NCEA LEVEL TWO CHEMISTRY REVISION GUIDE

2005 edition

Selected assessments with suggested answers

Really Useful Resources

REALLY USEFUL RESOURCES P.O. BOX 19-939 WOOLSTON CHRISTCHURCH N E W ZEALAND

ISBN (2005 edition)

1-877389-18-8

telephone fax e-mail website

(03) 377 4545 (03) 376 4545 rur@clear.net.nz http://www.rur.co.nz

COPYRIGHT 2005

Really Useful Resources Limited

All rights reserved. No part of this book may be reproduced, stored in a retrieval system, or transmitted, in any form or by any means, without the prior written permission of the copyright owner.

The writer gratefully acknowledges N Z Q A and the Sixth Form External Examination for their permission to reproduce past assessment questions.

The suggested solutions and notes are those of the author. NZQA and the Sixth Form External Examination take no responsibility for them.

Preface

This book is intended for students preparing for N C E A Level Two Chemistry. It includes a large number of appropriate assessments with suggested answers. There are useful hints included in both the question and answer sections to help students achieve with excellence.

The first section of the book is a series of questions in topic order following the seven achievement standards. The second section provides suggested answers with explanations. By practising questions based on each achievement standard, students will become more familiar with what is required.

Every effort has been made to make the revision guide consistent with the latest terminology and curriculum requirements. The 2005 edition takes into account the changes that arose from the 2004 review of the achievement standards. Obviously, we have tried to eliminate mistakes, but no doubt some remain so I apologise in advance for these. Please contact me if you dispute an answer. Constructive feedback is always welcome.

I sincerely thank the team who helped put the book together. They include Caroline Pau, Stephanie Woods, Anna Ferrier, Gabrielle Christenhusz, Helen Powell and Philip Arndt.

I sincerely hope that you will find this resource helpful and rewarding. I am sure that your results will improve with its use. Good luck in Chemistry this year and in the future, and I wish you every success in the NCEA Level 2 examination in November.

Gary Kennett Editor

25 January 2005

CONTENTS

Carry out Qualitative Analysis (AS90305)

Guidelines p 5

Perform an Acid-Base Volumetric Analysis (AS90306)

Guidelines p 6

Gravimetric or Colorimetric Analysis (AS90763)

Guidelines p7

Nature of Structure and Bonding (AS90308)

Questions p8 A n s w e r s and N o t e s p 6 5

Structure and Reactions of Organic Compounds (AS90309)

Questions p 2 0 A n s w e r s and N o t e s p 7 9

Principles of Chemical Reactivity (AS90310)

Questions p 3 6 A n s w e r s and N o t e s p 9 7

Oxidation-Reduction Reactions (AS90311)

Q u e s t i o n s p51 A n s w e r s and N o t e s p 110

Periodic Table at end of book Feedback and Order Forms

Copies at the b a c k of the book.

Qualitative Analysis (AS90305)

QUALITATIVE ANALYSIS (AS90305)

Carry out qualitative analysis (2.1) You will be expected to be able to: carry out procedures and use knowledge of precipitation reactions to determine ions present in solution. (3 credits - INTERNAL)

Key Points: 1. 2. A table of ions will not be provided. A procedure, such as a flow chart, to assist in determining the unknown ions will be provided. Solubility rules that are applicable will be provided. 3. Ions to be identified will be limited to: Ag+ , Al 3+ , Ba 2 + , Cu 2 + , Fe 2+ , Fe 3+ , Mg 2 ", Pb2+ N H / , Z n 2 t , , CO 3 2 ", I", NO3 , OH", and SO 4 2 ". Na + ,

Na+ and NO3" are identified by a

process of elimination. NH 4 + will be identified using its reaction with NaOH . 4. To gain Achievement the following will be required: Carry out given procedures to determine ions present in solution. Determination of the ions must be supported by experimental observations and identification of precipitates formed. This could include distinguishing between names pairs of anions or pairs of cations.

5.

To gain Achievement with Merit the following will be required: Carry out given procedures to determine ions present in solution, and justify the identification. Determination of the ions must be supported by experimental observations and identification of precipitates formed. Justification must include balanced equations for the reactions where precipitates are formed.

6.

To gain Achievement with Excellence the following will be required: Carry out given procedures, involving the formation of complex ion(s), to determine ions present in solution, and justify the identification. Justification must include balanced equations for the formation of complex ions. Complex ions may include FeSCN2+ and those formed when 0H"(aq) or NH3(aq) react with cations listed in 3. above, such as [Ag(NH 3 ) 2 ] + , [Al(OH)4]", Pb(OH)4]2", [Zn(OH)4]2", [Zn(NH 3 ) 4 ] 2+ , and [Cu(NH 3 ) 4 ] 2+ .

7.

The assessment task will be set by your teacher. It is not appropriate to provide sample tasks and answers for this achievement standard.

Acid-Base Volumetric Analysis (AS90306)

ACID-BASE VOLUMETRIC ANALYSIS (AS90306)

Carry out an acid-base volumetric analysis (2.2) You will be expected to be able to:

(3 credits - INTERNAL)

carry out an acid-base volumetric analysis using a given titration procedure.

Key points: 1. 2. 3. The titration procedure and balanced equation will be provided. The standard solution to be used in the titration will be provided. In solving volumetric problems, the titration data used may be that collected you, or that provided by your teacher. To gain Achievement you will be required to carry out an acid-base titration, and use titration data to calculate the concentration of a solution. At least two titre values must fall within a range of 0.4 mL. The average titre value must be within 0.8 mL of the expected outcome; The calculation must be carried out using an appropriate formula (not provided). Minor errors such as numerical errors or incorrect conversion of volumes will not be penalised.

4.

5.

To gain Achievement with Merit you will be required to carry out an acid-base titration with reasonable precision, and use titration data to correctly determine the concentration of a solution. At least three titre values must fall within a range of 0.4 mL. The average titre value must be within 0.5 mL of the expected outcome; A titration calculation must be carried out using only concordant titre values.

6.

To gain Achievement with Excellence you will be required to carry out an acid-base titration with high precision, and use titration data from a reaction where the stoichiometry is not one-to-one, to correctly determine the concentration of a solution. At least three titre values must fall within a range of 0.2 mL. The average titre value must be within 0.2 mL of the expected outcome; A titration calculation where the stoichiometry is not one-to-one must be carried out correctly using only concordant titre values. The final answer must have correct units and an appropriate number of significant figures.

7.

The assessment task will be set by your teacher. It is not appropriate to provide sample assessment tasks and answers for this achievement standard.

Quantitative Chemical Problems (AS90763) Q U A N T I T A T I V E C H E M I C A L P R O B L E M S (AS90763)

Solve simple quantitative chemical problems (2.3) You will be expected to be able to:

(2 credits - INTERNAL)

Solve simple quantitative chemical problems using the relationships

ancl c =

Key points: 1. To gain Achievement you will be required to solve simple quantitative problems. Solving simple quantitative problems may involve using the relationships n - and M = ^ to calculate one variable given the other two. Some problems may require you to 2. determine molar masses from given atomic masses and formulae. To gain Achievement with Merit you will be required to solve quantitative problems. You will be required to solve problems that require an application of the relationships n = and c = ^ . Example of suitable problems include: calculating % composition of a compound; determining empirical and molecular formulae; calculations involving determination of the mass of solid needed to prepare a given volume of a standard solution; determining, in moles, the amount of water removed on heating a sample of a hydrated salt to constant mass.

3.

To gain Achievement with Excellence you will be required to solve complex quantitative problems. Complex problems will typically involve more than two steps, and the use of stoichiometric principles. Examples could include: calculating the mass of a substance produced or consumed in a reaction given the mass of another reactant or product and the balanced equation; determining the number of waters of crystallisation in the formula of a hydrated salt; determining the concentration of a solution given titration data and the balanced equation.

4.

The assessment task will be set by your teacher. It is not appropriate to provide sample assessment tasks and answers for this achievement standard.

Structure and Bonding (AS90308) (AS90308)

S T R U C T U R E AND BONDING

Describe the nature of structure and bonding in different substances (2.4) (4 credits - EXTERNAL) You will be expected to be able to: describe bonding in simple molecules; describe the nature of various types of solids.

Key points: 1. Simple molecules have no more than four electron pairs about any atom (including multiplebonded species). You may be required to draw Lewis structures and determine shape and polarity. Types of solids are restricted to molecular, ionic, metallic and covalent networks. The nature of solids will be limited to the type of constituent particles (ions, atoms or molecules) and the attractive force between them (ionic, covalent or metallic bonds, or weak intermolecular forces). Properties of solids include electrical conductivity, melting point, and solubility in polar nad nonpolar solvents. To gain Achievement the following will be required: Describe the bonding in simple molecules and the nature of solids. A description requires you to identify, name, draw, and give characteristics, or an account of, the bonding.

2.

3.

4.

5.

To gain Achievement with Merit the following will be required: Link selected properties of simple molecules and different types of solids to their structure. To gain Achievement with Excellence the following will be required: Discuss properties of substances in terms of structure and bonding. A discussion requires you to show an understanding as to how or why something occurs by linking chemistry ideas/principles. It may involve you justifying, relating, evaluating, comparing, contrasting and/or analysing the nature or structure of bonding.

6.

QUESTION ONE

(Answerp65) - H

The Lewis structure for hydrogen chloride, HCl, is

Draw a Lewis structure for each of the following molecules. 1. 2. 3. 4. 5. CO2 PH3 CH2Cl2 H2CO F2O

Strucmre and Bonding (AS90308) QUESTION T W O (Answerp65)

For each of the following elements or compounds: (a) (b) (c) find the total number of valence electrons in the molecule;

draw a Lewis structure; give a name for the shape. 1. 2. 3. 4. 5. 6. 7. NH 3 H2O O2 BF 3 F2 Cl 2 O N2

QUESTION THREE (a)

(Answer p66)

For each of the following molecules: (i) (ii) (iii) 1. 2. 3. 4. name the shape of the molecule; draw a diagram to clearly illustrate the named shape; state whether the molecule is polar or non-polar. H2O SO 2 CCl 4 NCl 3

(b)

Explain why the molecules CCl 4 and NCl 3 are polar or non-polar (as described in your answer to (a) above).

QUESTION FOUR (Answer p67) For each of the Lewis structures below: (a) (b) (c) predict the shape of the molecule (by name or 3-D diagram); state whether the molecule is polar or non-polar; explain why the molecule is either polar or non-polar.

10

Structure and Bonding (AS90308)

I H-C-H I
H

2.

3.

: o = c = o :

H - N - H H

IF-S-FI

B I
IFt

H - C - F l IFI

QUESTION FIVE (Answer p68) When volcanoes erupt, a number of gases may be released. These include sulfur dioxide (SO 2 ), carbon dioxide (CO 2 ), hydrogen sulfide (H 2 S) and water vapour (H 2 O). At the surface, sulfur dioxide may also oxidise to form sulfur trioxide ( S O 3 ) . Complete the table below by: (a) (i) (ii) drawing a Lewis structure (electron dot diagram) for EACH of the formulae; naming the shape for CO 2 , H 2 S, and SO 3 Formula of molecule SO 2 CO 2 H2S H2O SO 3 bent or V-shaped (i) Lewis structure (ii) Name of shape

bent or V-shaped

Structure and Bonding (AS90308) (b)

11

State whether the molecules CO 2 and H 2 S from the table above are polar or non-polar. Explain your answers. (You may use Lewis diagrams in your explanation.) The shapes of SO2 and H 2 O molecules are both described as bent or V-shaped. The molecules are drawn below, with approximate bond angles shown.

(c)

O
120

H
109

Explain why the bond angles in these two molecules are different. (d) Following an eruption, lakes and streams become more acidic due to SO 2 dissolving in the water and reacting with it. Use the structure and bonding in H 2 O and SO2 to explain why SO2 is soluble in H 2 O.

QUESTION SIX (Answer p69) For each of the substances below: (a) (b) identify the type of solid it represents (metallic, ionic, molecular or extended covalent network); identify its name or formula (choose from magnesium chloride (MgCl 2 ), water (H 2 O), silicon dioxide (SiO 2 ), and silver (Ag). Solid Melting point ( 0 C) O Boiling point ( 0 C) 100 Conduct electricity? No Soluble in water? Yes Type of solid Name or formula

1.

2.

1700

2230

No

No

3.

961

2210

Yes

No Yes, and solution conducts electricity

4.

714

1418

No

12

Structure and Bonding (AS90308) (Answerp69) (SFEE)

QUESTION SEVEN

The table below gives some properties of chlorides of the period 3 elements sodium, magnesium, silicon, phosphorus and sulfur. Properties of the substances Melting point/C Boiling Pointz10C Electrical conductivity when solid Electrical conductivity when liquid pH of a water solution (a) Describe the bonding found in: (i) (ii) (b) (c) NaCl; SCi 2 . NaCl 801 1465 poor good 7 MgCl 2 714 1418 poor good 7 SiCl 4 -70 +58 poor poor <7 PCl 3 -92 76 poor poor <7 SCl2 -78 59 poor poor <7

Explain the difference in melting point between NaCl (+801 0 C) and SCl2 (-78C). Explain why MgCl 2 does not conduct electricity as a solid but does conduct electricity when liquid.

