heat energy is taken in (reaction is endothermic) from the

surroundings (test tube and everything outside it). As
a result, heat is being lost from the surroundings so the
Heat
temperature drops.
energy

Heat
energy
Water

\ J
80 Chemistry Achievement Standard 2.6

Enthalpy
Reactants and products have an amount of energy called enthalpy or heat content (symbol H). Enthalpy
cannot be measured.
Heat is given out or absorbed during a reaction, thus the heat content of the reactants and products is
different. The heat energy change is called the enthalpy change or heat of reaction (symbol AH). The
enthalpy change can be measured, and can be expressed as:

A/"/ = ^products ~~ ^reactants

The units for AH are ] or kj.

Enthalpy of reaction (ArH)

Enthalpy of reaction has the symbol A r H. Units are kj moH.

Example _
2H 2 (g) + 0 2 (g) 2H 2 0(I) A r H = -570 k] mol"1

The heat change is to be read per the chemical equation, ie kj per mole of reaction.

Energy diagrams
Energy

reactants
Exothermic reaction
Energy given out to surroundings.
The surroundings warm up.
Enthalpy
The products have less energy
Exothermic reactions:
than the reactants.
ArH is negative.
Endothermic reactions:
Reaction proceeds
ArH is positive.

products

Endothermic reaction
Energy taken in from the surroundings.
Enthalpy Surroundings cool down.
The products have more energy
than the reactants.

Reaction proceeds

Bond breaking is endothermic.

In a reaction, bonds break and bonds form. The energy given out or
absorbed in reactions comes from the making or breaking of bonds. Bond making is exothermic.

If the overall reaction is exothermic, then more If the overall reaction is endothermic, then more
energy is released when bonds of the products form energy is absorbed to break bonds in reactants
than is absorbed when bonds of the reactants break. than is released when bonds of the products form.

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 Describe principles of chemical reactivity 81

Using heat change information and heat change calculations

Heat change information can be used to calculate A r H.

Example
N 2 (g) + 3H 2 (g) -> 2NH 3 (g) A r H = -92 k| mol-1

For the reverse reaction, the sign changes:

2NH 3 (g) -> N 2 (g) + 3H 2 (g) A r H = + 92 kj m o H

Example
If 2 mol of nitrogen, N 2 , reacts with 6 mol of hydrogen, H2, the equation is written as:

2N 2 (g) + 6H 2 (g) -> 4NH 3 (g) and A r H = -184 kj mol"1

92 k] of energy is released w h e n 1 mol of N 2 reacts; therefore, 92 x 2 kj of energy is released w h e n

2 mol of N 2 reacts (ie 184 kj of energy is given out).

Examples
1. Determine the amount of energy released when 2 g of NaOH is dissolved. M(NaOH) = 40 g mol-1.

NaOH(s) Na + (aq) + OH-(aq) A,H = -20.2 kj mol"1

Answer. n(NaOH) = —
M
= 2_

40
= 0.05 mol

1 mol of NaOH releases 20.2 kj, so 0.05 mole releases 0.05 x 20.2 = 1.01 kj.

2. 504 J of energy is released when 1 g of NaOH dissolves in 40 mL of water. The temperature of the water
rises 3°C.

a. How much energy is released when 1 g of NaOH dissolves in 20 mL of water?

b. What is the rise in temperature of the water?

Answer, a. 504 J of energy. Same mass of NaOH dissolving so same amount of energy.

b. 6°C. As the volume of water is less, the amount of heat dispersing through
the water will cause a greater rise in temperature. As there is half the
amount of water (20 mL), then the temperature rise is double

Questions: Energy changes

1. Classify E A C H of the following processes as e i t h e r endothermic o r exothermic.

Process endothermic or exothermic

a. H2(g) + lO2(g) H20(g) A r H = - 2 8 6 kj mol" 1

b. Photosynthesis - food-making process in plants

c. Freezing of w a t e r

Dissolving sodium hydroxide in water

d
(the temperature increases)

e. Sublimation of solid carbon dioxide to carbon dioxide gas

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82 Chemistry Achievement Standard 2.7

2. Hydrogen peroxide, a common bleaching agent, decomposes as follows:

H 2 0 2 (l) -» H 2 0(l) + I 0 2 ( g ) ArH = -98.2 kj mol"1

a. Calculate how much energy is released when 5 moles of hydrogen peroxide decompose.

b. Calculate how much energy is released when 1.0 g of oxygen is formed by the decomposition of
hydrogen peroxide.

c. Calculate the mass of hydrogen peroxide that must decompose to produce 600 kj of energy.

3. State whether the following involve either endothermic or exothermic reactions.

a. Burning coal.

b. Clothes drying on a washing line.

c. Ammonium chloride dissolving in water causing temperature to drop.

d. Cyclohexane freezing.

e. Hydrated copper sulfate dissolved in water. ArH is positive.

f. C 3 H 8 (g) + 50 2 (g) 3C0 2 (g) + 4H 2 0(g) ArH = -2 044 kj mol"1

g. Reaction involved in launching the Space Shuttle.

4. In the production of ammonia, methane, CH4, is steam reformed to produce synthesis gas. The
reaction is:

CH 4 (g) + H 2 0(g) CO(g) + 3H 2 (g) ArH = +206 k) moH

a. Is the reaction exothermic or endothermic?

b. What is the value of ArH for the following reactions:

i. CO(g) + 3H 2 (g) CH 4 (g) + H 2 0(g) \H =

" 3CH 4 (g) + 3H 2 0(g) —> 3CO(g) + 9H 2 (g) A r H =

5. The initial temperature of a flask of water is 1 7°C. Ammonium nitrate is then dissolved in the water.
After dissolving, the temperature is 15°C. Explain the change in temperature of the water in terms of
energy changes.

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 Describe principles of chemical reactivity 83

6. The following reaction is involved in the manufacture of sulfuric acid:

2S0 2 (g) + 0 2 (g) 2S0 3 (g) 188 kj of energy is released.

a. Is the reaction exothermic or endothermic?

b. What is the value of ArH if 4 mol of S0 2 is used?

c. How many kilojoules of energy are released if 192 g of sulfur dioxide, S0 2 , reacts with excess
oxygen? /W(S02) = 64 g mol-1.

d. Calculate the heat energy released when 0.25 mol of sulfur trioxide, S0 3 , is formed.

7. The decomposition of calcium carbonate can be written as:

CaC0 3 (s) CaO(s) + C0 2 (g) ArH = +1 79 kj mol"1

a. Calculate the amount of energy absorbed for 0.2 mol of CaC0 3 decomposing.

b. Calculate the amount of energy absorbed if 15 g of CaC0 3 is used.

M(CaC03) = 100 g mol"1

c. Determine the mass (in grams) of CaC0 3 that reacts when 805.5 kj of energy is absorbed.

8. 32.2 kj of energy is released when 5 g of sulfuric acid, H 2 S0 4 , is added to 100 mL of water. The
temperature of the water rises 8°C.

a. How much energy is released when 10 g of H 2 S0 4 is added to 100 mL of water?

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84 Chemistry Achievement Standard 2.7

b. How much energy is released when 5 g of H 2 S0 4 is added to 50 mL of water?

c. What is the temperature rise when 5 g of H 2 S0 4 is added to 50 mL of water?

Rates of reactions
Rate of reaction is 'the speed at which a reaction occurs'.

Some reactions occur quickly (eg adding zinc to hydrochloric acid), others occur slowly
(eg rusting iron in a car).
Volume of hydrogen gas formed against time
Measuring rates of reactions
The rate at which a reaction occurs is measured
by how quickly reactants are consumed or how
quickly products form (eg a gas product can
be measured).

The graph shows how the volume of hydrogen

gas given off in the reaction between zinc and
hydrochloric acid, changes over time.

Collision theory
For a reaction to occur, particles must collide
(ie bump into one another). Bonds break and
new bonds form to make new substances.
Time (s)
Factors that control rates of reactions are:
• The frequency of collisions - the more collisions in a given time, the faster the reaction.
• The effectiveness of the collisions - this is in terms of orientation (reactant particles must be positioned
so that bonds break and bonds form) and sufficient energy (particles must collide with sufficient energy
to break existing bonds and make new bonds).
Particles must collide with enough kinetic ('moving') energy. Total kinetic energy must be greater than
the activation energy. Activation energy (£ A ) is the minimum amount of energy required for a reaction
to proceed between colliding particles. AH is always positive for activation energy.

Exothermic reaction energy diagram

Enthalpy

reactants y rv<
Energy given
out, A H
, products

Reaction proceeds

The total energy released is greater than the f A .

Exothermic reactions, once started, continue - this is because as the reaction proceeds enough energy is
provided to give reactant particles sufficient energy to overcome the activation energy (or more energy
than the activation energy).

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 Describe principles of chemical reactivity 85

Endothermic reaction energy diagram

Reaction proceeding

Factors affecting rates of reactions

The rate of a reaction depends on the concentration, surface area, temperature of reactants, and the
presence of catalysts.

Concentration
This affects reactions in which reactants are gases or at least one of the reactants is in solution.

With increased concentration, particles are closer together, so there is an increased chance of colliding.
As a result, the frequency of collisions increases and hence the rate of reaction increases.
The rate of a reaction will decrease as the reaction Dilute acid Concentrated acid
continues because the concentration of the reactants r
is decreasing.
For solutions, using a more concentrated solution
\ v;vy
will increase the rate of reaction.
1 1 ^ H"*" ions
% A •> *

h
- magnesium
metal
a
+

Fewer H + ions in More H + ions in

the same volume of the solution, so
solution, so fewer more collisions
collisions occur occur between
between H + and Mg. H + and Mg.
Reaction is faster
than in dilute acid.

For gases, increasing the pressure or introducing more Sulfur in air Sulfur in oxygen
of the reactant gas into the container will increase
concentration of gases.

deflagrating spoon

In air, only one in five In pure oxygen, all

particles colliding with particles colliding with
sulfur is an oxygen the sulfur are oxygen
molecule. molecules.
Reaction is faster than

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86 Chemistry Achievement Standard 2.7

Surface area Lump of calcium Powdered calcium

carbonate carbonate
Increasing the surface area means exposing a
-H+ions
greater part of one reactant to the other reactant,
CaC03
eg using a powder instead of a solid.
particles
Because there is an increase in the surface area exposed to H +

exposed, the frequency of collisions increases and

hence the rate of reaction increases. CaCC>3 particles
not exposed to
Stirring and shaking can expose the surface of H+
reactants. This increases the number of collisions. 2 g lump of calicum 2 g of powdered calicum
carbonate, fewer carbonate, more particles
particles exposed to H 4 exposed to H + .
Reaction is faster when
Temperature reactant is powdered.

Temperature is a measure of the average kinetic energy of particles. The collisions are more energetic
(effective) and more collisions will have more energy than the activation energy, so the reaction is faster. If
temperature is increased, particles also move faster and there is more chance of collisions. As a result, the
frequency of collisions increases and hence the rate of reaction increases.

Catalyst Enthalpy (kj)

A catalyst can speed up a reaction. A catalyst increases
the rate of reaction by lowering the activation energy for ^ E a for uncatalysed
2H202 1 reaction = 75 kj
the reaction. This means that collisions are more effective
reactant / \\
as more particles have sufficient energy to react.

A catalyst is not used up by a reaction and does not

/
E a for catalysed
AH = -189 kJ
, 2H20 + 0 2
reaction = 50 k j
change the products formed. It provides an alternative products
pathway for the reaction.
: •
Reaction proceeds
Biological catalysts are proteins called enzymes
(eg amylase in the mouth is involved in digestion,
breaking starch down into glucose).

Questions: Rates of reactions

1. A 1 g lump of calcium carbonate was added to a 250 mL beaker containing 100 mL of 1.0 mol L_1
hydrochloric acid solution, at room temperature (25°C). Bubbles of carbon dioxide were produced.

The experiment was repeated under different conditions, as given below.

a. For EACH change, describe how the reaction rate would be affected.
Use the words 'increase', 'decrease' or 'remain the same' in each answer.
Change 1
The temperature of the reaction mixture was increased to 40°C.

Effect:
Change 2
100 mL of water was added to the acid. 100 mL of this diluted acid solution was added to a 1 g
lump of calcium carbonate.

Effect:

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 Describe principles of chemical reactivity 87

Change 3

The 1 g lump of calcium carbonate was ground to form a powder, and then 100 mL of the

1.0 mol L _1 hydrochloric acid was added.

Effect:

Change 4

A 500 mL beaker was used instead of the 250 mL beaker, but the same amounts of reactants were used.

Effect:

b. Explain the effect on the reaction rate for Change 1 and Change 2 above by referring to the
collisions of particles.

Change 1:

Change 2:

a. Draw a line on the diagram to show how the energy diagram would appear with the addition
of a catalyst.

b. The equation for the decomposition of hydrogen peroxide is:

2H 2 0 2 (I)->2H 2 0(I) + 0 2 (g)

The catalyst manganese dioxide can be used to increase the rate of decomposition of the
hydrogen peroxide. State two characteristics of a catalyst.

c. Explain in terms of collision theory how a catalyst, such as manganese dioxide, increases the rate
of reaction.
88 Chemistry Achievement Standard 2.7

3. A student carries out an experiment in which zinc granules of the same mass are reacted with
2 mol L-1 hydrochloric acid. The student carries out the experiment under three temperature
conditions.

The reaction occurs according to the equation:

Zn(s) + 2HCI(aq) -> ZnCI 2 (aq) + H 2 (g)

The rate of reaction is measured by the volume of hydrogen gas released.

The student used the following table to record their results:

Experiment Temperature (°C) Volume of H 2 released ( m L )

1 10

2 20

3 30

a. Which experiment would have the slowest reaction rate? Explain your answer.

b. For Experiment 3, how would you expect the rate of production of hydrogen gas to change over
time? Justify your answer.

c. Which experiment would go to completion quickest? Explain your answer in terms of collision theory.

4. Which one out of the pair of substances below would react faster? Explain your answer in terms of
collision theory.

A Zinc sheet and dilute hydrochloric acid;

or

B Zinc sheet and concentrated hydrochloric acid.

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 Describe principles of chemical reactivity 89

5. The following graph shows the result of 2 g powdered marble (calcium carbonate) reacting with dilute

a. Explain why the graph levels off.

b. i. Draw another line on the graph to show what the graph would look like if 2 g of solid
marble pieces were used.
ii. Justify your answer in terms of collision theory.

6. Ammonia is produced commercially to make fertilisers such as urea. In producing ammonia, nitrogen
gas reacts with hydrogen gas according to the following equation:

N 2 (g) + 3H 2 (g) ^ 2NH 3 (g) ArH = -92 kj mol"1

Name ONE way in which it is possible to increase the rate of the reaction. Using collision theory,
explain how this rate is increased.

Equilibrium
Many chemical reactions effectively go to completion (ie occur in one direction).

Example
A strip of magnesium will react with excess oxygen gas until all the magnesium is used up:

2Mg(s) + 0 2 (g) 2MgO(s)

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90 Chemistry Achievement Standard 2.7

Some reactions occur in both directions, ie they are reversible. Reversible reactions are represented by the
symbol

Example
Orange iron(lll) ions, Fe3+, react with colourless thiocyanate ions, SCN", to form a blood-red complex, FeSCN2+:

Fe3+(aq) + SCN"(aq) ^ [FeSCN] 2+ (aq)

The f o r w a r d reaction goes from left to right. The reverse (or b a c k w a r d ) reaction goes from right to
left. Although the reaction is reversible, substances on the left-hand side of the equilibrium sign are called
reactants and substances on the right-hand side of the equilibrium sign are called products.
In the above Example, the reactants, Fe3+ and SCN~, react to form the product, [FeSCN]2+. As soon
as [FeSCN]2+ is formed, some of it begins to break up back into the reactants. This continues until
equilibrium is reached - the r a t e of the forward reaction is equal to the rate of the reverse reaction.

When equilibrium is reached, there is no observable change. In the preceding Example, the colour of
the blood-red complex remains at the same intensity at equilibrium, as reactants are still changing into
products and products are changing into reactants at the same rate. In an equilibrium system, both
reactants and products are present. In the preceding Example, Fe3+, SCN - and [FeSCN] 2+ will be all present
at equilibrium.

Continuous change in this way is described as a dynamic equilibrium.

As the forward and reverse reactions occur at the same rate, the concentration of products and reactants
remains constant. This does not mean there is an equal concentration of reactants and products.

For equilibrium to exist, a system must be closed, ie reactants and products are in a situation in which
particles cannot leave. In the preceding Example, the system is closed as the particles are contained in
aqueous solution.

Some equilibrium systems do not have new substances being formed. This is known as physical equilibrium.

Example
In a saturated solution of calcium sulfate, calcium sulfate is dissolving at the same rate as calcium ions and sulfate
ions are crystallising to form solid calcium sulfate.

E q u i l i b r i u m c o n s t a n t , Kc
In the following equation, amounts are a, b, c and d; reactants are A and B; products are C and D:

aA + bB ^ cC + dD
The ratio of products to reactants is expressed as the equilibrium constant K.
_ [C]' [D] d
C [A]a [B] b
[ ] is the concentration, measured in mol L~1 at equilibrium.

Example
For the reaction:
[NH 3 (g)] 2

Pure solids or liquids do not appear in the equilibrium expression because their concentration is constant.

If Kc is large (greater than 1 000 or 103), the concentration of products is large and the reaction almost goes
to completion - 'equilibrium favours the forward direction' and product(s) are favoured.
If Kc is small (less than 0.001 or 10-3), the concentration of products is small and only a small amount of
reactants has been changed into products - 'equilibrium favours the reverse direction (backward direction)'
and reactant(s) are favoured.

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 Describe principles of chemical reactivity 91

Changes to equilibrium
Changes in concentration, temperature or pressure can change the position of equilibrium. Predictions
about the direction of change when an equilibrium is disrupted can be made by applying Le Chatelier's
Principle:

'When a change is made to a system at equilibrium, the system responds to reduce the effects of the
change.'

The principle does not predict the extent of the change.

If the change results in more products, it is said that 'equilibrium has moved in the forward direction'. If
the change results in more reactants being formed, it is said that 'equilibrium has moved in the reverse
direction'.

Concentration
If the concentration is changed, the equilibrium system responds to counteract this change. For the
equilibrium reaction Fe3+(aq) + SCN _ (aq) ^ [FeSCN]2+(aq), if more Fe3+(aq) is added (ie concentration of
Fe3+(aq) is increased), the equilibrium shifts to reduce the effect of this change by moving to favour the
forward direction.

Pressure
Pressure can be altered by changing the amount of gas in a closed system or changing the volume of a
closed system.
An increase in pressure (by adding more gas or decreasing the volume of the closed system) will be
counteracted by decreasing the number of gas particles in the equilibrium mixture. Hence, the equilibrium
shifts to the side with the least number of moles of gas.

Example
N 2 (g) + 3H 2 (g) ^ 2NH 3 (g)
Decreasing volume will increase pressure. System will move to reduce the number of gas particles so will move
to the right, ie favours the forward direction.

A pressure change will only have an effect if gases are present.

Addition of unreactive gases has no effect on the position of equilibrium.

Temperature
Increasing the temperature will favour the Decreasing the temperature will favour the
endothermic reaction. This counteracts the effect exothermic reaction. This counteracts the effect
of the increase in temperature by energy being of the decrease in temperature by energy being
absorbed. released.
In equilibrium reactions, the A r H sign refers to the forward reaction. When A r H is positive, the (forward)
reaction is endothermic. When ArH is negative, the (forward) reaction is exothermic.
92 Chemistry Achievement Standard 2.7

Summary of responses of equilibrium system to changes

Change in conditions Direction of change in equilibrium position

Concentration - Increase products In the reverse direction

- Decrease products In the forward direction

- Increase reactants In the forward direction

- Decrease reactants In the reverse direction

Pressure Increase In the direction with the least number of moles of gas

Decrease In the direction with the greater number of moles of gas

Temperature Increase In the direction of the endothermic reaction

Decrease In the direction of the exothermic reaction

No change in equilibrium position or in Kc; equilibrium is

Catalyst added
reached more quickly (ie reaction rate changes)

Questions: Equilibrium
1. Write the equilibrium constant expression for EACH of the following reactions:
a. 2S0 2 (g) + 02(g) 2SO3(g) Kc =

b. 4NH 3 (g) + 502(g) 4NO(g) + 6H2Q(g) Kc =

c. C H 3 C O O H (oq) H+(oq) + CH 3 COO ~(aq) Kc =

2. Two oxides of nitrogen exist in the following equilibrium system:

2N0 2 (g) N 2 0 4 (g) ArH = -57 k] moM and Kc = 6.3 x 10"5 at 227°C

a. Which oxide would you expect to be present in the greater concentration at equilibrium?

(Circle your answer.) N02 or N204

b. Justify your answer to a. above.

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 Describe principles of chemical reactivity 93

c. N 0 2 is a brown gas and N 2 0 4 is a colourless gas.

What would you expect to observe when the following changes are applied to the equilibrium
system? In EACH case, justify your observation.

i. The temperature is increased to 500°C (without changing the pressure).

Observation:

Explanation:

ii. More N 0 2 gas is added to the system.

Observation:

Explanation:

3. Which of the following reactions are in equilibrium?

a. An open beaker containing a solution of table salt (sodium chloride).

b. A jar of water covered with tightly sealed cling film.

c. A test tube of hydrochloric acid and a zinc granule.

d. A 1.5 L bottle of lemonade.

4. Write the equilibrium constant expression, KCI for the following:

a. PCI 5 (g) ^ PCIj(g) + Cl 2 (g)

b. 2N 2 (g) + 0 2 (g) ^ 2N 2 0(g)

c. CO(g) + 2H 2 (g) ^ CH 3 OH(g)

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i
94 Chemistry Achievement Standard 2.6

5. Hydrogen gas and chlorine gas react according to the following equation:

H 2 (g) + Cl 2 (g) ^ 2HCI(g)

At 227°C, the equilibrium constant, Kc, is 4 x 1018.

a. Write an equilibrium expression for the reaction.

b. What does the size of Kc tell you about the concentration of the products compared with the
concentration of reactants at equilibrium?

c. What effect would the following have on the position of equilibrium:

i. Increasing the concentration of hydrogen gas?

ii. Removing hydrogen chloride gas?

iii. Decreasing the pressure?

6. The equilibrium between orange dichromate ions, Cr2072~ and yellow chromate ions, Cr042~, can be
written as follows:

Cr 2 0 7 2 "(aq) + OH-(aq) ^ Cr0 4 2 -(aq) + H+(aq)

a. Ba2+(aq) ions can be added to remove chromate ions, Cr042~(aq), from the system.

What would happen to the concentration of dichromate ions, Cr2072~(aq), if Ba2+(aq) ions were
added to the equilibrium system? Explain your answer.

b. What observation would you make if hydrochloric acid were added to the system? Explain your
answer.
 Describe principles of chemical reactivity 95

7. Equilibrium in industry - a m m o n i a production

a. In the first step of ammonia production, methane is reacted with steam according to the
following equation:

CH 4 (g) + H 2 0(g) ^ CO(g) + 3H2(g) ArH = 206 kj moh1

What effect would the following have on the a m o u n t of m e t h a n e present at equilibrium:

i. Increase in pressure?

ii. Decrease in temperature?

iii. Removal of CO?

iv. Addition of hydrogen gas? __ _

v. Addition of a catalyst?

b. Ammonia is formed by reacting nitrogen gas and hydrogen gas together:

N 2 (g) + 3 H 2 ( g ) ^ 2 N H 3 ( g )

i. Write the equilibrium constant expression, KCI for this reaction.

ii. State whether decreasing the pressure would favour product formation or reactant formation.

iii. State whether addition of nitrogen gas would favour product formation or reactant
formation.

8. Equilibrium in industry - sulfuric acid production

One of the steps involved in sulfuric acid production is the reaction between sulfur dioxide gas and
oxygen gas to form sulfur trioxide:
2S0 2 (g) + 0 2 (g) ^ 2S0 3 (g) AH = -100 kj moM

a. Theoretically, a decrease in temperature would result in the equilibrium favouring production

of S0 3 . However, in practice, a moderate temperature of 400-500°C is used. Why are low
temperatures n o t used?

b. A catalyst of vanadium pentoxide, V 2 0 5 , is used. Why would a catalyst be used?

c. To increase the yield of S0 3 , what changes could be made to the pressure?

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96 Chemistry Achievement Standard 2.7

Acids and bases

An acid is a proton, H+, donor; a base is a proton acceptor.

HCI + NaOH-> NaCI + H 2 0

HCI is the acid (proton donor). NaOH is the base (proton acceptor).

A reaction in which a proton is donated and accepted is called an acid-base reaction.

Properties of acidic solutions

• pH < 7.
• Turn litmus red, phenolphthalein colourless, methyl orange red.
• Neutralised by bases.
• React with carbonates to form a metal compound, water and carbon dioxide gas.
eg: Na 2 C0 3 (s) + 2H+(aq) -> 2Na+ (aq) + H 2 0(l) + C0 2 (g)
• React with most metals to form a metal compound and hydrogen gas.
eg: Zn(s) + 2H+(aq) -> Zn 2+ (aq) + H 2 (g)
• React with metal oxides to form a metal compound and water,
eg: CuO(s) + 2H+(aq) -> Cu2+(aq) + H 2 0(l)
• React with a metal hydroxide to form a metal compound and water,
eg: Mg(OH) 2 (s) + 2H+(aq) -» Mg 2+ (aq) + H 2 0(l)
• Have a sour taste (eg citric acid in lemons, ethanoic acid in vinegar).
• Conduct electricity (they contain hydrogen ions that are free to move).

Properties of basic solutions

• pH > 7.
• Turn litmus blue, phenolphthalein pink, methyl orange yellow.
• Feel soapy.
• Neutralise acids.
• Conduct electricity (contain hydroxide ions that are free to move).
• Alkalis are soluble bases that form OH - ions in solution. Alkalis are a subset of bases.

Acids
Hydrogen ions do not exist by themselves. They attach to water molecules forming hydronium ions,
H 3 0 + (aq):

H+(aq) + H 2 0(l) H 3 0 + (aq)

Example
HCI(g) + H 2 0(l) -H> H 3 0 + (aq) + Ch(aq) (Hydrochloric acid is H 3 0 + and C h )

acid base
Hydrochloric acid is made by dissolving hydrogen chloride gas in water. HCI acts as an acid as it donates a
proton. H 2 0 acts as a base as it accepts a proton. The resulting solution is an acid because it contains H 3 0 + (aq).
The HCI has ionised in the water (ie ions have been formed). HCI can also be said to have dissociated
('split up').

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 Describe principles of chemical reactivity 97

Ions t h a t a r e a c i d i c
Some ions are acidic because they donate protons.

Example
Ammonium chloride is an acidic salt.

NH 4 + and CI - ions separate when NH 4 CI is dissolved in water.

H 2 O(I)
NH 4 CI(S) > NH 4 + (aq) + Cl"(aq)

The chloride ion, CI", is the s p e c t a t o r Ion (does not take part in the reaction) and is neutral.

The ammonium ion, NH 4 + , acts as an acid, donating a proton to water:

NH 4 + (aq) + H 2 0 =^= N H 3 ( a q ) + H 3 0 + ( a q )

ammonium ion ammonia

Because hydronium ions are present, the ammonium chloride solution is acidic.

Bases
Alkalis form hydroxide ions in solution.

Example
Ammonia is a base.

NH 3 (g) + H 2 0(l) ^ NH 4 + (aq) + OH"(aq)

base acid acid base

Ammonia is a base as it accepts a proton. Water acts as an acid.

Ions that are basic

Some ions are basic because they accept protons.

Example
Sodium carbonate is a basic compound.

Na+ and C 0 3 2 - ions separate when N a 2 C 0 3 is dissolved in water.

Na 2 C0 3 (s) H2°(l)> 2Na + (aq) + C0 3 2 "(aq)

The sodium ion, Na+, is a spectator ion and neutral.

The carbonate ion, C0 3 2 - , acts as a base, accepting a proton from water:

C0 3 2 "(aq) + H 2 0 ( l ) ^ HC0 3 "(aq) + OH"(aq)

The solution contains hydroxide ions, OH _ (aq), therefore a solution of sodium carbonate is basic.

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98 Chemistry Achievement Standard 2.7

Amphiprotic and neutral substances

An amphiprotic substance can act as a proton donor (acid) or a proton acceptor (base), eg H 2 0, HC03~,
HSO4-.
Neutral substances do not accept or donate a proton (eg Na+(aq)).

Acidic substances and basic substances

Acidic substances
Some substances are not acids but are described as acidic.

Example
Si0 2 (s) + 20H-(aq) Si0 3 2 -(aq) + H 2 0(l)

Silicon dioxide is not an acid (it is insoluble), but since it dissolves in a base such as sodium hydroxide, it is said
to be an acidic substance.

Basic substances
Some substances are not bases but are described as basic.

Example
CuO(s) + 2H + (aq) Cu 2+ (aq) + H 2 0(l)
copper oxide acid copper ions water
(black) (blue)

Copper oxide is a base - although insoluble in water, it dissolves in an acid.

Amphoteric substances
Amphoteric substances act as acids or bases (eg aluminium oxide, Al 2 0 3 , and aluminium hydroxide,
AI(OH) 3 ; zinc oxide, ZnO, and zinc hydroxide, Zn(OH) 2 ; lead(ll) oxide, PbO, and lead(ll) hydroxide,
Pb(OH) 2 ) - they dissolve in both acidic and basic solutions.
The oxides of row-3 elements provide examples of both water-soluble and insoluble compounds that have
acidic, basic or amphoteric properties.

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 Describe principles of chemical reactivity 99

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100 Chemistry Achievement Standard 2.7

lonisation of water
Although water contains mostly water molecules, it ionises slightly and behaves as both an acid and base:

H 2 0(l) + H 2 0(l) ^ H 3 0 + (aq) + OH"(aq)

Experimental evidence shows that the product of the concentrations of H 3 0 + (aq) and OH"(aq) have the
constant value of 1 x 10-14 at 25°C. This value is called the w a t e r dissociation constant (K w ).

K„ = [H 3 0 + (aq)] [OH~(aq)] = 1 x 10~14 mol2 L"2

Strong and weak acids

Strong acids (eg sulfuric acid, H 2 S0 4 , and nitric acid, HN0 3 ), dissociate fully.

Example
Hydrochloric acid is a strong acid:

HCI(g) + H 2 0(l) H 3 0 + (aq) + Ch(aq)

Because HCI dissociates fully, a solution of HCI would contain H 2 0(l), H 3 0 + (aq), Ch(aq) and OH"(aq). (OH" ions
and some H 3 0 + ions are from the dissociation of water.)

A weak acid (eg ethanoic acid) partially dissociates.

Example
Ethanoic acid is a weak acid:

CH 3 COOH(aq) + H 2 0(l) ^ CH 3 COO"(aq) + H 3 0 + (aq)

The ionisation of ethanoic acid is written as an equilibrium reaction. Therefore, not all the acid molecules
dissociate in the solution. A solution of ethanoic acid contains H 2 0(l), CH 3 COOH(aq), CH 3 COO"(aq), H 3 0 + (aq)
and OH"(aq). (OH" ions and some H 3 0 + ions are from the dissociation of water.)

Strong acids conduct electricity more strongly than weak acids of the same concentration because there are
more ions in solution. They have a lower pH because the concentration of H 3 0 + ions is greater. They react
more vigorously with metals to produce hydrogen gas.

They react faster with carbonates to produce carbon dioxide gas.

The same mass of metal or carbonate would react with a strong acid compared to a weak acid of the same
concentration, but it would take more time to 'disappear' with a weak acid because the reaction would take
longer.

Strong and weak bases

A strong base has a greater tendency to accept a proton, eg NaOH, KOH, than a weak base which accepts
protons to a limited extent, eg NH 3 , Na 2 C0 3 .

The pH scale
The pH scale ranges from 0 to 14.

A low pH indicates a high concentration of H 3 0 + ions in solution.

The pH of a solution can be measured in the laboratory using universal indicator paper or a pH meter.

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 Describe principles of chemical reactivity 101

pH calculations
The relationship between pH and H 3 0 + concentration is:

pH = -log [ H 3 0 + ( a q ) ]

Example
To calculate the pH of a 0.1 mol L _1 solution of HCI:

pH = -log [H 3 0 + (aq)]

= -log 0.1

= 1

HCI is a strong acid that fully dissociates, so the concentration of the hydronium ion is 0.1 mol L _1 .

Example
To calculate the pH of a 0.01 mol L"1 solution of HCI:

pH = -log [H 3 0 + (aq)]

= -log 1 x 10"2

= 2

When H+ ions change by a factor of 10, the pH changes by 1.