QUESTION E I G H T

(Answerp70)

Melting points of the chlorides of selected third-row elements are given in the table below. Name of substance sodium chloride magnesium chloride silicon chloride sulfur dichloride (a) (b) Formula NaCl MgCl 2 SiCl 4 SCl 2 Melting point ( C) 801 712 -68 -80

Describe the trend shown by the melting points of third-row chlorides in the table above. This trend in melting points is due to the type of bonding involved in each of the substances. For each of the substances below, describe the type of bonding that must be broken to melt the substance. Name of substance sodium chloride magnesium chloride silicon chloride sulfur dichloride Formula NaCl MgCl 2 SiCl 4 SCl2 Melting point (*C) 801 712 -68 -80 Type of bonding

13 QUESTION NINE (Answer p70) Complete the table below by: (a) (b) (c)

Structure and Bonding (AS90308)

identifying the type of particle in EACH solid as atoms or ions or molecules. naming the attractive force that is broken when EACH solid melts. stating whether the relative melting point of EACH solid is high or low.

Name of solid

Type of solid

(a) Type of particle in solid - atoms or ions or molecules

(b) Attractive force broken when solid melts

(C) Relative melting point - high or low

ice (H 2 O)

molecular

silicon dioxide (SiO 2 )

covalent network

iron (Fe)

metallic

potassium chloride (KCI)

ionic

QUESTION TEN

(Answerp70)

For each of the following solid substances: (a) (b) (c) state the type of particle found in the solid substance (atoms, ions or molecules). specify the attractive force that is broken when the solid substance melts. describe the attractive force existing between the particles of the solid as either weak or strong. 1. 2. 3. 4. Sulfur(Se) copper (Cu) magnesium oxide (MgO) diamond (C).

14

Structure and Bonding (AS90308) (Answerp71) (SFEE)

QUESTION ELEVEN (a)

Consider the compounds HCN and NH 3 (i) (ii) (iii) (iv) Draw the three-dimensional skeletal shapes of the compounds above. Name the shape. Give the approximate bond angle. State whether the molecule is polar or non polar.

(b)

Justify your choice of polarity for NH 3 above.

QUESTION TWELVE (Answerp71)

(SFEE)

Swimming pool water is constantly recirculated and filtered. The filtration takes out some of the pool debris, but chemical treatment is needed to remove the bacteria introduced by people's bodies. Without chemical treatment, the bacteria would thrive at pool water temperature, typically around 22C-25C. Chlorine (Cl 2 ) reacts with water to form hypochlorous acid (HOCl) as shown in the equation below: Cl i + H 2 O (a) (b) > H O C l + H t +Cl"

Draw a Lewis diagram (electron dot diagram) for H0C1. Explain the angular/bent shape of the HOCl molecule.

QUESTION THIRTEEN (a) (b)

(Answerp71)

(SFEE)

What name is used to describe diamond and graphite? Explain how you could account for the differences in physical properties, like electrical conductivity, between these two substances.

QUESTION FOURTEEN

(Answerp71)

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 Diamond Graphite Use(s) Used to make saws to cut marble Used as a solid lubricant in machinery Used to make electrodes

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

Structure and Bonding (AS90308) QUESTION FIFTEEN (Answerp72)

15

The elements in Group 17 of the period table are called halogens. (a) (i) Complete the table below to show the states of the first four halogens at room temperature (25C). Name of halogen fluorine chlorine bromine iodine (ii) Formula F2 Cl 2 Br2 I2 Melting point
0

Boiling point
0

State at 25C

-220 -101 -7 114

-188 -35 59 184 solid

Describe how the state of bromine at room temperature (25C) can be determined from the data given.

(b)

The table below shows three properties of iodine crystals (I2). Explain, in terms of the structure and bonding within the solid, why the solid has EACH of the properties stated. Property Iodine crystals will readily sublime (change from a solid to gas) when heated gently over a Bunsen burner. Iodine crystals are more soluble in cyclohexane than in water. Iodine crystals do not conduct electricity. Explanation in terms of structure and bonding within the solid

(c)

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

QUESTION SIXTEEN

(Answerp73)

For each of the following explain, in terms of structure and bonding within each solid, why the solid has the property describe: (a) Solid magnesium chloride (MgCl 2 ) is a poor conductor of electricity. magnesium chloride is a good electrical conductor. Chlorine (Cl 2 ) has a low melting point of - 1 0 . A piece of zinc (Zn) can be easily re-shaped without breaking into smaller pieces. However, when melted,

(b) (c)

16

Structure and Bonding (AS90308) (Answer p73) (SFEE)

QUESTION SEVENTEEN (a)

Draw Lewis diagrams of the following, indicating molecule shapes and bond angles. You will also need to correctly name each of the shapes and the predicted bond angle. HCN H 2 CO CF 4

(b)

The type of bonding found in the carbon tetrafluoride you have just drawn is different from that found in substances such as KBr or MgCl 2 . Discuss this statement with reference to two types of bonding. Substances which have bonding like that found in NaCl have very high melting points and they conduct when molten or while in aqueous solution. Explain this statement. HCN and CF 4 both contain polar bonds. Yet one is a polar molecule and the other is not. Explain both these statements.

(c)

(d)

QUESTION EIGHTEEN (a)

(Answer p74)

(SFEE)

Fill in the missing information on the table relating to bonding: Substance CaCl 2 NH 3 K Physical property Bonding type Other example

(b)

Compare the following terms: (i) (ii) (iii) Allotropes and isotopes, using carbon as an example; A polar bond and a polar molecule, using ammonia and methane as examples; Formation of an ion and an ionic bond.

QUESTION NINETEEN (a)

(Answerp74)

(SFEE)

Draw Lewis or Electron Dot Diagrams for the species below. Those which are in bold, the shape will need to be named, while the one in italics, the expected bond angle will need to be indicated. (i) CO 2 (ii) CH3CI (iii) PH 3

(b)

The electron arrangement of some elements is indicated below: X Y (i) (ii) 2,8,2 2,8,4

What type of bonding will Y most likely exhibit? What would the formula be if X and Y were to combine?

Structure and Bonding (AS90308) (c) Explain the following observations: (i)

17

Magnesium oxide and water are both compounds involving the element oxygen. Magnesium oxide is a solid of very high melting point and water is normally a liquid and, as ice, has a reasonably low melting point. Sand is predominately silica, SiO2; silica is characterised by its low solubility and reactivity. It can be melted only by heating to 1700C. Another group 14 oxide, carbon dioxide, does not exist naturally as a solid, and when frozen as 'dry ice' it readily sublimes at -78C. Carbon dioxide is more soluble and reactive than silica. The conductivity of glacial acetic acid is very low. When glacial acetic acid is diluted with water, the conductivity increases.

(ii)

(iii)

QUESTION TWENTY

(Answerp75)

Carbon and silicon are both elements found in Group 14 of the periodic table. Both elements show a combining power of +4 in forming oxides, with the respective formulae CO 2 and SiO 2 . Some of the properties of these oxides are as follows: Oxide CO 2 SiO2 Melting point ( 0 C) Sublimes at -78 1700 Conductivity of solid poor poor Hardness of solid brittle very hard

Discuss the structure and bonding within carbon dioxide and silicon dioxide, and relate these to the properties shown in the table above. QUESTION TWENTY-ONE (a) (Answerp75) (SFEE)

For each of the following facts, write a sentence of explanation: (i) (ii) (iii) Sulfur has a low melting point. Diamond is an extremely hard substance. Petrol does not dissolve in water.

Write a clear definition of: (i) (ii) an Ionic Bond: a Covalent Bond. (Answerp75) (SFEE)
( C H 3 C I ) .

QUESTION TWENTY-TWO (a) (b) (c)

Draw Lewis Diagrams or Electron Dot Diagrams for ethyne (C 2 H 2 ) and chloromethane Which of these molecules would have a dipole moment? (i.e. be polar)

What effect does molecular polarity have on the boiling point of a compound? Explain why it has this effect. Describe the shapes of the following molecules. (i) (ii) (iii) H 2 O. NH 3 . CO 2 .

(d)

18 (e) (f)

Structure and Bonding (AS90308) Explain why CO 2 is a non-polar molecule even though it has polar bonds. Write the formula of a compound which contains both ionic and covalent bonds (Answerp76) (SFEE)

QUESTION TWENTY-THREE

Use the periodic table at the back of the book. Select the correct element out of the first 36 elements (Hydrogen to Krypton) as answers to the following questions. In some cases more than one element will be correct: (a) (b) (c) (d) (e) (f) (g) Which element is stored under oil? Which element exists as a green gas? Which element forms both a 2+ and a 3+ ion? Which element forms a giant covalent network solid? Which element has the highest electronegativity? Which element has a cation with an electron configuration of 2,8? Which element is a liquid at room temperature? (Answerp76) (SFEE)

QUESTION TWENTY-FOUR

Some elements such as gold, lead and sulfur have been known for thousands of years but others have been recent discoveries. In fact, early attempts to draw up the Periodic Table of the Elements resulted in gaps where the particular elements had not yet been discovered. Imagine it is your task to find element number 37 (which we now know as Rubidium). Using your Periodic Table, describe two important properties of this element that could assist you in searching for it and identifying it. QUESTION TWENTY-FIVE (a) (Answerp77) (SFEE)

Use your knowledge of structure and bonding to explain the following properties: (i) (ii) (iii) (iv) Magnesium oxide has a very high melting point. Copper metal is malleable. Oxygen is a gas at room temperature. Silicon dioxide does not conduct electricity.

(b)

Some molecules contain polar bonds but are non-polar molecules. (i) (ii) Which of the following molecules would be an example of this? HCl NH 3 CO 2 H2O Explain why the molecule you have chosen has no overall polarity.

(c)

Phosphorus, like nitrogen, has five electrons in its valence shell. It forms a compound called phosphine (PH 3 ) by reacting with hydrogen. (i) (ii) (iii) Draw a Lewis structure (or electron dot diagram) for PH 3 Name the shape of this molecule. Which of the following solvents would you expect phosphine to be most soluble in? water cyclohexane petrol tetrachloromethane

19 Structure and Bonding (AS90308) (iv) Select from the following options to complete the two sentences below: strong (d) (i) (ii) weak intermolecular forces that are . forces that are intramolecular

Covalent bonds are Van der Waals forces are

Explain why solid sodium chloride acts as an electrical insulator but molten sodium chloride acts as a conductor, Draw a sequence of at least two labelled diagrams to show how particles in a crystal of sodium chloride dissolve in water. (Answerp78) (SFEE)

QUESTION TWENTY-SIX (a) (b)

Explain why neon (Ne) is a gas under room conditions but carbon (C) is a solid. The following table represents the arrangement of particles in different types of substances at certain temperatures and gives some properties of the substances. Some numbered gaps have been left. ooooooooooo Structural diagram
0000000000 OO

00
OO

ooooooooooo oooooooooo Metallic (b)(iv). Usually high Good conductor

o*o*o*o* o*o*o*o* o*o*o*o* o*oo*o (b)(ii). (b)(v). Very high Conducts when... (b)(viii).

0*0 (b)(i). o*o

0*0 o*o

Type of substance Example Melting point Electricity conductor

Molecular Air O j X v ONonconductor

Simple atomic Neon (b)(vii). Nonconductor

(b)(iii). Water Low Nonconductor

For (b)(i). to (b)(viii) above, give an appropriate answer to complete the table. (c) Under the conditions of very high pressure at the core of the planet Jupiter, hydrogen exists as a solid and is thought to have a lattice structure similar to Lithium. Explain a property that such solid hydrogen would show on Jupiter which solid hydrogen would not normally show on the Earth. In New Zealand, common chemicals around hot springs are sulfur (Sg rings) and hydrogen sulfide (H 2 S) gas. (i) Draw a Lewis structure (or electron-dot diagram) for hydrogen sulfide and name its shape. (ii) (iii) (iv) Draw a simple diagram for a sulfur molecule. What colour is sulfur under room conditions? Why is sulfur a solid and hydrogen a gas at 25 0 C and 1 atmosphere pressure? M/gmol ': ( H ) = 1 (S) = 32

(d)

Answers-Structural Formulae and Reactions (AS90309) 20 S T R U C T U R A L F O R M U L A E A N D R E A C T I O N S OF C O M P O U N D S (AS90309) Describe the structural formulae and reactions of compounds containing selected organic functional groups (2.5) (4 credits - EXTERNAL) You will be expected to be able to: describe structural formulae and reactions of formulae containing selected organic functional groups.