Example
Hydronium ion concentration, [H 3 0 + ], can be obtained by rearranging the pH formula to [H 3 0 + ] = 10"PH

To calculate the [H 3 0 + ] in a solution of pH 4.3:

[H 3 0 + ] = 10"PH

= 10-43

= 5.01 x 10"5 mol L-1

Finding the pH of strong bases using Kw

Kw can be rearranged to give:
1 x 10 - 1 4

This formula can be used to find the pH of strong bases.

Example
To calculate the pH of a 0.1 mol L _1 solution of NaOH.

NaOH is a strong base that fully dissociates, so the concentration of hydroxide ions is 0.1 mol L _1 .
1 x 10-14
[H 3 0 + (aq)J =
[OH-(aq)]

1 x 10"14
[H 3 0 + (aq)] =
0.1

[H 3 0 + (aq)] = 1 x 10"13 mol L"1

pH = -log [H 3 0 + (aq)]

= -log 1 x 10"13

= 13

(The final value of 13 reflects the fact that NaOH is a strong base.)

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102 Chemistry Achievement Standard 2.7

Hints on setting out work and checking answers

• Set your work out clearly down the page.
• Check that your answer is 'appropriate' (eg, you would expect a strong acid to have a low pH).
• Include units where appropriate.

Questions: Acids and bases

1. The pH of a 0.10 mol L _1 solution of acid H X and the pH of a 0.10 mol L"1 solution of acid HY are
measured. The pH of acid H X is 3 and the pH of acid HY is 1.

a. Which of the two acids, H X or HY, is the stronger acid?

(Circle your answer.) HX or HY

b. Justify your answer to a. in terms of the measured pH.

c. Describe a n o t h e r test that could be carried out to confirm that the acid you selected in a. above
is the stronger of the two.

Describe what you would do and what you would expect to observe.

2. HC03~(aq) is a species that may act as an acid or a base. Consider the equilibrium system:

HCO3-(acj0 + H 2 0(l) ^ H 2 C0 3 (ag) + OH '(aq)

a. Is HCO 3 "(oq) acting as an acid or a base?

(Circle your answer.) ACID or BASE

b. Justify your answer to a.

3. A sample of solid ammonium chloride, NH4CI, is dissolved in water. The solution formed is tested and
is found to be acidic.
Explain why the solution is acidic. Include appropriate equation(s) in your answer.

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 Describe principles of chemical reactivity 103

4. Complete the following table by showing the:

• hydronium ion concentration for both solution A and solution B

• hydroxide ion concentration for solution B
• pH of solution A.
Kw = [ H 3 0 + ] [ O H " ] = 1.00 x 10" 1 4

Solution [H 3 0 + ] / mol L"1 [OH - ] / mol L"1 PH

A a. 0.0288 b.

B c. d. 5.24

5. H 2 S(g) + H 2 0(l) ^ SH-(aq) + H 3 0 + (aq)

For the equation above, decide which of the following statements are true and which statements are
false:

a. SH" is a base.

b. H 3 0 (aq) donates a proton to water. _ _

c. H 3 0 + (aq) is an acid.

d. H 2 S cannot act as a base.

6. Benzoic acid is a weak acid that can be used in preservatives.

C 6 H 5 COOH(aq) + H 2 0(l) ^ C 6 H 5 COO"(aq) + H 3 0 + (aq)

What species would be present in a 1 mol L-1 solution of benzoic acid?

7. A student has two bottles, A and B, of unlabelled acidic solutions. One bottle is known to contain
hydrochloric acid, a strong acid, and the other ethanoic acid, a weak acid. Both solutions have the
same concentration. The student carries out two tests to determine which acid is which.

The table below shows the tests carried out on each acid and the observations made.

Test Bottle Observation

Test a sample of each acid using A pH of 1

a pH meter B pH of 3

Test a sample of each acid using A Conducts strongly

a conductivity meter B Conducts weakly

a. From the observations, identify which bottle contains ethanoic acid.

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104 Chemistry Achievement Standard 2.6

b. For each of the tests, explain the observations in terms of the concentration of H 3 0 + ions present
in the solution.

pH meter test:

Conductivity meter test:

8. A student adds a small marble chip to 15 mL of 2 mol L~1 nitric acid (a strong acid) and another small
marble chip of the same mass to 15 mL of 2 mol L"1 ethanoic acid (a weak acid).

a. What observations would the student make for each of the acids?

Nitric acid:

Ethanoic acid:
b. With which of the two acids would the most marble chip react? Explain.

9. Complete the following table.

C o n c e n t r a t i o n of solution C o n c e n t r a t i o n of H 3 0 + ions
Solution pH
(mol L 1 ) (mol L 1 )
HNO3 0.0001 a. b.
HCI c. d. 2

10. Complete the following table. K w = [H3Q+] [OH"] = 1.00 x 10"14

C o n c e n t r a t i o n of Concentration of C o n c e n t r a t i o n of
Solution solution HjO + ions OH- ions pH
( m o l L- 1 ) ( m o l L" 1 ) ( m o l L" 1 )
HCI 2.5 x 10-2 a. b. c.
NaOH 0.01 d. e. f.
90311
Describe oxidation-reduction
reactions
Externally assessed
4 credits

Redox reactions
Redox reactions involve one substance being oxidised and another substance being reduced.
Oxidation always involves loss of electrons; it can also involve gain of oxygen and/or loss of hydrogen.
Reduction always involves gain of electrons; it can also loss of oxygen and/or gain of hydrogen.
The mnemonic Oil Rig may help to remember how electrons are lost/gained:
Oxidation is a loss of electrons; Reduction is a gain of electrons.

Oxidant (oxidising agent) - substance that causes oxidation of the other substance.
The oxidising agent is reduced.

Reductant (reducing agent) - substance that causes reduction of the other substance.

The reducing agent is oxidised.

Example
2Mg o2 2MgO
Mg loses electrons to form 0 2 gains electrons to form
Mg 2+ (MgO is Mg 2+ 0 2 -). O 2 " (MgO is Mg 2 + 0 2 _ ).
Mg also gains oxygen. 0 2 is reduced.

Mg is oxidised. 0 2 is the oxidant.

Mg is the reductant.

Oxidation states and oxidation numbers

The oxidation state describes the extent to which an element has been oxidised or reduced. The oxidation
state can be identified by oxidation numbers.
106 Chemistry Achievement Standard 2.7

Assigning oxidation numbers

Rules Examples

1. When atoms exist as elements, they Na, Cl2, Ne, C and H 2 all have an oxidation
have an oxidation number of zero. number of zero.

2. The oxidation number of a monatomic Cu2+ has oxidation number +2,*cr has
(one atom) ion is the same as the charge oxidation number -1.
on the ion.

3. Hydrogen in compounds has an oxidation Hydrogen in H 2 0, CH4 and NH3 has

number of +1* (except in metal hydrides oxidation number +1.
where it is -1). (In NaH, a metal hydride, the oxidation number
of hydrogen is -1.)

4. Oxygen in compounds has an oxidation Oxygen in MgO, H 2 S0 4 , H 2 0 and KMn0 4

number of -2 (except in hydrogen has oxidation number -2.
peroxide, H 2 0 2 , where its oxidation (In hydrogen peroxide, H 2 0 2 , the oxidation
number is -1). number of oxygen is -1.)

5. For polyatomic ions (ions containing more For NH4", the sum of the oxidation numbers is
than one atom), the sum of the oxidation +1. For S042", the sum of the oxidation
numbers equals the charge of the ion. numbers is -2.

6. The sum of the oxidation numbers The sum of the oxidation numbers for the
in a molecule is zero. elements in H 2 S0 4 , C4H10 and H 2 0 is zero.

"Note: It is important to use the '+' sign when writing positive ONs: use '+1' not '1', '+2' not '2', etc.

Examples
1. The reaction b e t w e e n magnesium and oxygen.
2MgO

2Mg + 02 2Mg2+02~

Rule 1 Rule 1 Rule 2 Rule 4

ON = 0 ON = 0 O N = +2 O N = -2

( O N represents oxidation n u m b e r )

2. The oxidation numbers of C and H in the methane, CH 4 , molecule.

CH4 1 x ON(C) + 4 x ON(H) = 0

O N ( C ) + (4 x 1) = 0

QRulej; QRule^) 0 N ( C ) =" 4

O N = -4 O N = +1

3. The oxidation numbers of C r and O in the dichromate, Cr 2 0 7 2 ~, ion.

2 x ON(Cr) + 7 x ON(O) = -2-4- Rule 5

2 x O N ( C r ) + (7 x - 2 ) =-2

2 x ON(Cr) =+12

ON(Cr) =+6

O x i d a t i o n n u m b e r s c a n b e u s e d t o establish w h a t e l e m e n t has b e e n o x i d i s e d a n d w h a t e l e m e n t has b e e n

r e d u c e d in a r e a c t i o n . T h i s is useful w h e n o x y g e n , h y d r o g e n o r e l e c t r o n transfer a r e n o t o b v i o u s . T h e r e is
a n i n c r e a s e in o x i d a t i o n n u m b e r w i t h o x i d a t i o n , a n d a d e c r e a s e ( r e d u c t i o n ) in o x i d a t i o n n u m b e r w i t h
reduction.

Oxidation n u m b e r s are assigned to elements.

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 Describe oxidation-reduction reactions 107

Example
During the reaction 2Mg + 0 2 —> 2MgO, there is an increase in oxidation number of Mg from 0 to +2.
Therefore, Mg is oxidised.

There is a decrease in oxidation number of 0 2 from 0 to -2. Therefore, 0 2 is reduced.

Balancing redox equations - The ion-electron method

In the reaction between acidified potassium dichromate solution, K 2 Cr 2 0 7 , and iron(ll) sulfate solution,
FeS0 4 , the potassium ions (from potassium dichromate) and sulfate ions (from iron(ll) sulfate) do not take
part in the reaction (ie are spectator ions) and are not shown in the reaction.
Cr 2 0 7 2- changes to Cr3+; the Fe3+ changes to Fe3+.

To balance t h e e q u a t i o n

Step 1: Separate the reaction into half-equations.

Reduction Oxidation

Cr 2 0 7 2 - Cr3+ Fe2+ Fe3+

Step 2: Balance atoms except hydrogen and oxygen.

Cr 2 0 7 2 - -> 2Cr3+ Fe2+ Fe3+
Step 3: Balance any oxygens by adding water.
Cr 2 0 7 2 " 2Cr3+ + 7H 2 0 Fe2+ Fe3+
Step 4: Balance any hydrogens by adding hydrogen ions.
Cr 2 0 7 2 - + 14H+ 2Cr3+ + 7H 2 0 Fe2+ -» Fe3+

Step 5: Balance charges by adding electrons to the most positive side of each half-equation - this will give
the completed half-equations.
Cr 2 0 7 2 " + 14H+ + 6e" 2Cr3+ + 7H 2 0 Fe2+ -> Fe3+ + 1 e~
-2 +14 -6 =(2x3)+ (7x0) +2 =+3 -1

(Each half-equation must have electrons on opposite sides of the arrows. Reduction should have electrons
on the LHS of the equation, oxidation should have electrons on the RHS of the equation.)

Step 6: Multiply the half-equations (by the lowest common multiple) so that the number of electrons is the
same for each half-equation.
(In this example, only the oxidation half-equation needs to be multiplied - in this case by 6.)

Cr 2 0 7 2 " + 14H+ + 6e" 2Cr3+ + 7H 2 0 6Fe2+ 6Fe3+ + 6e~

Step 7: Add the two half-equations together. (The electrons should cancel each other out; also cancel out
any species (ions, molecules) common to both sides, so a species only appears on one side.)
Cr 2 0 7 2 - + 6Fe2+ + 14H+ 2Cr3+ + 6Fe3+ + 7H 2 0

Note that water forms part of the reaction - as redox reactions occur in aqueous solutions, water or acid
provides the hydrogen ions.

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108 Chemistry Achievement Standard 2.7

Common oxidants and reductants

Oxidant Reaction as oxidant Examples of use

Oxygen gas, 0 2 0 2 + 4e" -> 202~ All combustion reactions eg:

2Mg(s) + 0 2 ( g ) -> 2MgO(s)
CH 4 (g) + 20 2 (g) -> C0 2 (g) + 2H 2 0(g)

Hydrogen ions, 2H+(aq) + 2e" -> H 2 (g) Metals above hydrogen in the activity series are oxidised
H+ (from acidic by H+(aq) eg:
solutions)
Mg(s) + 2H+(aq) Mg 2+ (aq) + H 2 (g)

Chlorine gas, Cl 2 + 2e- 2CI" Used as a disinfectant and to treat swimming pools, as
ci2 pale
green
colourless oxidising properties destroy bacteria; used as a bleach

Potassium Mn0 4 "(aq) + 8H+ + 5e"—> Mn 2+ (aq) + 4H 2 0 Common laboratory oxidant, eg to oxidise alcohols,
permanganate, purple colourless/ Fe2+(aq) and l"(aq) ions
pale pink
KMn0 4

Potassium Cr 2 0 7 2 "(aq) + 14H+ + 6e" 2Cr3+(aq) + 7H 2 0 Common laboratory oxidant (like permanganate),
dichromate orange green oxidant that was used in breathalyser test

Hydrogen Used as a disinfectant to killl bacteria and as a bleach

H 2 0 2 (aq) + 2H+ + 2e" -> 2H 2 0
peroxide, H 2 0 2

Iron(lll) ion, Fe3+ + e- -> Fe2+ Oxidised by KMn0 4

yellow green
Fe3+

Iodine, l 2 l 2 + 2e" -> 2l"(aq) Used as a disinfectant and antiseptic; a mild oxidant that
brown colourless can displace other halide ions, eg Cl"(aq) and Br(aq)

Reductant Reaction as reductant Examples of use

Metals high on Mg Mg2+ (aq) + 2e~ • Displacement reactions with ions of

the activity series, less reactive metals
eg Mg, Zn and Fe Zn —> Zn2+ (aq) + 2e~ • All corrosion reactions, ie when metals
Fe —> Fe2+(aq) + 2e- react with oxygen
pale green
Fe3+(aq) + e~
orange

Carbon, C, and C(s) + 2H 2 0 -> In the iron-making industry to reduce iron

carbon monoxide, C0 2 (g) + 4H+ +(aq) + 4e~ oxide to iron:
CO Fe304(s) + 4CO(g) 3Fe(l) + 4C0 2 (g)
CO(g) + H 2 0 iron iron
C0 2 (g) + 2H+(aq) +2e" oxide

Sulfur dioxide, S0 2 (g) + 2H 2 0 Delays oxidation of nutrients in food by

S0 2 (acidic, S042~(aq) + 4H+ + 2e" bacteria:
choking gas) • Preserves dried foods
• Prevents spoiling in wine and fruit drinks
• Mild bleach

Hydrogen gas, H 2 H2 2H'(aq) + 2e" To reduce metal oxides to elemental metal,

eg CuO(s) + H 2 (g) —> Cu(s) + H 2 0(g)
black red/brown
copper copper
oxide metal

Halide ions: Common laboratory reactant, eg reduces

• iodide ions, r 2l"(aq) l 2 (aq) + 2e~ dichromate or permanganate ions
• bromide ions, B r 2Br" -> Br2(aq) + 2e"

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 Describe oxidation-reduction reactions 109

Questions: Redox reactions

1. When acidified potassium permanganate solution is added to freshly prepared iron(ll) sulfate solution,
a reaction occurs. The unbalanced equation is shown below:

Mn0 4 - + Fe2+ > Fe3+ + Mn2+

a. Is the Mn0 4 ~ ion oxidised or reduced? Use oxidation numbers to justify your answer.

b. Identify the oxidant and reductant in the reaction above.

Oxidant:

Reductant:

c. Write balanced equations for the oxidation and reduction half-reactions.

Oxidation:

Reduction:

d. Combine the half-equations in c. to give the balanced equation for this oxidation-reduction
reaction.

e. Clearly describe what would be observed when this reaction is carried out, linking the
observations to the species involved in the reaction.

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110 Chemistry Achievement Standard 2.7

2. Wines often contain a small amount of sulfur dioxide that is added as a preservative. If too little is
added, the wine is oxidised to vinegar. If too much is added, it affects the taste of the wine.

The sulfur dioxide content of wine can be determined using a reaction with iodine, l2, to produce
sulfate and iodide ions.

a. What is the oxidation number of sulfur in EACH of the following?

i. S0 2

ii. S0 4 2 -
b. Write ion-electron half-equations for the oxidation and reduction reactions occurring between
S0 2 and l2.

c. Combine the half-equations in b. above to form a balanced equation.

d. The alcohol content of the wine can be determined by a reaction with acidified potassium
dichromate.

What colour change would be observed if excess wine is added to acidified potassium dichromate
solution? Link the colour change observed to the species responsible for the observed colour.
(Neither the alcohol nor its oxidation product is coloured.)

3. What is the oxidation number of each of the elements in the following substances?

a. Cl2

b. CaCI2

c. CO

4. What is the oxidation number of the bolded element in the following substances?

a. KN0 3

b. Na 3 P0 4

c. NaHCOj

5. What is the oxidation number of sulfur in each of the following compounds?

a. H 2 S0 4

b. H2S
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 Describe oxidation-reduction reactions 111

C. H2SO3
6. Which two of the following are not redox reactions?
a. Fe + Cu2+ -+ Cu + Fe2+
b. Fe 2 0 3 + 3CO -+ 2Fe + 3C0 2
c. Pb2+ + S042- PbS0 4

d. Ca(OH) 2 + 2HCI -+ CaCI2 + 2H 2 0

7. a. Balance the following half-equations:

i. I 2 -+ I-

ii. Fe2+ —• Fe3+

iii. H 2 O 2 -+ H 2 0 . ... __ _

b. Which one of the half-equations above is an oxidation reaction? Explain your answer using 'loss or
gain of electrons', or 'oxidation numbers'.

8. When a zinc granule is added to hydrochloric acid, bubbles of hydrogen gas are given off. Balance the
following half-equations for the acid and zinc reaction.
a. H+ -+ H 2

b. Zn -+ Zn2+
9. Iron(ll) sulfate reacts with hydrogen peroxide according to the balanced equation:
2Fe2+ + H 2 0 2 + 2H+ -+ 2Fe3+ + 2H 2 0
Use the information above to identify:

a. The oxidant.

b. A spectator ion

c. The substance that is oxidised.

10. What colour are the following species?

a. Cr3+

b. Mn2+

c. I-

d. Cl2

e. H202 —

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112 Chemistry Achievement Standard 2.7

11. Classify the following half-equations as either oxidation or reduction:

a. Br2(l) + 2e~ -+ 2Br (aq)

b. Cu(s) -+ Cu2+(aq) + 2e _

c. S0 2 (g) + 2H 2 0 -+ SO,,2 (aq) - 4H (aq) + 2e~

12. Complete the following table by identifying the reductant in each of the reactions.

E q u a t i o n f o r t h e reactions Reductant

Mg + 2Ag+ -+• Mg 2+ + 2Ag a.

2Mn0 4 " + 10h + 16H+ 2Mn 2+ + 5I2 + 8H 2 0 b.

Ca + 2H+ Ca2+ + H 2 c.

13. For the following reactions:

i. What observations would you make?

ii. Write half-equations and then a balanced equation for each reaction.

a. Bromine water is added to potassium iodide solution.

Observation:

Half-equation:

Half-equation: _

Balanced equation:

b. Sulfur dioxide gas is passed through acidified potassium dichromate solution.

Observation: _ _

Half-equation:

Half-eq uation:

Balanced equation:

Electrolysis
Electrolysis is the process in which an electrical current is passed through an electrolyte, and
consequently, oxidation and reduction reactions occur.

An electrolyte is either a molten ionic compound or a solution that contains ions that are free to move.

An electrode is a solid conductor that carries current to and away from the electrolyte. These are usually
made of inert (non-reactive) substances, eg carbon, C; platinum, Pt.

Reduction occurs at the c a t h o d e (the negative electrode).

Oxidation occurs at the a n o d e (the positive electrode).

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 Describe oxidation-reduction reactions 113

DC power
supply
Current is supplied to the cell.

Cations (positive ions) m o v e to the cathode.

Anions (negative ions) m o v e to the anode.

anode cathode
(oxidation) (reduction)

electrolyte

Electrolysis of molten ionic compounds

Example
Electrolysis of l i t h i u m chloride

Lithium ions (cations) move to the cathode; reduction occurs at the cathode - lithium ions gain electrons and
molten lithium metal is formed:

Li+(l) + e" -> Li(l)

Chloride ions (anions) move to the anode; oxidation occurs at the anode - chloride ions lose electrons and
chlorine gas is formed:

2CI"(I) Cl 2 (g) + 2e"

Electrolysis of aqueous solutions

The reactions occurring d e p e n d upon:
• H o w easily ions are reduced or oxidised compared with water.
• The concentration of the solution.

Example
Electrolysis of c o p p e r chloride solution
At the At the
Copper ions move to the negative electrode (cathode) and are
anode: CI" cathode: Cu 2+ (aq)
oxidised to Cl 2 (g) reduced to copper reduced to copper metal. A pinky/brown layer is observed on the
cathode.

Reaction at the cathode (reduction):

Cu2+(aq) + 2e" Cu(s)

Reaction at the anode (oxidation):

2Ch(aq) Cl 2 (g) + 2e~

Bubbles of gas will be observed at the anode.

copper
chloride solution

Examples in industry
Sodium production
Pure solid sodium chloride has a melting point of 801 ° C .

Reaction at a n o d e (oxidation): 2CI"(I) -> Cl 2 (g) + 2e~

Reaction at cathode (reduction): Na + (l) + e~ Na(l)

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114 Chemistry Achievement Standard 2.7

Extraction of magnesium
Magnesium is extracted from sea water.

Step 1: Magnesium is first precipitated from the seawater as magnesium hydroxide using calcium hydroxide:

Mg 2+ (aq) + 20H"(aq) M g (OH) 2 (s)

(from (from magnesium

sea water) calcium hydroxide) hydroxide

S t e p 2: The precipitate is filtered and dissolved in hydrochloric acid to form magnesium chloride.

S t e p 3: Water is evaporated from the solution, leaving hydrated magnesium chloride, MgCI 2 .6H 2 0. This is
then heated until it melts and electrolysed using graphite electrodes.

Reaction at anode (oxidation):

2d-(l) Cl 2 (g) + 2e~

Reaction at cathode (reduction):

Mg 2+ (aq) + 2e~ -H> Mg(s)

Extraction of aluminium
S t e p 1: Mining the aluminium ore.

A red-coloured clay called b a u x i t e is mined in Australia. Bauxite contains a l u m i n a (aluminium oxide,

AI 2 O 3 ).

S t e p 2: Ore purification.

The bauxite is crushed and heated with caustic soda solution (sodium hydroxide). Only the aluminium
oxide and silica impurities dissolve:

AI203(S) + 20H-(aq) + 3H20 2AI(OH)4-(aq)

(from (from aluminate ion

bauxite) sodium hydroxide)

The iron impurities do not dissolve and are removed by filtration.

The alumina solution cools. Aluminium hydroxide crystals are added. Aluminium hydroxide precipitates out
and the silica impurities remain dissolved in the solution:

AI(OH) 4 -(aq) AI(OH) 3 (s) + OH"(aq)

Solid aluminium hydroxide is heated to form pure alumina:

heat

2AI(OH)3(S) ^ AI203(S) + OH-(I)

This pure alumina is shipped to New Zealand to be electrolysed.

Step 3: Electrolysis of alumina.

Alumina is dissolved in cryolite, Na 3 AIF 6 (cryolite reduces the melting point of alumina). Electrolysis takes
place in a pot, in which the c a t h o d e is a lining of carbon at the bottom of the pot and the a n o d e s are
blocks of carbon held into the pot.

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 Describe oxidation-reduction reactions 115

Alumina,
Al 2 0 3

added alumina and

some hardened
'new' carbon cryolite
anode

old' carbon
anode

steel pot

Reaction at the anode (oxidation) :

202~ -+ 0 2 (g) + 4e" [x 3]
Reaction at the cathode (reduction):
Al3+ + 3e- -+ Al(l) [x 4]
Overall reaction:
2AI203 -+ 30 2 (g) + 4AI(I)

The anodes need to be replaced occasionally, as the oxygen produced at the anode reacts with the carbon
electrodes:
C(s) 0 2 (g) -+ C0 2 (g)
carbon anode oxygen gas carbon dioxide given off
(hence electrode 'disappears')

Production of Chlorine
Concentrated sodium chloride solution, NaCI solution (brine), is electrolysed.
Reaction at anode: 2Ch(aq) -+ Cl2(g) + 2er
Reaction at cathode: 2H 2 0(I) + 2e~ -+ H 2 (g) + 20H~(aq)
(The reaction at the cathode produces hydrogen because water is easier to reduce than Na+. Because the
concentration of the CI- ions is high, it is easier to oxidise the Ch ions rather than oxidising the water.
(Compare this with the electrolysis of molten NaCI (sodium production). In Example Electrolysis of
copper chloride solution, in which copper ions are more easily reduced than water, so copper forms.)

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116 Chemistry Achievement Standard 2.7

Electroplating
Electroplating uses electrolysis to coat a metal with another metal.

Example
Copper p l a t i n g

anode: piece
of copper

cathode: object to
be copper-plated

copper sulfate
solution

Reaction at cathode (reduction): Cu 2+ (aq) + 2e~ —> Cu(s)

(from CuS0 4 )

Reaction at anode (oxidation): Cu(s) —> Cu 2+ (aq) + 2e _

anode

The Cu2+ ions from the oxidation reaction replace those from the CuS0 4 solution.

Questions: Electrolysis
1. Aluminium is produced by the electrolysis of aluminium oxide that has been extracted from bauxite
ore. A typical electrolysis cell is shown in the diagram below. The oxygen gas produced reacts with the
carbon (graphite) electrodes, so that the electrodes have to be replaced from time to time.

Carbon (graphite) Solid crust of electrolyte floats on top

Tapping hole

Steel tank with carbon Molten electrolyte consisting Molten aluminium is

(graphite) lining of aluminium oxide dissolved tapped off at intervals
in cryolite

a. On the diagram above:

i. clearly label the anode and the cathode

ii. show the direction of movement of ions in the electrolyte.

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 Describe oxidation-reduction reactions 117

b. Write balanced half-equations for the reactions occurring at:

i. the positive electrode

ii. the negative electrode.

c. Write an equation for the reaction that occurs between the oxygen gas and the carbon electrode,
and hence explain why the electrode must be replaced from time to time.

Equation:

Explanation:

2. The diagram outlines the electrolysis of molten lithium chloride.

—HilK
+

a.

b.
©
©
© 11
Label the diagram to identify the anode and the cathode.
©
Write a balanced half-equation for the reaction occurring at the negative electrode.

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118 Chemistry Achievement Standard 2.7

3. Lead metal is produced by the electrolysis of molten lead bromide.

a. i. Which ions move to the negative electrode? _

ii. Which ions move to the positive electrode?

b. i. Write a balanced half-equation for the oxidation reaction.

ii. Write a balanced half-equation for the reduction reaction.

4. Electrolysis of sodium chloride

A concentrated sodium chloride solution, commonly called brine, can be electrolysed.

a. i. What gas is produced at the cathode?

ii. Write the balanced half-equation for the reaction occurring at the positive electrode.

b. The diagram illustrates the electrolytic process for m o l t e n sodium chloride.

i. Label the anode.

ii. Label the cathode.

iii. Identify and label the species that moves to the anode.

iv. Identify and label the species that moves to the cathode.

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 Describe oxidation-reduction reactions 119

c. The reaction at the cathode for the electrolysis of brine is different to the reaction occurring at
the cathode for the electrolysis of molten sodium chloride solution, NaCI. Explain this difference.

5. Electroplating

Steel cans are used in the manufacture of canned foods. The cans are electroplated with tin, Sn.

a. What is the meaning of the term 'electroplated'?

b. What is the purpose of electroplating the steel cans?

c. The reaction for tin in the electroplating of steel cans is:

Sn2+(aq) + 2e~ -> Sn(s)

Using your knowledge of electroplating, state the electrode that this reaction takes place at.

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120 Chemistry Achievement Standard 2.7

Chlorine and the halogens

Laboratory preparation
Prepared by:
• adding conc hydrochloric acid, HCI, to manganese dioxide, Mn0 2 , and heating; or
• adding conc HCI to potassium permanganate, KMn0 4 ; or
• adding dilute HCI to bleaching powder that contains calcium hypochlorite, Ca(OCI) 2 .
The reactions occurring are oxidation-reduction reactions.

Conc hydrochloric acid, HCI, and potassium permanganate, K M n 0 4

Half-equation (oxidation): 2CI_(aq) -> Cl2(g) + 2e_ [x 5]
Half-equation (reduction): Mn0 4 -(aq) + 8H+(aq) + 5e~ -> Mn2+(aq) + 4H 2 0(I) [X 2]
Overall equation: 10CI"(aq) + 2Mn0 4 "(aq) + 16H+(aq) -> 5CI2(g) + 2Mn2+(aq) + 8H 2 0(I)
Conc hydrochloric acid, HCI, and manganese dioxide, M n 0 2

Half-equation (oxidation): 2CI_(aq) Cl2(g) + 2e_

Half-equation (reduction): Mn0 2 (s) + 4H+(aq) + 2e~ Mn2+(aq) + 2H 2 0

Overall equation: Mn0 2 (s) + 2Ch(aq) + 4H+(aq) -> Cl2(g) + Mn2+(aq) + 2H 2 0

HCI hydrochloric acid and bleaching powder that contains calcium hypochlorite, Ca(OCI) 2
20CI"(aq) + 4H+(aq) + 2CI"(aq) -> 2CI2(g) + 2H 2 0(I)

from calcium from

hypochlorite dilute HCI

Industrial preparation
Chlorine is produced by the electrolysis of concentrated sodium chloride solution (brine).

Reactions of chlorine and other halogens

Reaction with metals
The halogens are strong oxidising agents.
Chlorine is such a strong oxidising agent that it will oxidise iron to the iron(lll) ion rather than the iron(ll) ion:
2Fe + 3CI2 ^ 2FeCI3
Iron wool burns in chlorine. A thick red-brown smoke is produced (FeCI3).
Reactions with non-metals
Chlorine oxidises non-metals such as phosphorus:

P4 + 10CI 2 ^4PCI 5

Reactions with halide ions

The oxidising strength of the halogens decreases in the order:
F2 > Cl2 > Br2 > l2
strongest weakest
Chlorine is a stronger oxidising agent than bromine; bromine is a stronger oxidising agent than iodine.
Consequently, chlorine will oxidise bromide ions and iodide ions, and bromine will oxidise iodide ions.
2h(aq) + Cl2(aq) -» l 2 (aq) + 2CI-(aq)
The presence of chlorine can be tested using starch-iodide paper. The paper contains starch and iodide

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 Describe oxidation-reduction reactions 121

ions; the chlorine gas reacts with iodide ions to form iodine:

21" + Cl2 l 2 (aq) + 2CI"(aq)

The iodine, l 2 (aq), then reacts with the starch and the paper goes a blue-black colour.

Reaction with water

Chlorine is moderately soluble in water, and forms an acidic solution:

Cl 2 (g) + H20 -+ HOCI(aq) + HCI(aq)

hypochlorous hydrochloric
acid acid

Hypochlorous acid is a strong oxidising agent, and responsible for chlorine's bleaching and disinfectant
properties.

Uses for Chlorine

• As a bleach or to make bleaching agents such as hypochlorous acid and the hypochlorite ion.
• Sodium hypochlorite is made by bubbling chlorine through sodium hydroxide:

Cl2 + 2NaOH -+ NaOCI + NaCI + H 2 0

Calcium hypochlorite is made by reacting chlorine with calcium hydroxide:

2CI2 + 2Ca(OH) 2 -+ Ca(OCI) 2 + CaCI2 +2H20

• Calcium hypochlorite is commonly called bleaching p o w d e r (the hypochlorite ions have oxidising
properties) and is a useful way of storing chlorine. It is used in swimming pools as it hydrolyses in water:

Ca(OCI) 2 + 2H 2 0 -+ Ca2+(aq) + 20H"(aq) + 2HOCI(aq)

• To make hydrochloric acid.