Key points: 1. 2. 3. 4. Naming of organic molecules is done according to IUPAC convention. Equations should be written using either names or structural formulae. When writing the structural formulae, either the condensed form or the expanded form is acceptable. Selected organic functional groups are limited to haloalkanes, alcohol, alkene, alkyne, ester, and carboxylic acid. Compounds are limited to those containing no more than eight carbon atoms. Larger organic molecules may be used in questions involving the linking of structure and reactivity. Isomerism is limited to structural and geometric (cis-trans) isomers. Knowledge of primary, secondary and tertiary classification of alcohols and haloalkanes is expected. Reactions are limited to: the addition reactions of alkenes with H2ZPt, Cl 2 , Br 2 , H 2 0/H + and HCl (including the identification of major and minor products on addition to asymmetric alkenes); 9. the reactions of alkenes with MnO4"; polymerisation of alkenes; halogenation of alkanes (limited to monosubstitution); oxidation of primary alcohols to form carboxylic acids; elimination of water from alcohols; acid reactions of carboxylic acids; formation of esters (may including triglycerides) from carboxylic acids and alcohols; hydrolysis of esters.

5. 6. 7. 8.

To gain Achievement the following will be required: Describe structures and reactions of organic compounds. A description requires you to identify, name, draw, and give characteristics, or an account of, the structures or reaction.

10.

To gain Achievement with Merit the following will be required: Link structure and reactivity of organic compounds.

11.

To gain Achievement with Excellence the following will be required: Discuss reactivity and structure of organic compounds. A discussion requires you to show an understanding as to how or why something occurs by linking chemistry ideas/principles. It may involve you justifying, relating, evaluating, comparing, contrasting and'or analysing the structure or reaction.

Structural Formulae and Reactions (AS90309) QUESTION ONE (Answerp79)

21

Complete the following table showing the structural formulae and IUPAC (systematic) names for some organic compounds. Structural formula (a) OH IUPAC name

I
CH 3 CH 2 CHCH 3 (b) CH 3 CHCH 2 Cl O

// C
OH

(c)

Methyl propanoate

(d)

2,4-dichlorobut-1 -ene

QUESTION TWO

(Answerp79)

(SFEE)

\ H H I O

I
H - C

I
C

H I
-C

H i l
H

H H i i
C C - H

I
H

I
H

I
H

l O-Hti

3.

(CH 3 ) 2 CHCH 2 CH j

4.
// CH, C \ OH 6.

CL
H

N
C = C \

/
H CH, C = C C H ,

/ H

Answers-Structural Formulae and Reactions (AS90309) 22 (a) Write the number of the compound above that is: (i) (ii) (iii) (b) an alkene; an ester; an alcohol.

Identify the compounds numbered 1. to 6. above.

QUESTION THREE

(Answerp80)

Vitamin C has the structure shown on the right. (a) On the molecule indicate the section that would readily react to decolourise bromine water. Two of the - O H groups in the molecule have been labelled as (A) and (B). Classify these - O H groups as primary, secondary or tertiary alcohol groups.
HO \ OH

(b)

QUESTION FOUR

(Answerp80)

Refer to the following compounds to answer questions (a)-(g) below.

CH 3 CH 2 CH 2 CH 2 OH

CH 3 CH=CHCH 3

HCOCH 2 CH 2 CH 3 O

A CH 3 CH 2 CH 2 CH 3

B CH 3 CH 2 CH 2 COH Il O E

C CH 3 C=CH 2 I CH 3 F

D (a) (b) (c) (d)

What type of alcohol is compound A? State the type of reaction that will change compound A to compound E. Describe what would be observed if compound E is added to sodium carbonate. Contrast the reactions of compound B and compound D with bromine. Include relevant observations and equations, and identify the type of reaction that occurs in EACH case. Explain what is meant by the term structural isomer. Use examples from the above compounds to illustrate your answer.

(e)

Answers-Structural Formulae and Reactions (AS90309) Compound B has two geometric isomers (cis and trans). Draw the TWO isomers. Compounds A, C and E are all colourless liquids. Describe tests that would identify EACH of these compounds if the labels were left off the bottles. Use the physical and chemical properties of these compounds to select suitable tests. Include any observations that would be made when carrying out these tests. Complete the table by writing: (i) (ii) the name of EACH functional group circled. the systematic name for EACH compound.

Compound

Name of functional group

Systematic name of the compound

3/\

/ Io J

CH 3 I CH 3 CCH 3

(^^2=23 CH 3

24

Structural Formulae and Reactions (AS90309) (SFEE)

QUESTIONTWENTY-SIX(Answer p94) The following flow diagram shows a series of reactions involving six carbon compounds.

(a)

Complete the table below by giving the structural formulae and naming the compounds involved. Compound A Structural Formula Name

D
CH 3

Il
CH 3

Answers-Structural Formulae and Reactions (AS90309)

Propanoic Acid

(b)

State the colour change that will occur in the mixture when C is converted to D. You need to state what the colour was originally and what it changed to. Give the name of the type of reaction that converts B into C. Predict the degree of solubility of compound A and B in water.

(c) (d)

QUESTION SIX

(Answerp83)

An unsaturated compound A, C 3 H 6 , reacts with water under acidic conditions to form two new products, B and C. Product B reacts with acidified potassium dichromate solution to form D. Product D reacts with a solution of sodium carbonate producing bubbles of gas. Product B reacts with D in the presence of sulfuric acid and compound E is formed. Compound E has a characteristic smell.

Identify the structural formula and name for each compound A, B, C, D and E.

26

Structural Formulae and Reactions (AS90309) (SFEE)

QUESTIONTWENTY-SIX(Answer p94)

Compound X is analysed and found to have the following percentage composition by mass: 38.40% carbon, 4.80% hydrogen and 56.8% chlorine. Compound X has molar mass of 125gmol"'. Relative atomic masses: H=I C = 12 Cl = 35.5 (a) (b) (c) Calculate the empirical formula of X. Determine the molecular formula of X. Compound X can exist as geometric isomers. Give the structural formula for a pair of geometric (cis-trans) isomers of X.

QUESTION E I G H T

(Answerp84)

(SFEE)

Hydrogenation is important commercially to convert unsaturated vegetable oils into solid margarine. When some of the unsaturated carbon bonds are hydrogenated, the melting point increases and the vegetable oil becomes a solid at room temperature. (a) (b) Explain what is meant by the term unsaturated. (i) Complete and balance the equation for the complete hydrogenation of pent-l,3-diene. CH 2 = CH - CH = CH - CH 3 + (ii) (c) H2 *

Give conditions and catalyst necessary for this reaction.

Complete and balance the equation for the complete combustion of pent-1,3-diene. CH 2 = CH - CH = CH CH 3 + 0, >

QUESTION NINE (a)

(Answerp85)

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. Propene can undergo other addition reactions, as given below. Complete the following equations, showing the structural formulae of the organic products. [For (ii), it is necessary to give BOTH of the possible organic products.] (i) CH 3 CH=CH 2
H 2 /Pt

(b)

H 2 0/H*

(")

CH 3 CH=CH 2

and

(iii)

Identify and explain which product in (ii) above is produced in the larger amount.

Structural Formulae and Reactions (AS90309) QUESTION TEN (Answerp85)

27

(SFEE)

Saponification is a process by which an animal fat such as glyceryl tristearate (a molecule containing three ester groups) can be hydrolysed by aqueous sodium hydroxide. The glyceryl tristearate is heated with a strong sodium hydroxide solution for a long time. (a) Complete the equation for the hydrolysis of the glyceryl tristearate molecule, giving the structural formula and the common or chemical name of product B. O
2

C-O-

C-(CH2)16CH3 H2C-OH I > HC-OH I H2C-OH

Il

O Il HC-O-C-(CH2)I6CH3+ O H
2

3NaOH(aq)

C-O-

C-(CH2)16CH3 glycerol (Product A) (Product B)

Il

(b)

Give one use for each of the products above. Glycerol: Product B:

(c)

When glycerol is heated, it decomposes to the aldehyde, acrolein. HCO HC H2C (i) (ii) What other substance is formed when glycerol decomposes to acrolein? Slowly, over time, a bottle of glycerol can become contaminated with acrolein. What chemical test could you perform to show the presence of acrolein? Give the reagent you would use and the result you would observe. Acrolein (Mr = 56) has a boiling point of 52.7C, while the corresponding alkene but-l-ene (Mr = 56) has a boiling point of -6.2C. Explain why acrolein has a higher boiling point than but-l-ene.

Ii

(iii)

Acrolein can undergo oxidation to form acrylic acid (propenoic acid) as shown below.
f0i

CH 2 = CH-CHO

>

CH 2 =CH-COOH

Acrylic acid is a very important industrial chemical and has a very pungent/acrid smell. It is used as a starting material to produce a number of important esters and polymers. (iv) Acrylic acid can undergo additional polymerisation. Draw a length of poly (acrylic acid) showing at least three monomer units linked together.

Answers-Structural Formulae and Reactions (AS90309) 28 QUESTION ELEVEN (Answerp86)

Two common polymers are polypropylene and polyvinyl chloride (PVC). A section of each polymer is shown in the table below. Draw the structural formula for the monomer molecule for each polymer. Section of the polymer (a) Polypropylene
CH2 CH CHI CH CH1 CH CHJ CH

Monomer molecule

/ l

/ l

I
,

CH,

CHJ

CH1

(b)

Polyvinyl chloride (PVC)

, CH CH CH1 CH CH2 CH CH2 \

I
CL

l
CL

l
CL

l
CL

QUESTION TWELVE (a) (b)

(Answerp86)

(SFEE)

Alcohols are an important group of organic molecules. What is the general formula of alcohols? Draw the structural formulae and name three isomers of the alcohol having the molecular formula
C 4 H 1 0 O .

(c)

Another form of isomerism involves the lack of free rotation around the C=C bond at room temperature. Draw the structural formula of /rans-but-2-ene. Alcohols may be produced industrially by a hydration (addition) reaction with an alkene in the presence of a catalyst such as dilute sulfuric acid. Write the balanced equation showing the formation of ethanol from ethene.

(d)

QUESTION THIRTEEN

(Answerp87)

(SFEE)

Carboxylic acids are a group of organic molecules which also contain oxygen atoms. They may also be used in the laboratory to produce esters. (a) What is the name of the ester drawn below?

CH

CHJ

(b) (c)

Name the alcohol and the carboxylic acid this ester was produced from. State what different physical or chemical properties you could use to distinguish clearly between separate samples of the alcohol, the carboxylic acid in (b) above and the ester in (a) above?

29 Structural Formulae and Reactions (AS90309) QUESTION TWENTY-SIX (Answer p94) (a) The flow diagram below may be useful to you in answering the following questions: (i) (ii) (iii) (iv) (v) (vi) Name the lettered substances of C and D. What is the general formula of the homologous family that compound B belongs to? Draw and name an isomer of compound D. In the reaction where compound D is produced from compound B, what conditions and reagents are necessary? What is the name of the process in which compound C is produced from compound A? Write the balanced equation for the formation of compound C from compound A. (SFEE)

(b) (c) (d) (e)

Define catenation. What is the electron configuration of carbon? What are 2 physical properties of the alkane C7H16? (i) (ii) Using structural formulae, write out the equation for the formation of propyl ethanoate. What is the name of the homologous family that this compound belongs to?

(f)

The formation of polyesters is a condensation reaction. Explain what is meant by this statement.

QUESTION FIFTEEN (a)

(Answer p88)

Draw the structural formula of the organic product in each of the following reactions, (i) OH CH3 + CH,CH, CH,OH

30

Structural Formulae and Reactions (AS90309) (ii)

CH CH,

HCI CH,

(iii)
CH
3

I
CH,

0 / H "

CH

(iv) H I
H - O - C H

H I I

H I
C - H

C H

CBO

2 7

" /

H~

(b) (c)

Name the functional group in each of the products of reactions (i) to (iv) above. Draw the structure of the major product formed when two molecules of HCl add to limonene (a substance found in citrus fruit).
CH,

HJC

CH

Limonene

1
H!C H1C T H

I
CH2 /

+ 2HC1

A
H,C CHi

QUESTION SIXTEEN

(Answer p89)

(SFEE)

Some of the reactions of ethanol are illustrated in the following flow chart. The reagents and conditions needed are written over the arrows. B&C

HT/Cr2O72

Cone. R S O , heat
2 4

CH3CH2OH
(a) (b) Write the formulae for the products , C, and D There are two possible products for A. Draw the structural formula for each product.

Answers-Structural Formulae and Reactions (AS90309) (c) Product D can be polymerised. (i) (ii) (d) Write the name of this polymer; Draw a structural formula for this polymer.

Explain why ethanol is very soluble in water.

QUESTION SEVENTEEN

(Answer p90)

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 a table that identifies the structural formula and name for EACH compound. (Hint: Begin with compound X, which is a straight chain molecule.)

QUESTION E I G H T E E N (a)

(Answerp91)

(SFEE)

Draw a structural formula for the primary, secondary and tertiary alcohol which all have the same molecular formula C 4 H 9 O H . In the homologous series what is the molar mass difference between any two consecutive numbers? Describe how you would distinguish between cyclohexane and cyclohexene using chemical tests. A student knows that three bottles which have lost their labels contain the following organic chemicals: Ethanoic acid, ethanol and ethyl ethanoate. Describe the simplest and quickest way you could decide what was in each bottle.

(b)

(c) (d)

32

Structural Formulae and Reactions (AS90309) (Answer p91)

QUESTION NINETEEN

Chemical test can be used to distinguish between pairs of compounds. Identify tests to distinguish between the following pairs of compounds shown below and: 1. 2. 3. describe the test to be carried out; describe the expected observations for the test used; clearly explain how the test results can be used to distinguish between the molecules in each pair of compounds and why the test used is a suitable one. butan-1 -ol and but-2-ene. butanoic acid and methylbutanoate. (Answer p91) (SFEE)

(a) (b)

QUESTION T W E N T Y

Crude oil is a complex mixture of hydrocarbon molecules. Many of these molecules belong to a homologous series called the Alkanes. The lowest members of the alkane series are gases and occur underground as a mixture called natural gas. (a) (b) (c) What is the meaning of the term hydrocarbon? Write the general formula of the alkane homologous series. What is the name and molecular formula of the alkane molecule in unrefined natural gas which has three carbon atoms in its molecule? One fraction of refined petroleum is called petrol. Petrol contains some alkane molecules with six carbon atoms in them. Draw TWO possible structural isomers of these alkane molecules.

(d)

QUESTION TWENTY-ONE (a) (b)

(Answer p92)

(SFEE)

Draw the structural formula of ethene. (i) (ii) Draw the structural formula of the substance formed when ethene reacts with bromine water. What type of organic reaction is this?

(c)

What observation would be made if the original reactants were compared to the final reaction mixture? (Answer p93) (SFEE)

QUESTION T W E N T Y - T W O

Lactic acid is an acid found in the body. The structural formula for lactic acid is shown below:

H-C
H

(a)

Draw a circle around the hydrogen atom that dissociates most easily from the molecule.

Structural Formulae and Reactions (AS90309) (b)

33

Suppose you wrote the formula for lactic acid as HLa. Using this shorthand for the formula, write the dissociation equation for this weak acid in water. Lactic acid contains two functional groups. One of these is called the carboxylic acid group. What is the name of the other functional group?

(c)

QUESTION TWENTY-THREE

(Answerp93)

(SFEE)

Analysis of aspirin tablets involves dissolving aspirin tablets in a known volume of standard sodium hydroxide. The following reaction takes place: 2NaOH(aq)+HOOCC6H4COOCH3(s) (a) (b) Name one of the products. Three bottles of organic liquids cyclohexene, ethanol and ethanoic acid have lost their labels. Using only aqueous solutions of bromine and sodium carbonate, explain how you could identify each chemical. * NaOOC6H,COH(aq)+CH3COONa(aq)

QUESTION TWENTY-FOUR (Answerp93) (a)

(SFEE)

Copy out the numbers A.(i) - A.(v) and write down the appropriate names or formulae which would complete the table below. Fuel Components (names and formulae) Name CNG LPG A.(i). A.(iii). Formula CH 4 A.(iv). and and Name A.(ii). Butane Formula C2H6 A.(v).

(b)

(i) (ii)

Explain what is meant by the term 'functional group' in organic chemistry. Give the names or formula of two different functional groups. homologous series). (Do not name the

QUESTION TWENTY-FIVE (Answer p94) (a) A compound of molecular formula C2H2CI2 can exist as cis-trans (geometrical) isomers. Draw, and name, the cis-trans isomers. There is another structural isomer of C2H2CI2 that cannot exist as cis-trans isomers. Draw the structural formula for this molecule and explain why this molecule cannot exist as cis-trans isomers while the one you have drawn above in (a) can.

(b)

34

Structural Formulae and Reactions (AS90309) (Answer p94) (SFEE)

QUESTION TWENTY-SIX

Study the flow chart diagram for the production of soap below and answer the questions following it.

(a) (b) (c) (d) (e) (f)

Give the formula for the two raw materials. Name another substance that could be used instead of sodium hydroxide. What type of reaction is Reaction 1? What is the role of the steam? What is reagent X? Give one use for glycerol. (Answerp95)

QUESTION TWENTY-SEVEN

Fats and oils are triester molecules. Hvdrolvsis of a fat can be represented bv the equation below. O Il CH 2 OC(CH 2 )I 6 CH 3 O Il CHOC(CH 2 )I 6 CH 3 O CH 2 OC(CH 2 )I 6 CH 3 O Il > 3CH 3 (CH 2 )i 6 CONa

3NaOH

Compound M

(a) (b)

Circle ONE of the ester groups in the fat. Write the name of the functional group that would be present in compound M.

Structural Formulae and Reactions (AS90309) Unsaturated fats are usually considered to be healthier than saturated fats. (c) (d) What is meant by the term unsaturated?

35

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. (Answerp95) (SFEE)

QUESTION TWENTY-EIGHT

Study the flow chart diagram for the production of margarine below and answer the questions following it. Substance X Sodium Hydrogen Hydroxide

Extraction and Heating

f V .

Commercial Margarine

Steam at 210 C

Additives (a) (i) (ii) (iii) (iv) (v) (vi) (b) What type of impurity is removed by adding sodium hydroxide? Identily substance X. What is meant by "volatile"? How does the steam treatment remove volatile impurities? Name the type of reaction involved for Treatment 2. Name two substances added to raw margarine to make commercial margarine.

Fats and oils are esters of long chain fatty acids and glycerol. (i) What is meant by "a long chain of fatty acid"? Use a diagram to illustrate your answer.

Oils are considered to be polyunsaturated. (ii) (c) (i) (ii) What is meant by the term "polyunsaturated"? Reducing sugars can be tested for by using Fehling's solutions A and B. Describe what colour change you would expect to see for a positive Fehling's test. What is the structural difference between soluble and insoluble starch?

Answers-Chemical Reactivity (AS90310) 36

CHEMICAL REACTIVITY (AS90310)

Describe thermochemical and equilibrium principles (2.6) You will be expected to be able to: understand the principles of chemical reactivity by describing and using simple thermochemical and equilibrium principles. (5 credits - EXTERNAL)

Key points: 1. Thermochemical principles are limited to: classification of reactions as exothermic or endothermic; determination of enthalpy changes; factors affecting rates of reaction - restricted to changes in concentration, temperature, surface area, and the presence of a catalyst.

2.

Equilibrium principles are limited to: dynamic nature of equilibrium and the effect of changes to the system. This is restricted to changes in temperature ( A r H given), concentration, pressure, or addition of a catalyst; equilibrium constant expressions for homogeneous systems and the significance of the magnitude K; the nature of acids and bases in terms of proton transfer; calculations involving Arii and pH; properties of aqueous solutions of strong and weak acids and bases including ionic species such as NH4+. The properties are restricted to conductivity, rate of reaction, and pH.

3.

To gain Achievement the following will be required: Describe thermochemical and equilibrium principles. A description requires you to identify, name, draw, and give characteristics, or an account of, the principles.

4.

To gain Achievement with Merit the following will be required: Interpret information about thermochemical and equilibrium principles. An interpretation requires you to provide reasons for how and why.

5.

To gain Achievement with Excellence the following will be required: Discuss information about thermochemical and equilibrium principles. A discussion requires you to show an understanding as to how or why something occurs by linking chemistry ideas/principles. It may involve you justifying, relating, evaluating, comparing, contrasting and/or analysing the thermochemical or equilibrium principle.

Chemical Reactivity (AS90310) QUESTION ONE (Answerp97)

37

(SFEE)

A commercially bought cold pack, which can be used for sports injuries, consists of a sealed outer plastic bag containing ammonium nitrate crystals and a thin inner plastic bag containing water. When the outer bag is bent and twisted, the inner bag breaks, allowing the ammonium nitrate crystals to come into contact with the water and the following dissolving takes place:
NH4NO3(S)

NH4+(aq)+N03"(aq)

AH = +25kJmol''

(a)

Which of the following are the most energetically stable species in the above dissolving process? (i) (ii) Reactants or products. Justify your answer.

(b)

If the outer bag contains 20g of ammonium nitrate, calculate the number of moles of ammonium nitrate present. Relative atomic masses: N = 14 H = I 0=16 Calculate the energy change caused by the dissolving of 20g of ammonium nitrate crystals. If the inner bag contains IOOmL of water, calculate the concentration of the resulting solution.

(c) (d)

QUESTION TWO (Answerp97)

(SFEE)

The curves shown below show the rate of production of hydrogen gas in various stated reactions. The curve labelled B involves the reaction between 20ml of ImolL 1 HCl and excess magnesium turnings at room temperature.

(a) (b)

Explain why excess magnesium turnings were used in each case. Match up the following reactions with the letter of a curve on the graph above. (i) (ii) (iii) 40mL of ImolL"1 HCl and excess magnesium turnings. 20mL of 2molL"' HCl and excess magnesium turnings. 20mL of 0.5molL'' HCl and excess magnesium turnings.

38 (c)

Chemical Reactivity (AS90310) A catalyst of Cu 2+ ions can be used to speed up the rate of reaction. Explain how a catalyst can increase the rate of reaction. Name two other variables, not mentioned above, that could also affect the rate of the reaction.

(d)

QUESTION THREE

(Answerp97)

A 1 g lump of calcium carbonate was added to a 250 mL beaker containing 100 mL of 1.0 molL 1 hydrochloric acid solution, at room temperature (25C). 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: Change 2: The temperature of the reaction mixture was increased to 40C. 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. The 1 g lump of calcium carbonate was ground to form a powdei, and then 100 mL of the 1.0 molL"1 hydrochloric acid was added. A 500 mL beaker was used instead of the 250 mL beaker, but the same amounts of reactants were used.

Change 3:

Change 4:

(b)

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

QUESTION FOUR (Answerp98) Consider a gas equilibrium reaction: reactants^) ~ productS(g) ~

(SFEE)

The following information for percentage conversion of reactants to products was obtained at different temperatures and pressures. The results are shown in the table below. Temperature 1.0 400C 600C 800C (a) State Le Chatelier's Principle. 15% 10% 5% Pressure/kPa 2.0 25% 20% 15% 3.0 35% 30% 25%

Answers (b)

Chemical Reactivity (AS90310)

39

Use the information in the table above to determine the correct equation below, which could represent the gaseous equilibrium. 1. 2. 3. 4. A(g)+B(g) < A(g)+B(g) 2($+2( v 2A(g)+2B(g) <
1

3C(g)+2D(g) 3 C(g)+2D(g) C(g)+2D(g) > C(g)+2D(g)

H i s positive AWis negative AH is positive H is negative

(c) (d)

For your chosen equilibrium in (b) above, write an expression for the equilibrium constant, Kc. For your chosen equilibrium equation in (b) above, use Le Chatelier's Principle to answer the following questions: (i) (ii) How would the equilibrium position be affected if extra reactant B was put into the reaction vessel? Explain. How would the equilibrium position be affected if the temperature of the reaction mixture decreased? Explain.

QUESTION FIVE (Answer p98)

(SFEE)

We may use chemicals in our everyday lives - cleaners, medicines, foods etc. Sulfuric acid is used in car batteries, sodium hydroxide is the active ingredient in drain cleaners, iodine is the active ingredient in Betadine and the ethanoic acid is present in vinegar. Sulfuric acid is produced by the Contact Process which involves, in the final stage, the addition of water to oleum, H 2 S 2 O 7 , as shown in the equation below.
H 2 S 2 0 7 (l)+H 2 0(l) > 2H 1 SO 4 (I)

(a)

What mass of the sulfuric acid can be obtained when 8.9g of oleum is reacted with excess water? Relative atomic mass: 0 = 1 6 S = 32 H=I If the mass of sulfuric acid in (a) above is dissolved in IOOOmL of water, a solution of concentration 0.1 molL' 1 is formed. Calculate the pH of this solution. A 25mL quantity of a different drain cleaner fluid, with a concentration of 5.5molL'' sodium hydroxide, is added to 50mL of hydrochloric acid of concentration 3.OmolL"1. (i) (ii) (iii) (iv) Write an equation for the reaction between sodium hydroxide and hydrochloric acid. Calculate the number of moles of sodium hydroxide in 25mL of the drain cleaner fluid of concentration 5.5molL"'. Calculate the number of moles of hydrochloric acid in 50mL of 3.OmolL acid. Calculate the pH of the final mixture.
1

(b)

(c)

hydrochloric

40

Chemical Reactivity (AS90310) (Answerp99) (SFEE)

QUESTION SIX

Consider the equilibrium equation for the conversion of SO2 to SO3 in the Contact Process:
2S0 2 (g)+0 2 (g> 2SO,(g>

AH = - 1 OOkJmol

(a) (b)

Write the equilibrium expression for this reaction: Kc = In this industrial process, both vanadium catalysts, as VO3" or vanadium pentoxide Explain how a catalyst works in a chemical reaction.
V 2 O 5

are used.

(c)

What effect do catalysts have on the equilibrium position for the formation of sulfur trioxide? Explain your answer carefully. Explain two factors which would increase the production of sulfur trioxide. Justify your answer with reference to Le Chatelier's Principles. IfATc = 2300 at 400C, what does this tell you about the relative concentrations of SO 2 and SO 3 in this reaction? (AnswerplOO) (SFEE)

(d)

(e)

QUESTION SEVEN (a)

On a graph, draw and label an energy diagram for the production of sulfur trioxide. Show reactants, products, activation energy and energy change. The x-axis is labelled Reaction Coordinate, and the>>-axis is labelled Enthalpy. If 1500 tonnes of SO 3 are produced, how many moles of oxygen are consumed'' What would be the value of AH in the above reaction producing 1500 tonnes of SO 3 ? (AnswerplOO)

(b) (c)

QUESTION EIGHT

Classify EACH of the following processes as either endothermic or exothermic. (a) (b) (c) (d) (e) H 2( g)+'/20 2 (g) - H 2 O te , ArH= -286 kJ mol"1.