Hydrogen produced in the electrolysis of brine reacts with excess chlorine to produce hydrogen chloride
gas:

H 2 (g) + Cl 2 (g) -+ 2HCI(g)

The HCI gas dissolves in water to make concentrated hydrochloric acid:

HCI(g) + H 2 0(l) -+ H 3 0 + (aq) + Cl"(aq)

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122 Chemistry Achievement Standard 2.7

Questions: Chlorine and the halogens

1. Complete the table below for EACH combination of species.

Does a
If a reaction occurs, If a reaction occurs, write
reaction
Species to be mixed describe what would be a balanced equation for the
occur?
observed. reaction.
(yes or no)
a. Cl 2 (aq) + Br(aq) i. ii. iii.

b. Cl"(aq) + l 2 (aq) i. ii. iii.

2. Sodium hypochlorite, NaOCI, reacts with hydrochloric acid to give sodium chloride, NaCI, and
chlorine gas, Cl2. It is the reaction between the CI- and OCI" ions that produces the chlorine gas.

a. What are the oxidation states of the chlorine in EACH of the following species?

i. OCI-

ii. CI"

iii. Cl2

b. Write balanced ion-electron half-equations for the formation of chlorine, Cl2, from:

i. chloride ion (CI - )

ii. hypochlorite ion (OCI")

c. Identify the reaction in part b. above that is an oxidation reaction, and give reasons for your
answer.

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 Describe oxidation-reduction reactions 123

d. If warmed, or left to stand, a solution of sodium hypochlorite decomposes as follows:

2NaOCI » 2NaCI + 02
Clearly identify the element that is being oxidised and the one being reduced.

Justify your decision.

e. A bottle of bleach contains sodium hypochlorite. The following information is written on the
bottle's label:
'This bleach decays into common salt and water after it has killed germs.
Do not use with lavatory cleaners containing acid.'
Discuss the validity of the claims made on this label.

3. Using your knowledge about the ability of halogens to act as oxidising agents, state whether the
following reactions will occur:
Yes/No

a. 2Br~+ Cl2 Br2 + 2CI"

b. I2 + 2CI" —» 21' + Cl2

c. 21-+ Br 2 -+l 2 + 2Br~
4. Reactions of Chlorine
a. When chlorine dissolves in water it forms an acidic solution. Write a balanced equation for the reaction.

b. Chlorine is a strong oxidising agent. It reacts with iron according to the following equation:
2Fe + 3CI2 -+ 2FeCI3
I. Describe the observations you would make when burning iron wool with chlorine gas.

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124 Chemistry Achievement Standard 2.7

ii. Explain why FeCI3 is formed rather than FeCI2.

5. Starch-iodide paper contains starch and iodide ions. The paper is used to test for the presence of
chlorine gas.

a. What would you observe when chlorine gas comes in contact with damp starch-iodide paper?

b. Explain the reaction that is occurring in terms of oxidation-reduction. Include balanced ionic
equations.

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 AME
Year 12
Answers and explanations Chemistry
Workbook

The 'Achieved', A, 'Merit' M, and 'Excellence' £, ratings given with the answers to NCEA questions for the
externally assessed Achievement Standards chapters are based upon the professional judgements of the author.

903OS AS 2.1: Carry out qualitative analysis

For all the answers, you do not need the states in the equations.

1. a. Yes. Zinc carbonate, ZnC0 3 . b. Yes. Lead sulfate, PbS0 4 . c. No.

d. Yes. Silver iodide, Agl. e. Yes. Iron(ll) hydroxide, Fe(OH) 2 . (3 out of 5 correct A)

2. a. No. b. No. c. Yes. d. Yes. e. No. (3 out of 5 correct A)

3. a. Pb 2+
20H"(aq) 30H~(aq) (2 out of 3 correct A)

4. a. Zn 2+ (aq) + 20H"(aq) -» Zn(OH) 2 (s)

b Fe2+(aq) + 20hr(aq) -> Fe(OH)2(s)

c. As no ppt forms, an equation cannot be written.

d. Ba 2+ (aq) + S0 4 2 "(aq) BaS0 4 (s)

e. Fe 3+ (aq) + 30H"(aq) Fe(OH) 3 (s)

f. Ag + (aq) + Cl'(aq) AgCI(s) (3 out of 5 correct M )

5. a. [Cu(NH 3 ) 4 ] 2 + (aq) ii. 20H~(aq)

b [Zn(OH) 4 2 -](aq)

c. Ag 2 0(s) ii. 4NH 3 (aq)

d. [Zn(NH 3 ) 4 ] 2 + (aq) ii. 20H-(aq)

e. AI(OH) 3 (S) ii. OH""(aq) (4 out of 5 equations correct M )

6. Pb(OH) 2 (s) + 20H"(aq) -> [Pb(OH) 4 ] 2 _ (aq) (£)

7. AI(OH) 3 (s) + OH~(aq) —> [AI(OH) 4 ]~(aq) (£)

For 'Excellence', you need to write complete ionic equations for the formation of complex ions rather
than just complete the ionic equations.

8. AgCI(s) + 2NH 3 (aq) [Ag(NH 3 ) 2 ] + (aq) + Cl"(aq) (£)

90306 AS 2.2: Perform an acid-base volumetric analysis

Significant figures AS 2.2

1. 1.23 x 10^ mol 4. 1.35 mol L"1

2. 26.2 mL S. 2.45 x 10" 3 mol L"1
3. 0.0743 g
126 Answers and explanations

Volumetric analysis AS 2.2

To gain 'Achieved' in Achievement Standard 2.2, you need to meet the minimum requirements for the
practical (carrying out the titration) and written (doing a calculation to find the concentration of an
'unknown').

A M E
Practical

At least two titre values within At least two titre values within At least two titre values within
a range of 0.6 mL and average a range of 0.4 mL and average a range of 0.2 mL and average
titre calculated within 1.0 mL of titre calculated within 0.5 mL of titre calculated within 0.2 mL of
expected volume. expected volume. All data (initial expected volume. All data (initial
and final readings) recorded. and final readings) recorded.

Calculation

Calculations carried out with Calculations carried out correctly; Titres within a range of 0.5 mL
appropriate formula; one minor titres within a range of 1 mL used used to calculate average volume.
error allowed (eg incorrect to calculate average volume. Calculations carried out correctly;
substitution of a numerical error or final answer has correct units and
incorrect conversion volumes such appropriate number of significant
as mL to L). No penalty if all titre figures. Evidence of 1 : 2 ratio
values used. needed also.

21.00 + 21.50 + 21.50

Average volume of HCI used =
3
= 21.33 mL

n(NaOH) = c x V

= 0.100x0.0200

= 0.00200 mol

From the equation, 1 mol NaOH reacts with 1 mol HCI;

therefore, 0.002 mol NaOH reacts with 0.002 mol HCI

0.00200 Number of moles of HCI.

c(HCI) =
0.021 3 Average volume of HCI in litres.

= 0.0939 mol L~1 Rounded to 3 sf. (A, M)

Average titre of HCI used = 14.8 mL

n(Na 2 C0 3 ) = c x V

= 0.210x0.010

= 2.10 x 10-3 mol

From the equation, 1 mol of Na2COs reacts with 2 mol of HCI;

therefore, 2.10 x 10-3 mol of Na2C03 reacts with 4.20 x 10~3 mol of HCI 2 x 2.10 x 10"3
n
c(HCI) = —
4.20 x TO-3

14.8 x 10"3
= 0.284 mol L"1 (A, M, £)

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 127 Answers and explanations

20.48 + 20.45 + 20.40

3. Average volume of NaOH used =

= 20.44 mL

Choose three concordant results and then average.

n(NaOH) = c x V

= 0.350 x 20.44 x 10"3

= 7.154 x 10"3 mol

From the equation, 1 mol CH3COOH reacts with 1 mol NaOH;

so, 7.154 x 10' 3 mol CH3COOH reacts with 7.154 x 10"3 mol NaOH
n
c (ethanoic acid) = —
V
7.154 x 10"3
10.0 x 10-3
= 0.715 mol L"1 (A, M)
26.26 + 26.18 + 26.21
Average volume of HCI used =

= 26.22 mL

n(HCI) = c x V
= 0.150x0.02622
= 3.93 x 10"3 mol

From the equation, 1 mol HCI reacts with 1 mol NaOH;

so, 3.93 x 10~3 mol HCI reacts with 3.93 x 10""3 mol NaOH

c(NaOH) = -

3.93 x 10"3 mol

20.0 x 10-3
= 0.197 mol L"1 (A, M)
20.56 + 20.50 + 20.48
Average volume of HCI used =
3
= 20.51 mL
n(HCI) = cx V
= 0.230x0.02051
= 4.72 x 10~3 mol
From the equation, 2 mol of HCI reacts with 1 mol of Na2C03;
so, 4.72 x 10"3 mol of HCI reacts with 2.36 x 10"3 mol of Na 2 C03

c(Na 2 C0 3 ) = -
V ,
2.36 x 10"3
20.00 x 10"3
= 0.118 mol L"1 (A, M, E)

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128 Answers and explanations

90307 AS 2.3: Carry out a gravimetric or colorimetric analysis

and solve related problems
Moles and stoichiometry AS 2.3

1. a M( CuS) = 63.5 + 32.1

= 95.6 g mol"1 (A)

b. M(CaC0 3 ) = 40.1 + 12.0 + (3 x 16.0) = 100 g mol"1 (A)

c. M(CaS0 4 .2H 2 0) = 40.1 + 32.1 + ( 4 x 16.0) + (4 x 1.0) + (2 x 16.0) = 1 72.2 g mol"1 (A)
2. a. m=nx M
= 5 x 32.0
= 160 g (A)
b. m=nxM = 2x 40.0 = 80.0 g (A)
c. m = nx M= 0.241 x 142.1 = 34.2 g (4)

The calculator value is 34.222, but the answer is rounded to 3 sf.

3. a-c; A - one mathematical error or calculating the molar mass correctly only; M - whole calculation
correct.
a. M(MgCI 2 ) = 24.3 + (2 x 35.5)
= 95.3 g mol"1
m
n(MgCI 2 ) = -
M
_ 60.0
95.3
= 0.630 mol (A, M)

b. M(KOH) = 39.1 + 16.0 + 1.0 = 56.1 g moM

m
n(KOH) = —
M
12.0
56.1
= 0.214 mol (A, M)

c. M(C 6 H 12 0 6 ) = (6 x 12.0) + (12 x 1.0) + (6 x 16.0) = 180 g mol"1

m
n=—
M
2000
= 2 kg C 6 H 12 0 6 is 2000 g of C 6 H 12 0 6 .
180
= 11.1 mol (ftf - no more than one mathematical error; E - correct answer)

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 129 Answers and explanations

m
4. n(MgO) = —
M
2. 60
= - — M(MgO) = 24.3 + 16 = 40.3g mol"1
40.3
= 0.0645 mol
From the equation, 2 mol of Mg reacts to form 2 mol of MgO;

therefore, 0.0645 mol of Mg reacts to form 0.0645 mol of MgO.

m(Mg) = n x M

= 0.0645 x 24.3

= 1.57 g

Therefore, 1.57 g of Mg has burned to form 2.60 g magnesium oxide.

(4 - one step correct; M - one mathematical error or 3 steps correct (eg calculating mass
Mg correctly); £ - w h o l e calculation correct)
m
5. n(CI2) = -
M
= M(Cl 2 ) = 2 x 35.5 = 71.0 g mol"1
71.0
= 0.180 mol
From the equation, 1 mol of chlorine reacts to form 2 mol of sodium chloride;

therefore, 0.180 mol of chlorine reacts to form 0.360 mol of sodium chloride.

m(NaCI) = n x M

= 0.360x58.5

= 21.1 g
(4 - one step correct; M - one mathematical error or 3 steps correct (eg calculating mass
NaCI correctly); £ - whole calculation correct)

Percentage composition and gravimetric analysis AS 2.3

1. M - whole calculation correct; A - only molar mass correct

a. /W(CH3NH2) = (1 x 12.0) + (5 x 1.0) + (1 x 14.0)

= 12.0 + 5.0 + 14.0

= 31.0 g moh1

12.0
% C = x 100 = 38.7%
31.0
5.0
% H= x 100 =16.1%
31.0
14.0
o/o N = x 100 = 45.2% (A, M)
31.0
% C + % H + % N = 100% (checked)

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130 Answers and explanations

b. M(NH 4 CI0 4 ) = (1 x 14.0) + (4 x 1.0) + (1 x 35.5) + (4x 16.0) = 14.0 + 4.0 + 35.5 + 64.0
= 11 7.5 g mol"1

% N = x 100 = 11.9% % H= x 100 = 3.40%

117.5 117.5
35.5 64.0
o/o CI = x 100 = 30.2% % O = x 100 = 54.5% (A, M)
117.5 117.5
M(Na 2 B 4 0 7 ) = (2 x 23.0) + (4 x 10.8) + (7 x 16.0) = 46.0 + 43.2 + 112.0 = 201.2 g mol"1
4x108
% B= — x 100 = 21.5 % (M - whole calculation correct; A - only molar mass correct)
201.2
3. M(CO(NH 2 ) 2 ) = (1 x 12)+ (1 x 16) + (2 x 14) + (4 x 1) = 60 g mol
2 x 14.0
% N= x 100 = 46.7 % ( M - whole calculation correct; A - only molar mass correct)
60.0
C H O

In 100 g of compound 52.1 7 g 13.04g 34.78 g

52.17 13.04 34.78

Mole
12 1 16.0
= 4.35 mol =13.04 mol = 2.1 7 mol

4.35 13.04 2.17

Mol ratio
2.17 2.17 2.17
2 : 6 1
Empirical formula = C 2 H 6 0 (flf)

5. N O

Assume 100 g of compound 30.43 g 69.57 g

30.43 69.57
Mole
14.0 16.0
= 2.17 mol = 4.35 mol

2.17 4.35
Mole ratio
2.17 2.17
1 2
Empirical formula = N 0 2
M(N02) = (1 x 14.0) + (2 x 16.0) = 46.0 g mol"1
molar mass
x =
molar mass of empirical formula
92.0
46.0
= 2

Molecular formula = N 2 0 4
(A - either empirical formula or molecular formula correct or small mathematical error overall;
M - all correct)

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 131 Answers and explanations

6. c H O
Assume 100 g of compound 40.0 g 6.67 g 53.33 g

40.0 6.67 53.33

Mole
12.0 1 16.0
= 3.33 mol = 6.67 mol = 3.33 mol

3.33 6.67 3.33

Mole ratio
3.33 3.33 3.33
1 : 2 1

Empirical formula = CH 2 0

M(CH 2 0) = (1 x 12.0) + (2 x 1.0) (1 x 16.0) = 30.0 g mol"1

molar mass
x =
molar mass of empirical formula
180

30.0
= 6

Molecular formula = C 6 H 1 2 0 6

(A - either empirical formula or molecular formula correct or small mathematical error overall;
M - a l l correct)

Concentration AS 2.3

1. Units and significant figures not required for A.

n
a. c(Na 2 S0 4 ) = —

_ 0.0102
0.0350
= 0.291 mol L"1 (A)
n 0.00100
b. c(KCI) = — = = 0.200 mol L-1 (A)
V 0.00500
2. a. Units and significant figures not required for A.

n(CuS0 4 .5H 2 0) = c x V Formula.

= 0.0200 x 0.5000 Substitute values.

= 0.0100 mol Appropriate number sf, correct unit(s). (A)

b. n(NaCI) = c x V= 0.100 x 0.0100 = 1.00 x 10"3 mol

Answer could also be 0.00100 mol. (A)

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132 Answers and explanations

A - calculating one part of calculation correctly or no more than one mathematical error; M- all
calculations correct.
m
n( Na 2 S0 4 ) = —
M
2.12
142
= 0.0149 mol 0.0149 is a rounded number. When showing working, you can
round your answers but keep the actual values in the calculator, then
give the correct sf in the final answer.

c(Na 2 S0 4 ) = —
V
0.0149

0.250
= 0.0597 mol (A, M)
m 0.0220
b. n(NaCI) = — = = 3.76x10^ mol
M 58.5
c 3.76 x 10"4
c(NaCI) = — = = 0.0188 mol L"1 (A, M)
V 0.020
A - calculating one part of calculation correctly or no more than one mathematical error; M - all
calculations correct.
n(NaOH) = cx V/ Formula.

= 0.100x0.250 Substitute values.

= 0.0250 mol Appropriate number sf, correct unit(s).

m(NaOH) = n x M Formula.

= 0.0250 x 40.0 Substitute values.

= 1.00 g Correct unit(s). (A, M)

A - calculating one part of calculation correctly or no more than one mathematical error; M- all
calculations correct.
a. n(CuS0 4 .5H 2 0) = cxV Formula.

= 0.100x0.250 Substitute values.