Photosynthesis - food-making process in plants. Freezing of water. Dissolving sodium hydroxide in water (the temperature increases). Sublimation of solid carbon dioxide to carbon dioxide gas.

Chemical Reactivity (AS90310) QUESTION NINE (Answer plO1)

41

Octane is a key component in petrol, and burns according to the following equation: C8Hmo + 12^02(g) (a) (b) 8C0 2 ( g ) + 9H 2 O 0 ) A1H = - 5 5 0 0 kJmol"1

Explain whether burning octane is an exothermic or endothermic reaction. 1.00 litre of octane contains 6.12 moles of the fuel. Calculate the energy released when 1 litre of the fuel is burnt. Using hydrogen gas (H 2 ) as a fuel for cars, rather than octane, is viewed as better for the environment. Calculate the mass of H 2 required to produce the same amount of energy as 1.00 litre of octane, as calculated in (b) above. State your answer to three significant figures. + | o 2 ( g ) H20(g) ArH = - 2 8 6 kJmol-1

(c)

QUESTION TEN

(AnswerplOl)

Hydrogen peroxide, a common bleaching agent, decomposes as follows: H 2 O 20 ) (a) (b) H 2 Q m + ArH= -98.2 kJmol" 1

Calculate how much energy is released when 5 moles of hydrogen peroxide decompose. Calculate how much energy is released when 1.0 g of oxygen is formed by the decomposition of hydrogen peroxide. Calculate the mass of hydrogen peroxide that must decompose to produce 600 kJ of energy. (AnswerplOl) (SFEE)

(c)

QUESTION ELEVEN (a) (b)

Define an acid, in terms of the Bronsted-Lowry definition. Hydrochloric acid can be described as a strong acid, whereas ethanoic acid is described as a weak acid. Explain this statement. Calculate the pH of a hydrochloric acid solution that has a concentration of 0.14molL~'. (Answerpi02)

(c)

QUESTION TWELVE

The pH of a 0.10 mol L 1 solution of acid HX and the pH of a 0.10 mol L"1 solution of acid HY are measured. The pH of acid HX is 3 and the pH of acid HY is 1. (a) (b) (c) Which of the two acids, HX or HY, is the stronger acid? Justify your answer to (a) in terms of the measured pH. Describe another 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.

Answers-Chemical Reactivity (AS90310) 42 QUESTION T H I R T E E N (Answerpi02)

(CH..CH2COOH),

Two acids of the same concentration, hydrochloric acid (HCl) and propanoic acid properties as shown below: Property Relative conductivity of solution pH of solution (a) Hydrochloric acid (0.100 molL"1) High

have

Propanoic acid (0.100 molL"1) Low

1.00

2.93

Complete the following equations to show the reaction of both hydrochloric acid and propanoic acid with water. HCl+H2O CH 3 CH 2 COOH + H 2 O ^ + +

(b)

Explain the differences in the conductivity and pH of the two acids. In your explanation include reference to the species present in each solution.

QUESTION FOURTEEN

(Answerpi02)

(SFEE)

When hard water is boiled in a jug, over time a deposit of calcium carbonate (scale > will form on the bottom and sides of the jug. This can be removed at home using vinegar. Sam decides to take a more analytical approach and brings an old metal jug into chemistry class. He determines the jug contains 4.5g of calcium carbonate. He decides to use 0.50molL"' hydrochloric acid to dissolve the scale. (a) (b) Write a balanced equation for the reaction Sam is carrying out. List an acid-base conjugate pair in the following equation: HCO ^H 1 O* - H 2 CO+H 2 O (c) (d) (e) How many moles of calcium carbonate has Sam estimated to be in the jug? What volume of hydrochloric acid will Sam need to use? In the laboratory, we often use sodium carbonate to prepare a standard solution. sodium carbonate be preferable to calcium carbonate? Why would

QUESTION FIFTEEN

(AnswerplOi)

(SFEE)

Four colourless solutions were investigated by pupils and the following data was obtained for them: Solution A - pH = 7 and no reaction with HCl; Solution B - pH = 13 and neutralised with HCl; Solution C - pH = 9 and fizzed when HCl added: Solution D - pH = 11 with a strong odour. Neutralised with HCl.

Answers-Chemical Reactivity (AS90310) The teacher told the students that the names of the 0.1 molL"' solutions were amongst the following list of chemicals: Water; Ammonia; Potassium hydroxide; Ethanoic acid; Sodium chloride; Sodium bicarbonate; Sulfuric acid; Ammonium chloride; Copper nitrate.

Mary identified them as follows: (a) Solution A - copper nitrate; Solution B - potassium hydroxide; Solution C - sodium bicarbonate; Solution D - ammonium chloride.

The teacher said that Mary had made two mistakes. Identify the ones she got wrong and select the correct solutions to replace them. Write an equation which shows why the pH of solution D i s 11. List one other solution that you think could qualify for being solution A. Write an equation which describes the reaction that happens when a few drops of pure sulfuric acid are added to water. (Answerpi03) (SFEE) Using

(b) (c) (d)

QUESTION SIXTEEN (a)

When carbon dioxide is bubbled through water the solution becomes slightly acidic. appropriate equations explain how this acidity is caused. (i) (ii) Write the equation for the reaction of the weak acid
C H 3 C O O H

(b)

with water,

Write the acid equilibrium constant expression (Ka) for this equilibrium. (Answerp 103)

QUESTION SEVENTEEN

Write the equilibrium constant expression for EACH of the following reactions: (a) (b) (c) 2S0 2 ( g , + 0 2 ( g ) =*==* 2S0 3 ( g ) 4NH 3(g) + 5 0 CH3COOH,.,,, < 4NO, gl + 6H 2 0 ( g ) ir ( a i l ) CH j COO
laq ,

44

Chemical Reactivity (AS90310) (Answerpi04) (SFEE)

QUESTION EIGHTEEN

Using your knowledge of the collision theory, explain the following observations: (a) Fine sawdust (wood) powder suspended in the air in saw mills can lead to explosions if it is accidentally sparked. Magnesium metal burns more vigorously in oxygen than it does in air. A mixture of oxygen gas and hydrogen gas will not react, but if a spark enters the mixture they react explosively.

(b) (c)

QUESTION NINETEEN

(Answer p 104)

The reaction between 20.0mL of 0.500 molL"1 hydrochloric acid and 20.0mL of 0.250 molL"1 sodium thiosulfate solution at room temperature (25C) produces a precipitate of sulfur that makes the solution go cloudy after about 5 minutes. (a) How would the time taken for the solution to go cloudy be affected if the reaction were carried out in a water bath at a temperature of 50 C ? (b) With reference to the collisions of particles, explain why the reaction is affected in this way.

QUESTION TWENTY

(Answer p 104)

(SFEE)

Sketch an appropriate energy diagram for an endothermic reaction that has a significant activation energy. Add to your diagram (using a different colour pen) the change made to it when a catalyst is used to help the reaction. Label your diagram clearly.

QUESTION TWENTY-ONE

(Answerpi04)

(SFEE)

When a solution containing iron III ions (Fe 3+ ) is added to a solution containing thiocyanate ions (SCN") at room temperature, a blood red product forms. The product is a complex ion with formula [FeSCN] 2+ . The test tube and its contents showed a slight increase in temperature during the reaction. (a) (b) Write the equilibrium equation for this reaction. Describe what you would observe, and explain why it happens, if more iron III ions are added to the original mixture.

QUESTION TWENTY-TWO

(Answerp 104)

(SFEE)

What effect does increasing the temperature of an equilibrium reaction have on: (a) (b) The speed of the forward reaction? The speed of the reverse reaction?

Chemical Reactivity (AS90310) QUESTION T W E N T Y - T H R E E For the gaseous reaction, 2NO, (Answerpi05)

45

(SFEE)

* \ ' ; 0 4 , explain what the effect would be of increasing the pressure.

QUESTION TWENTY-FOUR

(Answerpi05)

(SFEE)

A sample of stomach acid (HCl) was tested with universal indicator paper and gave a pH reading of 2. (a) (b) (c) (d) Would you classify HCl as a strong or weak acid? Write the equation for the dissociation of HCl in water. Assuming the pH of the acid is 2, determine its hydrogen ion concentration. Use your answer in (c) to determine what the concentration of hydrochloric acid is in your stomach.

QUESTION TWENTY-FIVE

(AnswerplOS)

(SFEE)

A student was investigating the reaction between two chemicals X and Y. In the reaction a colourless gas was produced which turned lime-water milky. The volume of gas production was recorded at regular time intervals giving a measure of the rate of reaction. The reaction was repeated using a different concentration of X but the same original concentration of Y and the results recorded below. Concentration of X = 0.5molL Volume of gas produced (mL) Time taken (s) Concentration of X = 0.2 moll/ 1 Volume of gas produced (mL) Time taken (s) (a) (b) (c) (d) (e) (f) 0 0 7 10 14 20 20 30 25 40 28 50 29 60 30 70 30 80 0 0 9 10 18 20 24 30 28 40 30 50 30 60 30 70 30 80

What is the most obvious conclusion that can be drawn from these results? What is the name of the gas produced? What is the chemical name for lime-water? Which of the two chemicals, X or Y is in excess? Why does the reaction rate slow down as each reaction proceeds? Chemical Z was added to the mixture and it increased the rate of the reaction. If Z was acting as a true catalyst, state TWO things about the way it works. (i) (ii) How would the rate of reaction between X and Y change if the temperature was increased? Explain why the higher temperature causes this change.

(g)

46

Chemical Reactivity (AS90310) (AnswerplOS) (SFEE)

QUESTION TWENTY-SIX

In New Zealand ammonia is produced on an industrial scale by reacting nitrogen gas with hydrogen gas as shown in the equation below. N2(g)+3H,(g) * (a) (b) (c) (d) 2NH,(g) ArH = - 9 2 k J m o r ' (of reactants as shown)

What name is given to this industrial process? Is a high or low industrial pressure used for this process? From the information provided, how do you know that the production of ammonia is exothermic? What effect on the amount of ammonia produced does: (i) (ii) adding a catalyst have? increasing the concentration of hydrogen have?

The graph below shows the effects of pressure and temperature on % yield of ammonia. (The pressures shown are 600, 300, 200, 100, 50 and 10 atmospheres.)

Effects of Pressure and Temperature on the Percentage Yield of Ammonia

- 600atm - 300atm - 200atm - 1 OOatm - 50atm - IOatm

350

400

450

500

550

600 C

650

700

750

Temperature

(e) (f) (g) (h)

What is the % yield for the process at 350C and 300 atmospheres? Why is the process carried out at 450C despite greater yields at lower temperahires? How is the overall efficiency of the entire process increased? If 28,000kg of nitrogen gas is introduced into the reaction chamber, what mass of ammonia would be formed (assuming the conversion was 15% efficient)? (Mgmol"': (N) = 14, (H) = 1)

Chemical Reactivity (AS90310) QUESTION TWENTY-SEVEN (a) (Answerpi06)

47

(SFEE)

Shown below are three possible fuels for car engines. Values for their molar mass (M/gmol 1 ) and the energy released on complete combustion (as kJmol"1 and kJg"1) are also shown: Fuel Molar mass/ gmol"1 Hydrogen H2 Methanol CH 3 OH Octane CgH i8 (i) (ii) (iii) 2 32 128 Energy of combustion kJmor 1 285 755 6118 kJg'
X

23.6 47.8

Calculate x - the maximum energy (in kj) that could be released on burning Ig of hydrogen. Why is hydrogen not commonly used as a fuel for cars? Assuming that the total energy efficiency of burning l.Og of octane in car engines is 15%, how efficient must the burning of l.Og of methanol be to release the same amount of energy? (Hint - compare the amounts of energy released on burning Ig of each fuel.)

(b)

Consider the following possible exhaust products from car engines: H2O (i) (ii) (iii) CO CO 2 SO2

Which is/are poisonous? Which cause(s) global warming? Which gas is a reactant in the catalyst converter used in many car exhaust systems?

QUESTION TWENTY-EIGHT (a)

(Answerpi06)

(SFEE)

Methanol can be produced commercially by reacting hydrogen with carbon monoxide.

C O ( g ) + 2 H 2 ( g ) - CH3OH(g)

(i) (ii)

Write out the equilibrium expression for this reaction: Kc Using Le Chatelier's Principle and the information supplied above, outline two factors which would favour the production of methanol.

(b)

Methanol undergoes complete combustion in oxygen, yielding 360kJ mol"1. (i) (ii) (iii) (iv) Write out the balanced chemical equation for this reaction. Is this reaction exothermic or endothermic? Draw and label an energy graph showing this combustion reaction. For every tonne of methanol produced, what mass of hydrogen gas must be supplied? Choose a

(c)

Explain one possible method for increasing the rate of the following reactions. different method in each case: (i) (ii) A large cube of zinc is added to 0.1 molL"1 of hydrochloric acid; Hydrogen peroxide spontaneously decomposes to water and oxygen.

Answers-Chemical Reactivity (AS90310) 48 QUESTION TWENTY-NINE (Answerpi07)

Two oxides of nitrogen exist in the following equilibrium system: 2N02(g) v ^ N2O4(Q) ArH = - 5 7 k J m o r ' and Kc = 6 . 3 * 1 0 " ' at227C

(a)

Which oxide (NO: or N2O4) would you expect to be present in the greater concentration at equilibrium? Justify your answer to (a) above.
N O 2

(b) (c)

is a brown gas and N 2 O 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. The temperature is increased to 500C (without changing the pressure). More NO 2 gas is added to the system.

(i) (ii)

QUESTION THIRTY (a)

(Answerpi08)

The following equilibrium system is established when thiocyanate ions (SCN'i are added to iron (III) ions (Fe ). The resulting aqueous solution is a dark red colour. The equation representing the equilibrium system and the colours of each species involved are given below. Fe 3 + ( a q ) + SCN
pale orange
(aq)

^FeSCN2
dark red

colourless

(i) (ii)

Complete the equilibrium constant expression (Kc) for the above reaction. When iron (III) ions (Fe 3 ') are removed from the equilibrium mixture (by adding sodium fluoride), a colour change is observed. Describe the colour change you would expect to see and explain why it occurs.

(b)

Ammonia is produced industrially according to the Haber process as shown below: N 2(g) + 3 H 2 ( g ) ^ 2 N H 3 ( g ) (i) (ii) Complete the equilibrium constant expression (ATc) for the above reaction. The pressure of the system at equilibrium is increased (by decreasing the total volume of the system). Describe the effect of this change on the amount of NH 3 in the system. answer. (iii) Explain you

The percentage of NH3 present in equilibrium mixtures at different temperatures and at constant pressure is shown in the table below. Temperature ( 0 C ) 200 300 400 500 Percentage NH 3 present in equilibrium mixture 63.6 27.4 8.7 2.9

Justify whether the reaction in which NH 3 is formed, is endothermic or exothermic.

Chemical Reactivity (AS90310) QUESTION THIRTY-ONE HC0 3

(a4)

49

(Answerpi08)

is a species that may act as an acid or a base . Consider the equilibrium system:
" H2C03(aq)+0H"(aq)

HC03(aq)+H20(l)

(a) (b)

Is HC03"(aq) acting as an acid or a base? Justify your answer to (a) above.

QUESTION THIRTY-TWO

(Answer pi 08)

Chickens make egg shell, CaCO 3 , using carbon dioxide gas from the air. The carbon dioxide forms carbonic acid (H 2 CO 3 ), which then reacts to form the carbonate ions (CO 3 2 ') needed to make egg shell. Two equations showing part of this process are given below. Equation 1: Equation 2: (a) (b) H 2 C0 3 ( a q ) + H 2 O ffl ^ HC0 3 ~ (aq) + H2O,;, ^ HC0 3 " ( a q ) + H 3 0 + ( a q ) C032
(aq)

- ,0,

Identify three conjugate acid-base pairs in the equations above. HCO3" can act as both an acid and a base. Specify which equation above (Equation 1 or 2) shows HCO3" acting as an acid. Give a reason for your answer.

QUESTION THIRTY-THREE

(Answer

pi09)

A sample of solid ammonium chloride, NH 4 CI 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.

QUESTION THIRTY-FOUR

(Answerpi09)

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.

* = [H 3 O + ] [OH ] =1.00 x IO"14 Solution A B [H 3 O + ] / mol L 1 [OH ] / mol L"1 0.0288 5.24 pH

Answers-Chemical Reactivity (AS90310) 50 QUESTION THIRTY-FIVE (a) (Answerpi09) Each solution contains both hydronium ions

The table below shows four different solutions. (H 3 O + ) and hydroxide ions (OH").

Complete the table, showing the relative concentrations of these two ions in solution, by placing H 3 O + ions and OH" ions in the appropriate box. The first one has been done for you. Solution Concentration OfH 3 O + and OH" in solution Greaterthan IxlO 7molL"' Na 2 CO 3 0.1 OOmolL 1 HNO 3 0.100 molL"1 NaOH 0.100 molL"1 NH 4 Cl 0.100 molL"1 (b) Calculate the pH of a solution with a hydronium ion concentration, [H 3 O + ], of 0.0350 molL"1. State your answer to three significant figures. If a solution of sodium hydrogen carbonate has a pH of 9.20, calculate the concentration of hydroxide ions, [OH ], present in the solution. State your answer to three significant figures. Kw = LOOxlO' 14 OH Less than IxlO 7InolL"1 H3O+

(c)

51Answers-Oxidation-Reduction Reactions (AS90311)

OXIDATION-REDUCTION REACTIONS (AS90311)

Describe oxidation-reduction reactions (2.7) You will be expected to be able to describe oxidation-reduction reactions. (3 credits - EXTERNAL)

Key points: 1. Knowledge of appearance and state of the following reactants and their products is required. 2. Oxidants are limited to O 2 ,1 2 , Cl,, H' Fe 3 *, H 2 O 1 , MnO4 Iaq) / F f , Cr,072"(aq) /H + ; Reductants are limited to metals, C , CO, H , , Fe 2+ , Br , r , SO 2 , (HSO,~); Appropriate information relating to any other oxidants or reductants will be provided.

Aspects of oxidation-reduction include: determine oxidation numbers; write balanced oxidation-reduction equations; identify oxidants and/or reductants; recognise the ability of halogens to act as oxidants in reactions with other elements, water or halide ions.

3.

Oxidation-reduction reactions may be assessed in the context of simple electrolytic cells. Knowledge of preferential discharge is not required. To gain Achievement the following will be required: Describe oxidation-reduction reactions. A description requires you to identify, name, draw, and give characteristics, or an account of, the reactions.

4.

5.

To gain Achievement with Merit the following will be required: Apply oxidation-reduction reactions.

6.

To gain Achievement with Excellence the following will be required: Discuss oxidation-reduction reactions. A discussion requires you to show an understanding as to how or why something occurs by linking chemistry ideas/principles. It may involve you justifying, relating, evaluating, comparing, contrasting and/or analysing oxidation-reduction reactions.

52

Oxidation-Reduction Reactions (AS90311) (AnswerpllO) (SFEE)

QUESTION ONE

Hypochlorous acid (HOCl) is a weak acid. The hypochlorous acid reacts with ammonia (which can come from swimmers' urine) in a redox reaction to produce chloramine: NH +HOCl Give the oxidation state of the following atoms: (a) (b) Oxidation state of chlorine in: HOClandNH 2 Cl: (NB: NH 2 Cl = -I). Oxidation state of nitrogen in: NH 3 and NH 2 Cl. (AnswerpllO) > NH2CH-H2O

QUESTION T W O (a)

Write the oxidation number of the underlined element in each of the following species. (i) (ii) (iii) (iv) (v) Mn 2+ H2O2 Br2 SO 2 CO Use the

(b)

Two oxidation-reduction reactions were carried out and the observations recorded. information provided to answer the questions that follow. Reaction One Reactants Acidified hydrogen peroxide, H2O2caq) and bromide ions in solution, Br"(aq). (i) (ii) Identify the species oxidised and the species reduced in the above reaction. Use oxidation-reduction processes to explain why the solution goes orange. Observation

Both reactant solutions were colourless but when added together an orange colour was observed.

Reaction Two Reactants Chlorine gas, 1, was bubbled into a solution containing iron (II) ions, Fe2+(aq) (iii) Observation The pale green solution changed to a pale orange colour.

Explain this observation in terms of oxidation-reduction processes.

Oxidation-Reduction Reactions (AS90311) QUESTION T H R E E (AnswerpllO)

53

(SFEE)

Chlorine can be used to remove other impurities in the swimming pool water besides bacteria. Some metal ions such as Fe 2+ , can discolour the water and cause staining of the pool area. These can be removed as solids when the recirculating water passes through the filters. d+6H,0+2Fe2" (a) (b) (c) (d) What species is the precipitate? What colour is the precipitate? The chlorine has undergone either oxidation or reduction. Choose one and justify your answer. C b can be reacted with aqueous sodium hydroxide to form the bleaching agent sodium hypochlorite. Write a balanced equation for this reaction. > 2Cl"+2Fe(OH) 3 +6H'

QUESTION FOUR (Answerplll)

(SFEE)

Tablets containing a small quantity of potassium permanganate can be used to sterilise water supplies when you are camping in areas where the water is not treated. The quantity of potassium permanganate (KMnO 4 ) in the tablets can be determined by titration with a colourless solution of standardised sodium oxalate (Na 2 C 2 O 4 ). (a) (b) (c) Write the half reaction for the reduction of the permanganate ion under acid conditions. Write the half reaction for the oxidation of the oxalate ion to carbon dioxide. Combine the two half reactions above to write the overall redox reaction between the acidified permanganate ion and the oxalate ion.

QUESTION FIVE

(Answerplll)

When sulfur dioxide gas (SO 2 ) is bubbled into a solution of acidified potassium dichromate solution, a colour change is observed. The unbalanced equation for this reaction is given below. Cr 2 O 7 2- + SO 2 -> SO42" + Cr 3+ (a) (b) (c) Identify the reductant in this reaction. Justify your answer using oxidation numbers. Write balanced half-equations for the oxidation and reduction reactions that occur. Combine the half-equations in (b) to give the balanced equation for this oxidation-reduction reaction. Describe the observations that would be expected when this reaction occurs. expected observations by referring to the species involved in the reaction. Explain these

(d)

54

Oxidation-Reduction Reactions (AS90311) (Answerplll)

QUESTION SIX

Iodine (I2) can be produced from the reaction between potassium iodate (KIO 3 ) and potassium iodide (KI). The iodide ions (I") and iodate ions (IO3 ) react together to form the iodine (I2). (a) Iodide ions (I") and iodate ions (IO3 ) both contain the element iodine (I), but in two different oxidation states. What is the oxidation number of iodine (I) in each species? Identify the oxidant and reductant in this reaction. Complete and balance the half-equations for the reactions of iodide ions (I") and iodate ions (IO 3 ) forming iodine (I2). : IO3": (d) IO 3 I2 I2

(b) (c)

Combine these two half-equations to give a balanced equation for the reaction.

QUESTION SEVEN

(Answerpi

12)

(SFEE)

Electrolysis is a very important industrial process and has many applications for extractions and purification of metals, electroplating and the production of other important chemicals. (a) For the electrolysis of the following substances, complete the table by giving the product formed at the anode and the product formed at the cathode. Product at positive anode Cone, sodium chloride solution Molten lead bromide Dilute sulfuric acid (b) (i) (ii) Bromine Product at negative cathode Hydrogen

Write an equation for the reaction that occurs at the negative cathode in the electrolysis of the concentrated sodium chloride solution. Write an equation for the reaction that occurs at the positive anode in the electrolysis of lead bromide.

(c)

In the membrane cell for the electrolysis of sodium chloride solution, a third commercially important product is produced. This product is not directly given off at the anode or the cathode. Give the name or formula of the product.

QUESTION E I G H T

(Answerpi

12)

(SFEE)

Redox reactions are occurring all around you, and inside you. Combustion of fuels is a redox reaction. Write a balanced equation for the complete combustion of propane.

Oxidation-Reduction Reactions (AS90311) QUESTION NINE (Answer pi 12)

55

(SFEE)

Acidified potassium permanganate may be used in the laboratory to oxidise iron (II) to iron (III). The permanganate is reduced to manganese (II) ions. (a) (b) (c) What name would you give to the potassium ions in this reaction? Explain your answer. Write a balanced equation for the above reaction, using the ion-electron half equation method. What is the oxidation number of sulfur in: (i) (ii) (d) sulfate ion? sulfur dioxide?

Some alcohols may be oxidised readily. Dichromate ions may be used to oxidise butan-l-ol. Write the balanced ion-electron half equation for the oxidation of butan-l-ol to butanoic acid. Write out the balanced ion-electron half equation involving the ion responsible for the colour change you would observe in the above reaction. Now write out the complete balanced equation for this reaction.

(e)

(f)

QUESTION TEN (Answerpi

13)

(SFEE)

Electrolysis is an important industrial process used to reduce metals or to plate other metals. In the laboratory, we can demonstrate this process using a power source, an electrolyte, and electrodes with suitable glassware and connectors. (a) (b) Explain what an electrolyte is. The electrolysis of magnesium from seawater involves, in its final step, the use of molten magnesium chloride. Write out the redox reaction which occurs at the anode.

QUESTION ELEVEN

(Answerpi

13)

(SFEE)

A student decides to investigate electroplating for her practical investigation. In her initial experiments, she copper plates some iron nails. Draw and label a diagram showing how she might set up her experiment in a beaker. Be sure to include in your drawing: A power source; An electrolyte - state what she will use; Suitable electrodes (including the nail); Be sure to label the cathode and anode.