= 0.0250 mol Appropriate number sf, correct unit(s).

m(CuS0 4 .5H 2 0) = nx M Formula.

= 0.0250 x 249.5 Substitute values.

= 6.24 g Appropriate number sf, correct unit(s). {A, M)

For following, all calculations must be correct.

CiV, =c2V2 Formula.

Vi
c2 = c, x —

= 0.5 x 0.02 Substitute values.

0.1

= 0.100 mol L"1 (A)

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 133 Answers and explanations

b •1 x —
V2
c(HCI) =
0.1 x 0.001
0.010
Total volume of water is 1 OmL.

= 0.01 mol L"1 (/VI)

7. A - calculating one part of calculation correctly or no more than one mathematical error; M - all
calculations correct.
n
a. c(NaCI) = Formula.

0.1
Substitute values.
0.250
= 0.4 mol L"1
Vi
c(NaCI) = c, x —

= 0.4 x 0.25
0.5

= 0.2 mol L"1 (M)

n 0.05
b. c(HCI) = = 2 mol L"1
V 0.0250

C2 = C, X —

c(HCI) = 2 x 0.025
0.1
= 0.5 mol L-1 (M)

8. All calculations must be correct.

0.0333 x 58.5 = 1.95 g L " 1 (A)

9. All calculations must be correct.

= 3.58 x 10-3 mol L"1 (4)

106

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134 Answers and explanations

90308 AS 2.4: Describe the nature of structure and bonding in

different substances
Chemical bonding and Lewis structures AS 2.4

b. Name of shape
a. Lewis structure
Formula (A-2 out of 3 correct; M - all
( 4 - 3 out of 5 correct; M - all shapes correctly drawn)
3 shapes correctly identified)

** S
S0 2 Bent or V-shaped
• q•i ' V o
••:
or s o. .* N .d:
..

co2 :b::c::o: or :b = c = o: Linear

•V. -s-
H2s U U or / \ Bent or V-Shaped
H H H H

.-0-. -o-
H2O or / \ Bent or V-shaped
H H H H

.. ..

ossssbs *
so 3 Trigonal planar
" 80S" °r I
SOS
..

Covalent bonds can be shown as 'sticks' or dots (ie pairs of electrons).

c. i. Non-polar.
ii. Polar.
iii. H2S contains polar bonds. S is more electronegative than H (ie it attracts electrons more
strongly); non-symmetrical arrangement of H-S bonds means an uneven charge distribution
over the whole molecule.
5 - . . 8-
•C •
V.*
H H
8+ 8+
C0 2 contains polar bonds but symmetrical arrangement of C-0 bonds means there is an even distribution
of charge over the whole molecule and therefore the polar bonds cancel. 5- 5+ 5-
:p::c::o:

(A - i, ii, correct, plus one correct statement; M - A plus two correct statements; £ - all correct)
d. With H 2 0 there are four pairs of electrons around the central atom. The electron pairs repel one
another to give maximum separation. In a tetrahedral shape (4 pairs of electrons) the angle
between the bonds is 109°. With S0 2 there are 3 pairs of electrons around the central atom,
giving a trigonal planar shape and therefore the angles of maximum separation are 120°.

(A - angle difference related to shape, limited discussion; M - angle difference related to electrons
around the central atom, repulsion and shape)
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 135 Answers and explanations

e. H 2 0 is polar and S0 2 are polar. Polar substances dissolve in polar solvents. (A)

The attractive forces between H 2 0 and S0 2 are the same as the forces between the S0 2 molecules
and the same as the forces between the H 2 0 molecules. Positive end of one molecule, eg water, is
attracted to negative end of S0 2 . Hence, S0 2 dissolves. ( M - correct explanation given)

2. a. Covalent.

b. Covalent.

c. Ionic. (A - all correct) u

n
3. a. •<:• + 4H* —> H :c*: H
• • •
H
b. Covalent. (A - both correct)

H'N'H H—*N — H
4. a. HV.*H or I
H A

Covalent bonds can be shown with a pair of electrons but not both, eg •• or — ,but not ••—.

b. :p:SO: or :p = q :

H
H I
c. H:C:O:H 0R H—C — O—H
•• •• 1
H
H

d. H:O:G: or H — 0 — cj: (A - at least 3 correct)

HHH
5. a. H:C:C:C:H
HHH

H . ## #>H
b. »C»»Cm
H H

:ci
• • —p—ci:
| ••
:CI:P:CI:
c.
:cj:

d. :Ci:o:a: (A - at least 3 correct)

6. A polar bond is an attraction between two atoms; one atom has a greater electronegativity than the
other / has a non-zero dipole moment. For example, the C-CI bond in carbon tetrachloromethane,
CCI4, is polar. CI is more electronegative than C, so the electrons are found closer to the CI atom than
the C atom / CI carries a partial negative charge, C carries a partial positive charge. A polar molecule
has polar bonds and the charge distribution is uneven over the whole molecule / bond dipoles do not
cancel because of the unsymmetrical shape of the molecule, eg ammonia, NH 3 . A molecular dipole
exists.

(4 - mentions polar molecules have polar bonds; M - plus partial explanation; £ - full explanation-
example chosen must clearly define difference between a polar bond and polar molecule)

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136 Answers and explanations

7. a. .g. 8CIS {A)

H S C J H or H—C—H
H J,
b. Tetrahedral. (M)

c. Polar. CHCI3 contains polar bonds (ie each C-CI and C-H bond is polar). Because of the lack of
symmetry of the molecule, the charge distribution is uneven (ie the polar bonds do not cancel
each other). The molecule is therefore polar.

(4 - states molecule is polar and notes polar molecules contain polar bonds; M - plus partial
explanation; E - full explanation)

Is a polar molecule?
Lewis structure Shape
(Yes/No)

•cr
•ClI
CCI 4 raicja: OR : a - c _ a : Tetrahedral No

•n*
.u.

co 2 :o::c::o: or :o=c=o: Linear No

•v.
SCI 2 :CI:S:CI: OR / \ Bent Yes
• ••••• *r\* vi*
vi* V>
H2 HIH or H —H Linear No

(A - 3 Lewis structures correct; M - 3 shapes correct or 3 polarities correct;

£ - all correct with shapes identified correctly and polarities correct)

Types of substances AS 2.4

a. b. c.
Ice Molecules Weak intermolecular Low
Silicon dioxide Atoms Covalent High
Iron Atoms Metallic High
Potassium chloride Ions Ionic High ( M - 3 rows correct)
( 4 - 3 correct; ( 4 - 3 correct) ( 4 - 3 correct)
( M - 3 solids correct for a, b, c)

a. i. Iodine is a molecular solid. It is made up of covalently bonded iodine atoms that are held
together by weak intermolecular forces. When heated, the weak intermolecular forces break
easily, hence iodine sublimes easily.

ii. Iodine molecules are non-polar. Cyclohexane is a non-polar solvent and water is a polar
solvent, and hence iodine dissolves in cyclohexane.

Answer that states 'like dissolves like' is not a full answer.

iii. Iodine is made up of molecules and there are no free-moving charged particles. Therefore,
iodine does not conduct electricity.
(4 - recall simple ideas; M - clearly explains two; E - full explanation of all)

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 137 Answers and explanations

b. Magnesium chloride - ionic bonding. MgCI2 is made up of ions held together by strong
electrostatic forces between positive and negative ions.

Sulfur dichloride - covalent bonding between S and CI. Weak intermolecular forces between the
molecules. (A - identifies 2 out of 3 types of bonds; M - correct discussion of one of the substances;
£ - full discussion)

3. Diamond is a giant covalent network made of carbons atoms held together by strong covalent bonds.
The 3-dimensional structure formed is rigid and strong and the bonds are not easily broken. Hence,
diamond is used to make saws to cut marble as it is hard.
Graphite is a giant covalent network made of 2-dimensional layers. The layers contain carbon atoms
covalently bonded to three other carbon atoms. The remaining valence electron from each carbon
atom is free to move through the structure. Because these electrons are free moving, graphite
conducts electricity.
The atoms in the layers are held together by strong covalent bonds, whereas the layers themselves are
held together by weak forces. Because they are easily broken, the layers can slide over one another,
and hence graphite can be used as a solid lubricant. (4 - briefly describe either diamond or graphite
structure; M - links properties and structure for two uses; £ - full explanation)
4. a. Molecular.
b. Covalent network.
c. Ionic.
d. Metallic.
e. Ionic.

f. Covalent network. (A - at least 5 correct)

5. a. Molecular. b. Covalent network, c. Ionic. d. Metallic. ( M - all correct)

6. a. Potassium chloride.
b. Wax.
c. Wax and copper carbonate.
d. Ammonia. ( M - all correct)
7. Place a small sample of both in water. Silicon dioxide does not dissolve in water, sodium chloride does.

Tests that will not distinguish between the two substances are:
• Conductivity - both do not conduct.
• Dissolve in cyclohexane - both do not dissolve in non-polar solvents.
• Melting point - both have high melting points.
(A - answer indicates solubility test; M - solubility test stated with observations correct for both
substances)
8. a. Hydrogen sulfide is a molecular substance. Although there are strong covalent bonds holding the
atoms together, the forces between the molecules are weak. Therefore, only a small amount of
energy is needed to pull the molecules apart and hydrogen sulfide has a low melting point.
Copper sulfide is an ionic substance made of ions held together by strong electrostatic attractions
(ionic bonds). A large amount of energy is required to break the ionic bonds and separate the
ions. Hence, copper sulfide has a high melting point.
b. Sodium sulfate is an ionic substance made of ions held together by strong electrostatic attractions.
Water molecules are attracted to the ions with sufficient strength to pull the ions out of the lattice
- the sodium sulfate dissolves.

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138 Answers and explanations

Sulfur is a non-polar molecular substance. Forces between water molecules are stronger than the
forces between the water and the sulfur molecules. Therefore, water molecules do not separate to
allow the sulfur molecules in between. Hence, sulfur does not dissolve in water.
( M - both answers provide at least partial correct explanations; £ - both answers provide full
correct explanations)
9. Make sure that you use the terms atoms, molecules, ions correctly.
a. Carbon dioxide is a non-polar molecular solid. It contains weak forces between molecules. Only a
small amount of energy required for molecules to break apart, therefore carbon dioxide sublimes
at low temperatures.

b. Iodine and cyclohexane are non-polar molecular substances. As attractive forces between iodine
molecules are of the same magnitude and type as forces between hexane molecules, iodine
dissolves in hexane.

c. Aluminium is a metal with delocalised electrons free to move - therefore aluminium is able to
conduct electricity.

d. Calcium is a metal made up of positive ions in a 'sea' of delocalised electrons. Electrostatic forces
exist between the ions and electrons - this metallic bonding is strong. Atoms must be separated
for metals to melt. A large amount of energy is required for the 3-D lattice to break apart - hence
melting point is high.
e. Diamond is a covalent network solid made of atoms held together by strong covalent bonds.
Large amounts of energy are required to break the covalent bonds and separate the atoms.
Hence, diamond has a high melting point.

f. Graphite is a covalent network solid made up of carbon atoms arranged in 2-D layers. In the
layers, only 3 of the 4 electrons for each C atom are involved in bonding - the remaining
'delocalised' valence electrons are free to move through the structure, allowing graphite
to conduct electricity. ( M - at least four correct partial explanations; £ - at least four full
explanations)

The Periodic Table AS 2.4

1. a. i. MgCI 2 ii. SiCI4 (A for both correct)

b. Solid. Melting point and boiling point are both greater than room temperature, therefore AICI3
would be solid, (flf)
c. i. Ionic. ii. Molecular. (A - both correct)
d. Sodium chloride is an ionic substance. It is made up of ions held together by strong electrostatic
forces. Considerable energy is required to overcome these forces and melt sodium chloride, hence
it has a high melting point. Phosphorus trichloride has a low melting point. It is a molecular
substance with only weak intermolecular forces needing to be broken in order for the substance to
melt. (A - both substances identified correctly; M - partial explanation; £ - full explanation)
For £ need to compare the two substances and mention what the substances are composed of
and how they are bonded, and then link this to the property. (In this case, the properties are the
high and low melting points.)

2. a. Liquid.
Melting point is less than room temperature and boiling point is greater than room temperature,
therefore bromine would be liquid. (A)
b. Cl2 has low melting point and low boiling point, which suggest it is molecular. The formula is
Cl2, therefore chlorine is made up of chlorine atoms covalently bonded with weak intermolecular
forces between the Cl2 molecules. (M)

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 139 Answers and explanations

90309 AS 2.5: Describe the structural formulae and reactions

of compounds containing selected organic functional groups
Characteristics and physical properties of hydrocarbons AS 2.S

1. a. Alkene.

b. 5-methylhex-1 -ene. (A - both correct)

H

H— C —H
CH 3 H H H H H
| 1 1 1 1
i i I I 1
A CH 3 CCH 2 CH 2 CH 2 CH 3 OR — C— ( C — c —C — C —
I I i I I
I 1 1 1 1 1
CH 3 H H H H H
H— C —H

Condensed or expanded structural forms are allowed for each answer.

CH 3 CH 2 CHCH 2 CH 2 CH 2 CH 3
I c. HC = CCH 3
CH 3

CH 3 CH 3

' CH = CCHCH 3 E' CH 3 CH = CHCHCH 3

(A - three answers show correct carbon backbone number with functional group; M - at least three
answers show carbon backbone number with functional group and alkyl groups in the correct place)
3. a. Butane.

b. 2-methylhexane.

c. 2,4-dimethylpentane.

d. But-1-ene.

e. Pentane.

f. 2-methylbutane.
(A - four answers show correct carbon backbone number with functional group; M - at least four
answers show carbon backbone number with functional group and alkyl groups in the correct place)

Chemical properties of hydrocarbons AS 2.5

1. Compound A

A reaction occurs with bromine.

Observation: Bromine changes from orange to colourless.

H H
I I
Equation: CH 3 CH = CHCH 3 + Br2 > CH 3 — C — C — CH 3
I I
Br Br

Type of Reaction: Addition.

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140 Answers and explanations

Compound A is recognised as an alkene - it has a double bond. The colour change is to colourless
(not clear). Each Br atom adds to either side of the double bond.

Compound B

No immediate reaction occurs with bromine.

Observation: Bromine remains orange. In the presence of sunlight bromine changes from orange to
colourless.

Equation: CH 3 CH 2 CH 2 CH 3 + Br2 u v ) CH 3 CH 2 CH 2 CH 2 Br + HBr

Type of reaction: Substitution.

(A - one comparison (eg colour difference correct); M - two comparisons correct; £ - clear comparisons
plus equations)

H H H H
I I I I
a. ---C — C — C — C - - - (A)
I I I I
CH 3 H CH 3 H

b. i. CH 3 CH 2 CH 3

H H H H H H
I | |
1
ii. H- C —C —C —H and H — C —C —C — H *
1 1
1
H H OH H OH H

iii. *The larger amount occurs where H attaches itself to the C with the greater number of H's.

(A - two correct products; M - all three correct and correctly identified product produced in the
larger amount)

3. Add non-polar solvent to fat. Add measured amounts of bromine to fat solution. More bromine water
decolourises with the fat that has a higher degree of unsaturation. (A - bromine decolourises; M - plus
explanation)
4. a. Complete combustion. b. Addition. (A - all correct)

5. A Secondary. B Primary. C Tertiary. (A - all correct)

6. a. H OH H H b. H CI H H H CI
I I I I I I I I I I
H —C —C —C —C —H H— C— C— C—H + H—C —C —C —H
I I I I I I I I I I
H H H H H H H H H H
Major product.

c. H H d. H Br Br H
I I I I I I
H—C—C—H H—C—C—C—C—H
I I I I I I
H H H H H H
(A - three reactions show correct organic product; M - all reactions correct)
7. a. H H Br H
1 1 r ht 1 1
H — C — C — H + Br2 ^ ^ H — C — C — H + HBr
I I I I
H H H H
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 141 Answers and explanations

H H H H H H H H H
I I I I
pt
H—C—C=( C -- C - - C > H C — C — C -- C — C — C — H
i i i I i i i I
I I I I I I I I I
H H H H H H H H H H
(4 - reactions show correct organic reactants; M - reactions show correct organic reactants and
products)

Answers can be shown using condensed form.

8.
Colourless
Bromine water Acidified potassium p e r m a n g a n a t e
liquid

Alkane Reacts slowly with bromine water in the Stays purple.

presence of sunlight to decolourise (ie
orange -> colourless).

Alkene Reacts quickly with bromine water to Decolourises acidified potassium

decolourise bromine water (ie orange -> permanganate (ie purple colourless).
colourless).

Only one chemical test needed. When describing 'no colour', use the term 'colourless', not 'clear'.

( M - mentions alkene decolourises; £ - compares and contrasts different observations for alkane
and alkene)
9. F F

\ =C (4)
/ \
F F

Alcohols AS 2.5

1. a. Primary alcohol. (4)

b. Oxidation reaction. (A)

2. H OH CH 3 H
I I I I
H—C —C —C —C —H (4)

H H H H

3. a. i. Methanol.

ii. Pentan-1-ol.

iii. Butan-1 -ol.

iv. 2-methylpentan-1-ol.

v. 2-methylpropan-2-ol.
(4 - three answers show correct naming of carbon backbone number and functional group; M - at least three
answers include correct carbon backbone number with correct functional group and alkyl group numbering)
b. i. Primary, ii. Primary, iii. Primary, iv. Primary, v. Tertiary. (4)

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142 Answers and explanations

4. a. H HH H H b. H OH H H H
1
C —C— C H H—C—C—C—C—C—H

H H H H H H H H

OH

CH 3 CH 2 CHCHCH 2 CH 3 (4 - two correct needed)

CH 3

5. a. Orange dichromate turns green. b. Propanoic acid.

c. Methanol. d. Mn0 4 "/H + (4 - two correct; M - all correct)
6. a. CH 2 =CH 2 + H 2 0 2CH 3 CH 2 OH
/H
b. CH 3 CH 2 CH 2 CH 2 OH CR2°7 ) CH 3 CH 2 CH 2 CH 2 COOH
warm

(4 - one reaction correct; M - both correct)

7. Add a few drops of acidified potassium dichromate solution to the unknown. W a r m .

Could use acidified permanganate.

Observation for alkane: orange potassium dichromate stays orange.

Observation of alcohol: orange potassium dichromate goes green.

(flf- evidence that potassium dichromate goes green; £ - correct method and observations.)

Isomers AS 2.5

1. a. Structural isomers: Compounds that have the same molecular formula but their atoms are
arranged differently.

Example: B and F are structural isomers - each has 4 C's and 8 H's but these are arranged in
different ways. (4 - correct definition or correct isomers identified; M - correct definition and
correct isomers identified)
b. CH3 CH 3 CH 3 H
/ \ /
= C^ X C = C\ (4 - both isomers correct)
H 7 H H 7 CH3
cis isomer trans isomer

2. A and D. Same molecular formula but different structure. (4)

3. CH 3 CH 2 CH 2 CH 2 CH 3 CH 3 CH 3

pentane CH 3 CHCH 2 CH 3 CH 3 CCH 3

methylbutane ^^

dimethylpropane

(4 - two correct; M - all correct and no additional compounds drawn)

4. a. B (4)

Alkanes do not exhibit cis-trans isomerism (A and D); C has the same groups on the same side of
the molecule.

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 143 Answers and explanations

CI H CI CI
\ / \ /
C = C C
/ \
H CI H
\H
c/s-1,2-dichloroethene
trans-1,2-dichloroethene
5. H Br H H
Br H H H
I I I I
I I I I
H—C—C—C—C—H H—C—C—C—C—H
I I I I
H H H H H H H H
1-bromobutane 2-bromobutane

H H

H - C- H H— C H
Br H H H

H —C —C —C —H H —C- H
I I I
H H H H Br H
1 -bromomethylpropane 2-bromomethylpropane

(A - two correct; M - all correct and no additional compounds drawn.)

6. A, B and D. (A)

All have the molecular formula C 5 H 1 2 0. If you only wrote down two isomers, remember that
isomers do not necessarily come in pairs.

7. a. When rotated around in space they are the same molecule. Structural isomers would have
different arrangements.

b. The methyl groups are on the same end of the double bond. ( M - one clear explanation; £ - both
explanations clear)

Carboxylic acids and esters AS 2.5

a. Bubbles would appear or fizzing or effervescence.

(A - need to write an observation - 'gas formed' is not an observation)

Could state sodium carbonate disappears (it is not clear from the question whether sodium
carbonate is a solid or in solution).

b. A is an alcohol:
• Soluble in water.
• Acidified dichromate and warm - orange dichromate goes green.
• No reaction with blue litmus - stays blue.

B is an ester:

• Insoluble in water.

• Smell - fruity smell.

• No observation with dichromate - stays orange.

• No reaction with blue litmus - stays blue.

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144 Answers and explanations

C is a carboxylic acid:

• Soluble in water.

• Bubbles of gas with sodium carbonate.

• No observation with dichromate - stays orange.

• Turns moist blue litmus red.

(A - o n e compound distinguished and identified using chemical and physical properties; /Vf-two
compounds distinguished and identified using chemical and physical properties;
E — ail three compounds distinguished and identified using physical and chemical properties)

N a m e of f u n c t i o n a l g r o u p Systematic n a m e of t h e c o m p o u n d
Carboxylic acid/carboxyl Propanoic acid

Ester Methyl ethanoate

Compound Structural formula Name

X CH 3 CH 2 CH 2 CH 2 OH butan-1-ol

Y CH 3 CH 2 CH 2 COOH butanoic acid

0
Z CH3CH2CH2C^ butyl butanoate
\
OCH 2 CH 2 CH 2 CH 3

w CH 3 CH 2 CH = CH 2 but-1 -ene

V CH 3 CH 2 CH 2 CH 2 CI 1 -chlorobutane

CH 3 CH 2 CHCH 3
V' 1 2-chlorobutane
CI

(A - three answers showing correct structure or named; M - four answers showing correct structure or
correct names; f - f i v e compounds correctly identified with structural formulae and correct names)
0
3. a. || (A)
OC

b. Alcohol/hydroxyl. (flf)

The functional group is asked for and not the name of the compound.

c. Unsaturated means the compound contains double or triple bonds. More atoms can by added to
the compound. (4)

4. H H O CH 3 CH 2 COOH also acceptable.

H—C — C— C— O — H (A)
1 I
H H
5. Hexanoic acid. (4)

6. a. C b. A (A for both correct)

7. Ethanol and methanoic acid. (A, M)

(A - one organic substance identified; M - both organic substances identified and no additional
substances identified)

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 145 Answers and explanations

H 0 H H H
1 II 1 1 1
H — C — C — 0 — C — c —C — H
I 1 I L1
1 1 1
H H H H
a. (A - correct formula)

b. (A - functional group)
9. a. Provides maximum product formation and speeds up the reaction by condensing vaporised
reactants so they do not escape from the reaction vessel. (A)

b. B (A)

c. Acts as a catalyst and displaces the equilibrium in favour of products. (A)

d. Ester. (A)
O

e. CH 3 CH 2 OH + CH 3 CH 2 CH 2 COOH -> CH 3 CH 2 CH 2 COCH 2 CH 3 + H20

ethanol + butanoic acid -> ethyl butanoate + water

(A - correct structure of ethanol and butanoic acid drawn; M - also correct equation)

10. a. i. Methanol.

ii. Butanoic acid,

b. i. Propanol.

ii. Ethanoic acid. (A - at least two correct; M - all correct)

11. a. Esters or triesters or triglycerides. (A)

b. Glycerol (propan-1,2,3-triol). (A)

c. O
II
C 1 7 H 3 5 -C-O-CH 2 H 2 C — OH
0

C 17 H 35 — c — O — C H + 3NaOH ^ 3C 17 H 35 COONa + HC — O H
O
II
C 17 H 35 — c — O — CH 2 H2C — O H

glycerol

(A - part of equation correct; M - all equation correct)

d. Saponification. (A)
O

12. a. CH 3 CH 2 CH 2 COCH 3 + H20

methanol + butanoic acid —> methyl butanoate + water

,0
CH3C^ Na+ CH 3 CH 2 OH
O"
ethyl ethanoate + sodium hydroxide —> sodium e t h a n o a t e + ethanol

(A - two products correctly identified; M - all correct)

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146 Answers and explanations

13. a. Ethyl propanoate. b. Methyl ethanoate. c. Butanoic acid,

d. Methyl propanoic acid. e. Butyl propanoate.
(.A - at least three answers show correct number of carbons and functional group endings (ie 'acid' or
'oate'); M - at least four correct)
14. Test 1: Add litmus paper to a sample of the ester and a sample of the carboxylic acid.

Observation: Carboxylic acid - blue litmus paper turns red; ester - no change observed.
Test 2: Add baking soda to a sample of the ester and a sample of the carboxylic acid.
Observation: Carboxylic acid - bubbles given off; ester - no change observed.
(4 - show evidence of one correct test and observation; M - discuss clearly difference (ie compared
and contrasted) between a carboxylic acid and ester)

90310 AS 2.6: Describe principles of chemical reactivity

Energy changes AS 2.6

1. a. Exothermic. AH is negative.
b. Endothermic. Energy (sunlight) is used.
c. Exothermic. Liquid to solid.
d. Exothermic. Increase in temperature of surroundings.
e. Endothermic. Solid to gas - bonds breaking. ( 4 - 4 out of 5 correct)

2. a. 1 mol releases 98.2 kj, so 5 mol releases 5 x 98.2 = 491 kj (4)

b. n(0 2 ) = m
M

1.0 M(0 2 ) = 16 x 2 = 32 g mol"1

32.0
= 0.03125 mol

0.5 mol 0 2 releases 98.2 kj of energy, therefore 0.03125 mol 0 2 releases 6.14 kj of energy.
(4 - correct molar mass for oxygen calculated or correct answer given with no units; M correct answer
including units)

c. 1 mol H 2 0 2 produces 98.2 kj of energy, so 6.11 mol H 2 0 2 produces 600 kj of energy.

m(H 2 0 2 ) = nx M

= 6.11x34 M(H 2 0 2 ) = (2 x 1) + ( 2 x 16)

= 207 g = 34 g moh1
(4 - one step correct; M - two steps of calculation correct; £ - correct answer including units)
3. Exothermic - a, d, f, g.
Endothermic - b, c, e. (4 for at least four correct)
4. a. Endothermic.
b. i. -206 kj mol"1 Reverse the sign. (4)
ii. +618 kj moM 3 x 206 kj moH =+618 kj mol"1 (4)
5. Ammonium nitrate dissolving in water is an endothermic reaction. Heat is absorbed from the
surroundings, ie from the water. Consequently, the temperature of the water drops. (M)

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 147 Answers and explanations

6. a. Exothermic. Energy is released.

b. -376 kj mol"1

188 kj of energy is released when 2 mol of S0 2 is used (according to the equation). Therefore,
4 mol of S0 2 (double 2 mol) releases 2 x 188 kj = 376 kj.
As energy is released, the sign of AH is negative; therefore the value of ArH is -376 kj mol-1. (M)

192
64
= 3 mol
2 mol of S0 2 reacts and releases 188 kj of energy.
So, 3 mol of S0 2 reacts and releases 282 k) of energy.

(A - ArH calculated using incorrect molar mass or correct answer with no sign or unit; M - correct
answer including unit)
d. When 2 mol of S0 3 is formed, 188 kj of energy is released.

Therefore, when 0.25 mol of S0 3 is formed, 23.5 kj of energy will be released.

0 25

— — x 188 = 23.5 ( A - correct method; M - also answer correct)

7. b.
a. n(CaC0 3) = —
1 mol absorbs 1 79 k] of energy. So, 0.2 mol absorbs 35.8 kj of energy. (A)
According to the equation, 1 mol of CaC0 3 absorbs 1 79 kj of energy.
Therefore, 0.15 mol of CaC0 3 absorbs 26.9 kj of energy.
(A - ArH calculated using incorrect molar mass or correct answer with no sign or unit; M - correct
answer including unit)
c. When 1 mol CaC0 3 reacts, 1 79 kj energy is absorbed. Therefore, when 4.5 mol CaC0 3 reacts,
805.5 kj energy is absorbed.

m= nx M = 4.5 x 100 = 450 g

(A - one step correct; M - two steps correct)
8. a. 64.4 kj 5 g releases 32.2 kj of energy; 10 g = 2 x 5 g. (A)
b. 32.2 kj There is less water but still the same mass of H 2 S0 4 being dissolved. (A)
c. The temperature rises 8°C when 5 g sulfuric acid dissolves in 100 mL.

Therefore, when 5 g sulfuric acid dissolves in 50 mL, the temperature rises 16°C. (4)
There is still the same mass of sulfuric acid being dissolved and the same heat energy being released.
Because there is only 50 mL of water, there is less water for the heat to disperse through, and
consequently the water temperature rises.
( M - reason correct)

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148 Answers and explanations

Rates of reactions AS 2.6

1. a. Change 1 Increase.

Change 2 Decrease.
Change 3 Increase.

Change 4 Remain the same. ( A - 4 correct)

b. Change 1 An increase in temperature increases kinetic energy and causes the particles to move
faster and there is more chance of collision. As a result, the frequency of collisions in a given time
increases and the rate of reaction increases. (M)
Also, the collisions are more energetic and more collisions will have more energy than the
activation energy, so the reaction is faster. (£)

Change 2 The addition of water dilutes the acid. There are fewer hydrogen ions (A) in the same
volume of solution (ftf), so less frequent collisions occur between hydrogen ions and calcium
carbonate so the reaction is slower. (£)

With catalyst

Reaction coordinate

b. Does not get used up in the reaction. Does not change the products formed. (A)

c. The manganese dioxide provides an alternative pathway of lower activation energy.

Consequently, more collisions will have the required activation energy for the reaction.
(4 - first sentence; M - also second sentence)

3. a. Experiment 1. The lower the temperature, the slower the reaction. (A)
b. Rate of hydrogen gas produced would decrease over time.
A diagram could also be used:

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 149 Answers and explanations

Initially, the rate is rapid as there are many reactant particles colliding. The rate slows down after
time passes. The graph levels off as one or both of the reactants have been used up.
{A - diagram or description; M - also explanation)
c. Experiment 3.
Increase in temperature increases the rate of reaction - when the temperature increases, the
reactant particles have increased kinetic energy (ie they move faster) and therefore there is more
chance of an increase in the frequency of collisions. Also, there is an increased chance of
particles reaching the required activation energy, ie collisions are more effective.

(A - identified Experiment 3; M - explaining one aspect of collision theory; £ - explain both

aspects of collision theory)
4. B
There is a greater number of acid particles per volume in concentrated hydrochloric acid compared
with dilute hydrochloric acid.
With increased concentration, particles are closer together so there is an increased chance of colliding.
As a result, the frequency of collisions increases and hence the rate of reaction increases. (A - identified,
also first sentence; M - collision theory included)

An answer such as 'Concentration increases reaction rate' is not sufficient for M - need to explain
why, using collision theory rather than making a statement of fact.
5. a. The rate of a reaction decreases as the reaction continues because the concentration of the
reactants is also decreasing. (M)

(A - line drawn below the graph line but stays below; M - dotted line under solid line - ends up at the
same vertical level as the original line)

ii. With solid marble there is less surface area exposed to the acid, so there are fewer particles
colliding and hence the reaction begins more slowly.
However, because the same mass is used as in the case of the powder, over time the same
volume of gas is given off and the graphs level out the same, ( M - first sentence only; £
- second sentence)

6. Any one of the following:

• Increase concentration by increasing the pressure.
With increased concentration, particles are closer together so there is an increased chance of the
particles colliding.
As a result, the frequency of collisions increases and hence the rate of reaction increases, (ftf)
• Use a catalyst.
A catalyst increases the rate of reaction by lowering the activation energy for the reaction.
This means that the collisions are more effective as more particles have sufficient energy to react. (M)
© ESA Publications (NZ) Ltd. Freephone 0800-372 266
150 Answers and explanations

Increase the temperature.

When temperature increases, reactant particles have increased kinetic energy (ie move faster) and
therefore there is more chance of collisions.
Also, there is an increased chance of particles reaching the required activation energy, ie more collisions
are effective. Question asks about rate - therefore, equilibrium effects should not be discussed.

(4 - first sentence; M - also second sentence (explanation); f - all sentences)

Equilibrium AS 2.6

[so3]2
1. a. Kc =
[S0 2 ] 2 [0 2 ]

[NO] 4 [H 2 0] 6
Kc =
[NH 3 ] 4 [0 2 ] 5

[H+] [CH3COO-
c. Kc ="
[CH3COOH]

Charges must be inside the square brackets. (A - at least 2 correct)

2. a. N0 2 should be circled.

b. Kc is small (less than 10~3) therefore the concentration of products is small and only a small
amount of reactants has been changed into products. Therefore the reactant, N0 2 , would be
expected to be in greater concentration. (M)

c. i. Observation: Goes darker brown. (A)

Answer should be an observation, ie don't write 'equilibrium moves to the right/forward

direction'.