56

Oxidation-Reduction Reactions (AS90311) (Answerpi 13) (SFEE)

QUESTION TWELVE (a) (b)

Magnesium metal is combusted in excess oxygen. Explain why this is a redox reaction. Silver plates can 'tarnish' after time. The tamish (Ag 2 S) is caused from sulfur and sulfur compounds in the atmosphere and foods. (i) (ii) (iii) Write out the balanced half-equation for the oxidation reaction above. Write out the balanced half-equation for the reduction reaction above. Write the completely balanced redox equation for this reaction.

(c)

In the breath-alyzer test, ethanol is oxidised to ethanoic acid by acidified dichromate. The police officer looks for a colour change to verify his suspicions. What are the colours of the following ions - Cr2O?2 and Cr 3+ .

(d)

(i) (ii) (iii)

Write out the balanced half-equation for the oxidation of ethanol by dichromate. Write out the balanced half-equation for the reduction of dichromate by ethanol. Write the balanced equation for this reaction, using your two half equations.

(e)

Metal ores can be reduced by chemical means, for example, reducing copper from copper sulfate. Electrolysis usually is the only method to reduce very reactive metals such as magnesium. (i) (ii) (iii) Why, then, is electrolysis the method used to reduce aluminium? In New Zealand, most of the raw product is shipped to the South Island for electrolysis. What is the name of the raw material, and where is its place of origin? Indicate on the following electrolytic cell where the anode, and cathode are found.

(iv) (v) (vi) (vii)

Indicate on the diagram above where the reduction occurs in the electrolysis. Give one important use for the aluminium produced. Explain what physical property of aluminium allows for the use outlined in (v) above? Give another example of a physical property of aluminium.

Oxidation-Reduction Reactions (AS90311) QUESTION T H I R T E E N (AnswerplN)

57

(SFEE)

A 5.Og sample of brass (an alloy of zinc and copper) was reacted with concentrated nitric acid in a fume cupboard. A brown gas was generated, and the resulting solution was a green colour. The cooled solution was mixed with sodium hydroxide and a blue precipitate was filtered off. After drying, this precipitate was found to have a mass of 4.95g, and was heated in a crucible over a Bunsen burner. The resulting black solid was weighed and the resultant mass was 4.05g. (a) (b) (c) (d) What is the name of the brown gas generated? What is the name, and symbol, of the ion resulting in the green colour of the solution? This reaction is an example of a redox reaction. What is the oxidation half-equation? Write the balanced reduction half equation.

QUESTION FOURTEEN

(AnswerplH)

(SFEE)

When a piece of copper metal is placed into a solution of silver nitrate, a deposit forms on the surface of the copper.
copper '-'

Silver nitrate solution

_ _ deposit on surface of the copper

(a) (b) (c) (d) (e)

Describe one other observation you would make as the reaction proceeded over a period of time. Write the ion-electron half equation for the redox reaction taking place. Write the overall ionic equation for the reaction. Write down the oxidation state of each element present in silver nitrate. (Ag, N and 0 ) In this reaction between copper and silver nitrate identify which species is acting as the oxidant (oxidising agent) and which is acting as the reductant (reducing agent). In another redox reaction, a greenish coloured gas was bubbled through a solution of potassium iodide in a fume cupboard and the solution turned brown. What is the brown coloured chemical produced by this reaction?

(f)

58

Oxidation-Reduction Reactions (AS90311) (Answerpi 15)

QUESTION FIFTEEN

Chlorine is made industrially by the electrolysis of brine, a concentrated solution of sodium chloride. A simplified diagram of the cell is shown below.

(a) (b)

Label the anode and the cathode clearly in the dashed boxes on the diagram above. The two half-reactions occurring in the cell are shown below. Complete and balance the equation for Reaction Two. Reaction One: Reaction Two: 2 H 2 0 + 2e" - 2 0 H +H 2 Cl 2 >

(c)

Gases are produced at each electrode as the electrolysis proceeds. Identify which gas (Gas A or Gas B) in the diagram above is chlorine. Justify your choice by discussing the reactions that occur during electrolysis, the electrodes where these reactions occur, and the products that are formed.

QUESTION SIXTEEN

(Answerpi

15)

(SFEE)

Hydrated magnesium chloride is crystallised from MgCl 2 solution. It is heated and then mixed with some sodium chloride and calcium chloride before being electrolysed. The mixture is heated sufficiently to

(b)

Using the terms, left hand electrode or right hand electrode, state which of them is the anode.

Oxidation-Reduction Reactions (AS90311) (c) (d) (e) Magnesium will be produced by one electrode. Which one? Write the ion-electron half equation for the reaction occurring at the other electrode.

59

Suggest a reason why the electrolysis is carried out at a temperature high enough to melt the magnesium chloride. Graphite electrodes obviously conduct electricity. Suggest another reason why they are used.

(f)

QUESTION SEVENTEEN

(Answerpi

16)

(SFEE)

When iron is extracted from magnetite, scrap iron consisting of such things as old car bodies, structural steel and railway lines is added towards the end of the process. Obviously, some of this scrap iron is rusty and the rust is converted back to iron in the process. The formula for rust is Fe 2 O 3 and the chemical that causes it to change back into iron is carbon monoxide gas. (a) (b) (c) Write an equation for the reaction which takes place. What are the oxidation states of iron and oxygen in Fe 2 O 3 ? State one reason why the reaction works only at high temperatures.

A MCEA Level 2 Chemistry student came up with a novel way of recycling scrap iron. He suggested that the scrap should be put into a bath containing sulfuric acid which would dissolve out both the iron and its oxides and leave behind any other materials to be filtered off and discarded. (d) (e) Assuming there was both iron and iron (III) oxide in the scrap, write balanced equations for the two reactions which would occur with the sulfuric acid. The solution resulting from the acid treatment of the scrap contained sulfates of iron. The student suggested that the solution could be reacted with magnesium metal to form iron. (i) (ii) (iii) (iv) (v) Write an ion-electron half equation showing what would happen to the magnesium metal in this reaction. Write a similar half equation showing what would happen to Fe 2+ ions in this reaction. Add these two half equations together to make an ionic redox equation. Which metal, magnesium or iron, is the stronger reducing agent? Suggest TWO reasons why this student's recycling process would not be a good economic proposition.

(f)

One of the reactions in (d) produces a gaseous by-product. The student suggested this by-product could be used to make hydrochloric acid by reacting it with chlorine gas. Write a balanced equation for his proposed reaction.

Another student, after hearing of this novel approach to recycling, suggested that it might be used to reclaim other important elements from their oxides. Her list of possible oxides was: ZnO (g) (h) CuO SiO 2 SO2

Select one from her list which would react in the required way with the sulfuric acid. Choose one of the four oxides which will not work and explain why.

60

Oxidation-Reduction Reactions (AS90311) (Answer pi 17) (SFEE)

QUESTION E I G H T E E N

The following oxidation-reduction reaction was carried out in the laboratory. Iron (II) sulfate solution was added to acidified potassium permanganate solution. For this reaction: (a) (b) (c) What colour is potassium permanganate solution? Explain why the potassium permanganate needs to be acidified. Write the half equation for the oxidation of the iron (Il) ions.

QUESTION NINETEEN

(Answerpi

17)

(SFEE)

H'lh
Electrode B

/
Electrode A Electrolyte solution

- h

(a)

(i) (ii) (iii) (iv)

Do cations in the electrolyte move towards electrode A or B? Name an electrolyte other than NaCl. At which electrode does oxidation occur? Name the electrodes, A and B.

(b)

If A and B are made of graphite and the electrolyte is concentrated sodium chloride solution, write the half equation representing what takes place; (i) (ii) At electrode A; At electrode B. Complete the diagram of the following electroplating cell by drawing a spoon at the electrode you wish to plate with copper metal.

(c)

(i)

(ii) (iii)

Draw and label what the other electrode should be made of. Add a label showing what solution you would use.

Oxidation-Reduction Reactions (AS90311) QUESTION T W E N T Y (Answer pi 17)

61

(SFEE)

Read the following passage on fuel cells and answer the questions which follow. A fuel cell directly reacts a fuel such as hydrogen with an oxidant such as oxygen to produce electrical energy. The chemicals are supplied continuously and the electrical energy is generated under control for as long as the raw materials are supplied. In the fuel cell used on some space-craft such as the Space Shuttle, hydrogen gas is supplied to one electrode and oxygen gas to the other electrode, as shown in the diagram below.
hydrogen gas

At the negative electrode, hydrogen reacts with aqueous hydroxide ions to form water and releasing electrons. At the positive electrode, oxygen gas removes electrons for the nickel electrode and reacts with water to regenerate the hydroxide ions. To generate electricity, fuels cells are much more efficient than combustion reactions because chemical energy is converted directly into electrical energy. Combustion reactions are used to convert chemical energy to heat energy to mechanical energy and then to electrical energy. Fuel cells using other fuels such as methanol (CH 3 OH) and hydrazine (N 2 H 4 ) have been developed. The advantages of fuel cells is that they are mostly pollution free, noiseless and produce a high energy return, but disadvantages include their expense and in some cases the toxicity of the fuels (i.e. hydrazine). (a) (b) (c) (d) (e) Suggest a label for Y on the diagram. Accurately name the oxidant and reductant. Write ion-electron equations of the two half reactions. Give an overall balanced equation for the overall fuel cell reaction. Why are fuel cells a more efficient method of converting chemical energy into electrical energy than a generator involving combustion and dynamos? Explain one advantage this fuel cell would have over lead accumulator batteries for space flights.

(f)

QUESTION TWENTY-ONE

(Answerpi

18)

(SFEE)

When using certain reagents in the laboratory, some chemicals must be acidified. (a) (b) Identify two such chemicals which must be acidified. Name precisely the acid that is used to acidify these chemicals and give the reason why this acid is chosen.

62

Oxidation-Reduction Reactions (AS90311) (Answerpi 18) (SFEE)

QUESTION T W E N T Y - T W O

Aluminium metal is extracted from aluminium oxide ore shipped into Bluff from Australia. (a) To extract and purify the aluminium oxide from the ore, sodium hydroxide solution is needed. What property of the aluminium oxide allows this method of extraction and purification?

Shown below is a simple diagram of the electrolytic cell used in the extraction of aluminium.
solid crust graphite anode (+) carbon cathode (-) lining the ceil molten aiuminia dissolved in cryolite steel casing molten aluminium flows out through tap hole

(b)

Write an ion-electron equation for each electrode reaction, identifying the electrode and the products. Explain the function of the cryolite (Na 3 AlF 6 ) used in the electrolysis. (Answerpi 18)

(c)

QUESTION TWENTY-THREE

When acidified potassium permanganate solution is added to freshly prepared iron(II) nitrate solution, a reaction occurs. The unbalanced equation is shown below: MnO 4 ' + Fe 2+ (a) (b) (c) (d) Fe 3+ + Mn 2+

Is the MnO 4 ' ion oxidised or reduced? Use oxidation numbers to justify your answer. Identify the oxidant and reductant in the reaction above. Write balanced equations for the oxidation and reduction half reactions. Combine the half equations in (c) to give the balanced equation for this oxidation-reduction reaction. Clearly describe what would be observed when this reaction is carried out, linking the observations to the species involved in the reaction. Complete the table below for EACH combination of species. Species to be mixed Does a reaction occur? (yes/no) I f a reaction occurs, describe what would be observed. If a reaction occurs, write a balanced equation for the reaction.

(e)

(f)

(i)

Ch(aq) + B r

(aq)

(ii) Cl ( a q )

h(aq)

Oxidation-Reduction Reactions (AS90311) QUESTION TWENTY-FOUR (Answerpi 19)

63

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, I2, to produce sulfate and iodide ions. (a) What is the oxidation number of sulfur in EACH of the following? (i) (ii) (b) SO 2 SO42"

Write ion-electron half equations for the oxidation and reduction reactions occurring between SO 2 and I2. Combine the half equations in (b) above to form a balanced equation. 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.)

(c) (d)

QUESTION TWENTY-FIVE

(Answerpi

19)

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) S o W crust of
ETORTROLYTE K O H I S O H

top

Tapping hole

Steei tank witft carbon (graphite) lining

Molten Gteclrolyte consisting of aluminium oxide dissolved in cryolite

Molten aluminium is tapped oft at intervals

(a)

On the diagram above: (i) (ii) clearly label the anode and the cathode. show the direction of movement of ions in the electrolyte.

(b)

Write balanced half equations for the reactions occurring at: (i) (ii) the positive electrode. the negative electrode.