Explanation: ArH is negative, ie reaction is exothermic in the forward direction. Therefore,

the reaction is endothermic in the reverse direction. Increase in temperature changes the
equilibrium position in the direction of the endothermic reaction. Therefore, more N0 2 is
produced and a darker brown colour is observed. (£)

ii. Observation: Colour goes darker brown. (A)

Explanation: Adding more N0 2 increases the pressure. The equilibrium shifts in the direction
with the least number of moles of gas, ie in the forward direction producing N 2 0 4 . N 2 0 4
is colourless. (M) Some N 0 2 will react, but not all, so still more N 0 2 in new equilibrium
mixture, so it will be a darker brown. (£)

At equilibrium, both reactants and products are present, so there is a tendency for the
mixture to go from dark brown to light brown rather than brown to colourless, as indicated
by the colours of each gas.

3. b and d. Both are closed systems. (A)

4. a. Kc = m [ C t i b. [N2OP c [CH3OH] (4at|easttwocorrect)

[PCI5] [N 2 ] 2 [o 2 ] [CO][H 2 ] 2

5. a. /Cc = [HC']2 (4)

[H2] [Cl2]
b. Kc is large, therefore the equilibrium lies to the right and the concentration of products is greater
than the concentration of reactants. (4)
c. i. Equilibrium favours the forward direction and therefore product formation,
ii. Equilibrium favours the forward direction and therefore product formation.
 151 Answers and explanations

iii. No change (there are equal numbers of moles of gas on both sides of the equation).
(A at least two correct)
6. a. The concentration of dichromate ions would decrease. The barium ions cause a reduction in the
concentration of chromate ions. The equilibrium shifts in the forward direction to counteract the
change in the decrease in concentration of chromate ions. As a result, the concentration of
dichromate ions decreases.
(A - first sentence only; M - also explanation (which includes direction of equilibrium))

b. A change in colour - to a darker orange - would occur. Adding hydrochloric acid adds H+
ions to the system. The position of equilibrium will shift to use up some of the added H+ ions. The
equilibrium shifts in the reverse direction so that more dichromate ions are formed and this is seen
as a colour change to a darker orange.
(A - first sentence only; M - also explanation (which includes direction of equilibrium))
7. a. i. Increased amount of methane. ii. Increased amount of methane.

iii. Decreased amount of methane. iv. Increased amount of methane,

v. No change.

A catalyst does not affect the direction of the equilibrium; it increases

the rate at which equilibrium is reached. (A at least three correct)
[NH 3 ] 2
b 1 Kc = [N 2 ][H 2 ] 3 W
ii. Favours reactant formation. (A)
iii. Favours product formation. (A)
8. a. If the temperature were too low the reaction rate would be too slow. (M)
b. Increases the rate at which equilibrium is reached. (A)
c. Increase the pressure. (A)

Acids and bases AS 2.6

1. a. HY should be circled.

b. HY has a pH of 1. This means that the concentration of hydronium ions is greater in solution than
HX (pH 3). This means that HY has fully dissociated in solution, ie it is a strong acid.
(A - correct justification in terms of lower pH implies a stronger acid; M - considers concentration
of hydronium ions)
c. Add a small amount of magnesium ribbon to each of the acids. HY will produce greater fizzing/
bubbles. Could also add carbonate or test conductance.
(A - test described; M - correct explanation given)
2. a. BASE should be circled.
b. Bases are proton acceptors. HC0 3 _ accepts a proton from H 2 0 to produce H 2 C0 3 and OH". (A)
3. Ammonium chloride dissolves in water:
NH4CI + H 2 0 > NH4+ + ci-
The ammonium ions react with water:
NH4+ + H 2 0 > NH 3 + H 3 0 +
NH4+ donates a proton to water and H 3 0 + ions are formed. Hence the solution is acidic.
(A - recognises NH4+ present or increase in H+; M - identifies H 3 0 + present, changes in pH linked to
NH4+; E - explains ammonium ions are acidic and react with water and equations correct)

© ESA Publications (NZ) Ltd, Freephone 0800-372 266

152 Answers and explanations

4. a. 3.47 xlO" 1 3

Kw 10-14
[H 3 0 + ] = [OH-] = q Q283 = 3.47 x 1CH3 mol L-1 Requires rearranging a formula.

b. 12.46 pH =-log [H 3 0 + ] = 12.46 Requires recalling a formula.

c. 5.75 x 10"6 [H 3 0 + ] = 10"PH = 5.75 x 10~6 mol L"1 Requires recalling a formula.

d. 1.74 xlO" 9

Kw i x io-14
[OH~] = ^ = 5 75 x •] Q-6 = 1 -74 x 10"9 mol L _1 Requires rearranging a formula.

(A - correct answer by rearranging one formula; M - one row correct; £ all answers correct)

5. a. True. b. False. c. True. d. True. (A at least three correct)

6. C 6 H 5 COOH, H 2 0, QHJCOO-, H 3 0 + , OH".

(A - at least three correct; M - all correct and no additional species identified.)
7. a. B

b. pH meter test: Hydrochloric acid is a strong acid as it dissociates fully. This means it has a high
concentration of hydronium ions in solution and consequently a low pH. Ethanoic acid is a weak
acid as it only partially dissociates. This means it has a lower concentration of hydronium ions in
solution and consequently a higher pH than hydrochloric acid.

Conductivity test: Hydrochloric acid is a strong acid as it dissociates fully. This means it
has a high concentration of hydronium ions in solution, and as these ions are free to move,
the hydrochloric acid conducts electricity very well. Ethanoic acid is a weak acid as it only
partially dissociates. This means it has a lower concentration of hydronium ions in solution and
consequently does not conduct electricity as well as hydrochloric acid.
(A - recognition of lower pH and higher [H+] for stronger acid; M - one test answered fully or both
tests answered correctly but discussion limited to one acid; £ — full explanation comparing and
contrasting differences)

8. a. HNO3, nitric acid - vigorous bubbling/effervescence. Ethanoic acid - bubbles given off. (A)

An answer of 'gas given off' would not be correct as this is not an observation - it is a conclusion
or inference made from the observation.

b. Neither. Both acids would react with the same amount of marble chip as the acids are the same
concentration. However, the marble chip would take longer to fully react with the ethanoic acid.
(M)
9. a. 1 x 1CH b. 4.0 c. 0.01 or 1x10~ 2 d. 1x10" 2 or0.01

(A at least three correct)

10. a. 2.5 x 10"2 b. 4x10" 1 3 c. 1.6 d. 1x10~ 12
e. 1 x 10-2 f. 12 (A- a. and b. correct; M - also c. correct; £ - all correct)

© ESA Publications (NZ) L t d , Freephone 0800-372 266

 153 Answers and explanations

90311 AS 2.7: Describe oxidation-reduction reactions

Redox reactions AS 2.7

1. a. Reduced. ON of Mn decreases (reduces) from +7 to +2. A decrease in oxidation number is

reduction. (4 - reduction; M - correct process and justification)
b. Oxidant: Mn0 4 ~
Reductant: Fe2+ (A - both correct)
c. Oxidation: Fe2+ > Fe3+ + e~
Reduction: Mn0 4 " + 8H+ + 5e~ > Mn2+ + 4H 2 0 (A - one half-equation correct)

d. 5Fe2+ > 5Fe3+ + 5e~ ( M - both half-equations only correct or

Mn0 4 " + 8H+
+ 5e" » Mn2++ 4H 2 0 overall equation correct but not balanced
~T7 ~~~ 7 m T m TTTTT correctly; E - overall balanced equation
5Fe2+ + Mn0 4 - + 8H+ > 5Fe3+ + Mn2+ + 4H 2 0 / M
correct)

e. Pale green Fe2+ would turn into orange-brown Fe3+.

Purple Mn0 4 " would turn into colourless/pale pink Mn2+.
In the test tube, the resultant solution would be an orange-brown colour.
(A - colour change stated correctly; M - colour change linked to correct species)

2. a. i. +4 S + 2(0) =0
S + (2x-2) =0
S =+4

H. + 6 S + 4 x (O) =-2
S + (4 x -2) = -2
(A - both correct)
S =+8-2
S =+6

b. S0 2 > S042- \2 > I-

S0 2 + 2H 2 0 > S0 4 2 " + 4H+ + 2e- I 2 + 2e" > 21"
(A - one product correctly identified and half-equations correctly balanced; M - A plus correctly
balanced equation)

c. Overall: S0 2 + l 2 + 2H 2 0 > SOA2' + 21" + 4H+ (£ - correctly balanced equation)

d. Orange dichromate ions, Cr 2 0 7 2- , turn into green chromium(lll) ions, Cr3+.
(A - correct colour or one species and one colour; M - correct observations linked to species
correctly)
3. a. CI = 0 b. Ca = +2, CI = -1 c. C = +2, 0 = -2 (4 - three or more correct)
4. a. N = +5 b. P = +5 c. C = +4 (4 - two or more answers correct)
5. a. +6 b. -2 c. +4 (4 - for two or more correct)
6. c and d. (4)
7. a. i. I 2 + 2e_ —> 21" ii. Fe2+ Fe3+ + e" iii. H 2 0 2 + 2H++ 2e"-+2H 2 0
(4 - for all half-equations correct)
b. ii. Increase in ON from 2 to 3 or loss of electrons shown on RHS of equation. (4)
8. a. 2H+ + 2e~ H2 b. Zn Zn2+ 2e" (4 - for both half-equations correct)
9. a. H202 b. Sulfate ion. c. Fe2+ (4 - for all correct)

© ESA Publications (NZ) Ltd, Freephone 0800-372 266

154 Answers and explanations

10. a. Green, b. Pale pink or colourless. c. Colourless, d. Green, e. Colourless.

(.A for at least three correct)

11. a. Reduction. Electrons gained is reduction.

b. Oxidation. Electrons lost is oxidation. Electrons released are on the RHS of the equation.
c. Oxidation. (A for two or more correct)
12. a. Mg b. I" c. Ca (A for at least two correct)
Only need to consider the reactants. The reductant is the reactant which is oxidised, ie loses electrons

13. For each equation:

A - both products correctly identified; M - both half-equations correctly balanced; £ - correctly
balanced overall equations and observations appropriate.

a. i. Observation: Orange solution turns brown,

ii. Reduction half-equation Br2 + 2e~ —> 2 B r
Oxidation half-equation 21" —> l2 + 2e~
Overall equation Br2 + 21" —> 2 B r + l 2
b. i. Observation: Orange solution goes green.
ii. Reduction half-equation Cr 2 0 7 2 " + 14H+ + 6e~ 2Cr3+ + 7H 2 0
Oxidation half-equation 3S0 2 + 6H 2 0 -» 3S0 4 2 " + 12H+ + 6e~
Overall equation Cr2072~ + 3S0 2 + 2H+ -> 2Cr3+ + 3S0 4 2 " + H 2 0 (A, M, £)

Electrolysis AS 2.7

1. a. i. Anode - carbon (graphite) / positive electrode. Cathode - carbon (graphite) lining / negative
electrode. (A - one correct)
ii. Oxide, 02~, ions move to carbon (graphite).
Aluminium, Al3+, ions move to carbon (graphite) lining. (A - one correct)
b. i. 20 2- —> 0 2 + 4e_ (A - one correct)
ii. Al3+ + 3e" Al ( M - both correct)
c. Equation: C(s) + 0 2 (g) C0 2 (g)
Explanation: Oxygen produced at the anode reacts with the carbon electrodes.
(.A - equation correct or explanation correct; M - answer clearly links idea with observation,
equation and explanation correct)
2. a. Anode - positive electrode; cathode - negative electrode. (A)
b. Li+(l) + e- —> Li(l) States not necessary.
(A - product identified correctly; M - half-equation also correct)
3. a. i. Lead ions, Pb2+.
ii. Bromide ions, Br~.
Need to state the specific ions. (A for both correct)
b. i. 2Br(l) -» Br2(g) + 2e"

ii. Pb2+(l) + 2e- -> Pb(l) (A - half-equation correct)

Equations need to be balanced. States not essential.

© ESA Publications (NZ) Ltd, Freephone 0800-372 266

 155 Answers and explanations

a. i. Hydrogen gas, H2. (A)

Either name or formula.

ii 2C\- -> Cl 2 (g) + 2e_ (A - product identified correctly; M - half-equation also correct)

b i. Anode - positive electrode. Oxidation (loss of electrons)

+,
II- occurs at the anode.
ii. Cathode - negative electrode.
iii. Chloride ions, CI".
iv. Sodium ions, Na+.
anode cathode (.A - i. and ii. correct; M- iii. and iv. also correct)

Must identify the substance that moves rather than the

substance that is formed. Need to label
diagram with correct species attached to correct electrode.

Electrolysis of brine. Reaction at cathode:

2H 2 0(I) + 2e" -> H 2 (g) + 20H"(aq)

Electrolysis of molten NaCI. Reaction at cathode:

Na+(l) + e" Na(l)

For the electrolysis of brine, the reaction at the cathode produces hydrogen because water is
easier to reduce than Na+. For the electrolysis of molten sodium chloride, there is no water and
the sodium ions move to the cathode to form sodium.

( M for correct equations only; equations and explanation to be correct for £)

5. a. An application of electrolysis, whereby a thin layer of a metal is plated onto another metal. In this
case, tin is plated onto the steel. (4)

b. Any one of: stops corrosion / stops rusting / stops steel oxidising / stops iron from being in contact
with food to prevent rusting. (A)

c. Cathode. (/4)

Chlorine and the halogens AS 2.7

1. a. i. Yes.
ii. Pale green (or colourless) solution turns orange.

iii. Cl2(aq) + 2Br(aq) -> Br2(aq) + 2CI"(aq)

b. i. No. ii. - iii. - (A - reactions correct or reaction i. correct with balanced equation;
M - reaction i. correct with equation and reaction ii. correct; £ - all correct)

2 a i. +1 O + CI =-1
-2 + CI = -1
-2 + (+1)=-1

ii. -1 O N of an ion is the same as the charge on the ion.

iii. 0 Elements have an oxidation number of 0. ( 4 - 2 out of 3 correct)

© ESA Publications (NZ) L t d , Freephone 0800-372 266

156 Answers and explanations

b. i. CI" Cl2

2CI" Cl2 + 2e-

ii. OCI- H> Cl 2

20CI" + 4H+ + 2e- Cl2 + 2H 2 0 (A - one half-equation correct)

c. 2CI" -» Cl2 + 2e~ (reaction i.)

Electrons are lost or the oxidation number of chlorine increases.

(A - correct reaction identified; M - A plus correct reason given)

d. O is oxidised, CI is reduced. (A)

Oxidation number of O increases from -2 to 0. An increase in oxidation number is oxidation.

Oxidation number of CI decreases from +1 to -1. A decrease in oxidation number is reduction.
( M - both elements correctly identified; £ - M plus decision justified appropriately and full
explanation given)
e. The claims are mostly valid, ie:
• Sodium hypochlorite does kill germs.
• Lavatory cleaners containing acid should not be used. The acid would react with the
hypochlorite to produce chlorine gas, which is toxic.

However, sodium hypochlorite in bleach decomposes/decays into NaCI (common salt) and
oxygen rather than water after killing germs:

2NaOCI 2NaCI + 0 2
(/W- partially discusses claim and links to chemistry accurately; £-fully discusses claim and
chemistry concepts are accurate)

Information for e. is provided throughout the question.

3. a. Yes. b. No. c. Yes. (A for all correct)

4. a. Cl2 + H 2 0 HCIO + H+ + Ch (M)

All reactants and products must be correct,

b. i. Thick, dense brown/orange gas forms. (A)

ii. Chlorine is such a powerful oxidising agent that iron is oxidised to Fe3+ rather than Fe2+.

Must recognise that chlorine is a strong oxidising agent. (M)

5. a. The paper turns a blue-black colour. (A)

b. The chlorine reacts with the iodide ions to produce iodine; the iodine reacts with starch to give a
blue-black colour. (M)
This occurs because chlorine is a stronger oxidising agent than iodine. Consequently, chlorine
oxidises the iodide ions to iodine:
21- + Cl2 l 2 + 2CI" (£)

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