64 ()

Oxidation-Reduction Reactions (AS90311) 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. (Answer pi20)

QUESTION TWENTY-SIX

An electrolytic cell can be used for electroplating. Electroplating is a process where a metal object is coated with a thin layer of another metal. This process is shown in the diagram below. The spoon is electroplated with silver metal and the silver electrode gets smaller. Power supply

silver metal electrode

Ag I

spoon

Using principles of electrolytic cells, discuss how the layer of silver is plated onto the spoon. Include relevant oxidation-reduction half equations in your discussion. QUESTION TWENTY-SEVEN (Answerpi20)

Sodium hypochlorite, NaOCl, reacts with hydrochloric acid to give sodium chloride (NaCl) and chlorine gas (Cl 2 ). It is the reaction between the and ions that produces the chlorine gas. (a) What are the oxidation states of the chlorine in EACH of the following species? (i) (ii) (iii) (b) OCl" ClCl 2

Write balanced ion-electron half equations for the formation of chlorine, Cl 2 , from: (i) (ii) chloride ion (). hypochlorite ion (OCl ).

(c)

Identity the reaction in part (b) above that is an oxidation reaction, and give reasons for your answer. If warmed, or left to stand, a solution of sodium hypochlorite decomposes as follows: 2NaOCl 2NaCl + O 2 Justify your

(d)

Clearly identify the element that is being oxidised and the one being reduced. decision.

Answers - Structure and Bonding (AS90308)

65

STRUCTURE AND BONDING (AS90308)

We have chosen not to identify each 'answer' as 'achieved', 'merit' or 'excellence'. Students who wish to do so can determine the 'level' by referring back to the standard specified at the beginning of the 'question' chapter. QUESTION ONE (Question p8)

I- CO 2

c = < 5

H-P-H I H

3. CH 2 Cl 2

H-cSb I "
H

4. H 2 CO

5 f

-^ O

?-"-?
WNN

QUESTION TWO (Question p9) Formula of element or compound 1. NH 3 Total number of valence electrons in molecule 8 Lewis structure H-N-H I H Name of shape Trigonal Pyramid or triangular pyramid Bent (planar) 'O Hx 4H 12
4

2.

H2O

or V-shaped Linear

3.

O2

Answers - Structure and Bonding (AS90308) 66 Trigonal planar or I

I t F

m
5. F2

24

triangular planar

14

M M
IF -

M aa

Fl

Linear

[Should be drawn 'bent')

6.

Cl 2 O

20

ICI O C l l

Bent

7.

N2

10

IN =

NI

Linear

QUESTION THREE (a) Molecule H2O

(Questionp9)

Shape Bent / V-shaped / angular 'o* ' 4H

Polar or Non-polar Polar

SO 2

Bent / V-shaped / angular

Polar

M CCl 4

M Non-polar

Tetrahedral ICIt ICI C

"

ICIl m

Sil "

NCl 3

Triangular Pyramid ICI N C l l M M ICII M

Polar

Answers - Structure and Bonding (AS90308) (b) 1. 2.

67

It has four polar bonds but its tetrahedral shape means that the molecule is symmetrical and so the bond dipoles (or polarity) cancel. Therefore, CCl 4 is non-polar. It has three polar bonds and is not a symmetrical shape (since the nitrogen has non-bonding valence electrons) and so the bond dipoles cannot cancel. Therefore, NCl 3 is polar.

QUESTION FOUR Lewis structure 1.

H

(Question p9) Shape Tetrahedral Polarity Non-Polar Explanation 4 polar bonds; Tetrahedral shapes means molecule is symmetrical. Bond dipoles cancel. Atoms of electronegativity; No polar bonds. similar

I
H - C - H

I
H

2. Linear 3.
: = c = o : 4. H - N - H

Non-polar

Linear Trigonal pyramid or triangular pyramid

Non-polar

2 double bonds (polar); Molecule is symmetrical. Bond dipoles cancel. 3 polar bonds; Shape is not symmetrical due to lone pair of electrons. Bond dipoles do not cancel. 2 polar bonds; Not symmetrical molecule. Bond dipoles do not cancel. 3 polar bonds; Symmetrical molecule. Bond dipoles cancel.

Polar

I
H

5.
F-

S -

Fl

Bent (planar) or V-shaped Trigonal planar or triangular planar

Polar

6.
'F4

Non-polar

%-BI
SFt

M 7. I~l I I
I I F

Tetrahedral ~

Polar (slightly)

H - C - F l

4 polar bonds; Shape is slightly unsymmetrical due to different bond dipoles. C is more strongly attracted to F than H. Bond dipoles do not cancel. 3 polar bonds; Not a symmetrical shape. Bond dipoles do not cancel.

8.
ClPCll

Trigonal pyramid or triangular pyramid

Polar

ICIt

Answers - Structure and Bonding (AS90308) 68 QUESTION FIVE (Question plO) (a) Formula of molecule (i) Lewis structure (ii) Name of shape

SO 2 W W

bent or V-shaped

CO 2

= =

linear

H2S

H m

bent or V-shaped

(should be drawn bent)

H2O H'

bent or V-shaped
4

SO 3

Si J =
S - S i

triangular planar / trigonal planar

(other structures are possible; could draw S without electrons)

(b)

CO 2 is a non-polar molecule. CO 2 contains polar bonds as atoms have different electronegativity, but the molecule is symmetrical due to the double bonds. This means that the bond dipoles cancel. H 2 S is a polar molecule. H 2 S contains polar bonds and the molecule is not symmetrical. This means that the bond dipoles do not cancel.

(c)

SO2 has three regions of electron density (clouds) around the S and repulsion results in a bond angle of 120. H 2 O has four regions of electron density (clouds) resulting in a bond angle of 109". The greater repulsion means O atoms are further apart in the SO2 molecule and hence are less bent. SO2 and H ; 0 are both polar molecules because they contain polar bonds. They don't have symmetry to cancel the dipoles because their central atoms have non-bonding valence electrons. Since "like dissolves like" SO2 is soluble in H 2 O. Furthermore, hydrogen atoms can form between the oxygen atoms in SO2 and the hydrogen atoms in H 2 O, increasing the solubility of SO2 in H 2 O.

(d)

Answers - Structure and Bonding (AS90308) QUESTION SIX (Question pi 1)

69

Solid

Melting point ( 0 C) 0

Boiling point ( 0 C) 100

Conduct electricity? No

Soluble in water? Yes

Type of solid Molecular

Name or formula H2O (water)

1.

2.

1700

2230

No

No

Covalent network

SiO2 (silicon dioxide)

3.

961

2210

Yes

No

Metallic

Ag (silver)

4.

714

1418

No

Yes and solution conducts electricity

Ionic

MgCl j (magnesium chloride)

QUESTION SEVEN (a) (i) (ii) (b)

(Question pi2)

(SFEE)

NaCl is made up of Na + and Cl" ions with strong electrostatic forces of attraction/ionic bonds between them. The S and Cl share electrons to complete valence levels in a covalent bond.

NaCl: strong ionic bonds hold the ions together, therefore lots of energy is needed to overcome them. This means a high melting point of 801 0 C. SCl 2 : weak forces of attraction between molecules, therefore less energy is required to overcome them. This means a lower melting point of-78C.

(c)

As a solid, the ions are fixed in space and cannot move, therefore cannot conduct electricity. As a liquid the ions are free to move and therefore can conduct electricity.

70

Answers - Structure and Bonding (AS90308) (Question pl2)

QUESTION E I G H T (a)

The melting point decreases across the row (from left to right), with a significant decrease from Mg to Si.

(b) Name of substance sodium chloride magnesium chloride silicon chloride sulfur dichloride Formula NaCl MgCl 2 SiCl 4 SCl2 Melting point ('C) 801 712 -68 -80 Type of bonding Ionic bonding Ionic bonding covalent covalent

QUESTION NINE

(Questionp!3)

Name of solid

Type of solid

(a) Type of particle in solid - atoms or ions or molecules molecules

(b) Attractive force broken when solid melts van der waals forces / hydrogen bonds

(c) Relative melting point - high or low

ice (H 2 O)

molecular

low

silicon dioxide (SiO 2 )

covalent network

molecules

covalent bonds

high

iron (Fe)

metallic

atoms

metallic bonding

high

potassium chloride (KCI)

ionic

ions

ionic bonding

high

QUESTION TEN

(Question

pl3)
T y p e of particle in solid Attractive force broken w h e n solid melts A t t r a c t i v e f o r c e between particles

N a m e of solid s u b s t a n c e

Sulftir (S 8 ) Copper (Cu) Magnesium oxide (MgO) Diamond (C)

molecules atoms ions atoms

van der Waals metallic bonding ionic bonding covalent

weak strong strong strong

Answers - Structure and Bonding (AS90308) QUESTION ELEVEN (Question pi 4) (a) HCN (i) Skeletal Shape
H-C =
NI

71

(SFEE)

NH 3 (i) Skeletal Shape

H - N - H

I H (ii) Name of shape: Linear (iii) Approx bond angle: 180 (iv) Polar or non polar: polar (b) One of the following points is required: the bond dipoles do not cancel out; vector addition of the bond forces gives a non-zero resultant. (ii) Name of shape: Trigonal pyramid (iii) Approx bond angle: 109 (iv) Polar or non polar: polar

QUESTION TWELVE (Question pl4) (a)

(SFEE)

(b)

There are 4 groups of electrons around the central oxygen atom. Due to e -e" repulsion, they go towards the corners of a tetrahedron. Since two positions are occupied by lone (non-bonding) pairs, the shape is bent.

QUESTION THIRTEEN (Question pi4) (a) (b) Allotropes.

(SFEE)

Bonding - diamonds are made up of C atoms covalently bonded to 4 other C atoms forming a strong 3-D network. No free e" - no conductivity. Graphite has a 2-D structure made of layers of covalently bonded C atoms with delocalised 4,h e' holding layers loosely together via Van der Waals forces. The 4th e" is free to conduct.

QUESTION FOURTEEN (Question pi4) In diamond, each carbon atom forms single bonds with four adjacent carbon atoms at the corners of a tetrahedron. This results in a rigid, covalent, three-dimensional structure that makes diamond the hardest known substance. Because diamond is so rigid and hard it can be used to cut other very hard substances, such as marble.

Answers - Structure and Bonding (AS90308) 72 Graphite consists of layers of two-dimensional carbon sheets. Each layer is made up of six-member rings, and these rings have mobile electrons attached to them. The presence of mobile electrons means that graphite is a good conductor of electricity and can be used to make electrodes. Also, although there are weak van der Waals forces, there is still a relatively significant gap between the layers. This gap makes graphite slippery and makes it suitable as a lubricant.

QUESTION FIFTEEN (a) (i)

(Question

pi5)

Name of halogen fluorine chlorine bromine iodine (ii)

Formula F2 Cl 2 Br2

Melting point
0

Boiling point
0

State at 25C gas gas liquid solid

-220 -101 -7 114

-188 -35 59 184

Its melting point is - 7 C so at 2 5 C it has melted from a solid to a liquid. Its boiling point is 59 0 C so at 25 C it has not yet boiled to become a gas. Therefore at room temperature bromine is a liquid.

(b)

Property

Explanation in terms of structure and bonding within the solid

I2 molecules contain a covalent bond. However, during sublimation it is the intermolecular forces that break. Iodine crystals will readily sublime These are very' weak van der Waal's instantaneous dipole (change from a solid to gas) when attractions since I2 molecules are non-polar. Therefore heated gently over a Bunsen burner. the attractions are easily broken so sublimation occurs at low temperatures. I2 is non-polar since it contains two identical atoms. Iodine crystals are more soluble in Water is polar and cyclohexane is non-polar. Since "like dissolves like" I2 is more soluble in cyclohexane than cyclohexane than in water. water. Iodine crystals electricity. do not In order to conduct electricity there must be mobile ions conduct or electrons. I2 molecules have neither of these since they are covalently bonded I atoms, are discrete molecules and are not ionic. Therefore they do not conduct electricity.

(c)

MgCl 2 is ionic so has ionic bonds (both intermolecular and intramolecular forces) between molecules and ions (i.e. forms an ionic lattice when solid). It is ionic because it contains a metal bonded to a non-metal. SCl 2 is covalently bonded between the S and Cl atoms (intramolecular forces). This is because S and Cl are both non-metals. Between the molecules (intermolecular forces) are instantaneous dipole weak van der WaaIs attractions.

Answers - Structure and Bonding (AS90308) QUESTION SIXTEEN (a) (Question pi5)

73

Solid magnesium chloride (MgCl 2 ) is a poor conductor of electricity. However, when melted, magnesium chloride is a good electrical conductor. Solid magnesium chloride is an ionic solid. In this state the ions are held in fixed positions but when melted the ions are free to migrate (due to increased energy) ad so are free to conduct electricity.

(b)

Chlorine (Cl 2 ) has a low melting point of - C . Chlorine is a covalent, molecular substance. The attractive forces between molecules (van der Waals) are weak and so require little energy to be broken.

(c)

A piece of zinc (Zn) can be easily re-shaped without breaking into smaller pieces. Zinc is held together by non-directional, attractive forces between an array of positive ions and a sea of electrons. Its shape can be changed without disrupting the forces.

QUESTION SEVENTEEN (a) HCN

(Question pi6)

(SFEE)

H,CO
Hx

CF4 X X * Q
1

" c ! ; o* ; s : N:
*

Sc x^

I/1

H OR: OR: H > = < 5

H

Xr-X V>

OR:
H - C = NI

l"l

. m

I F - C - I I

I m IFI m

Name of Shape: Linear PredictedBondAngle: 180 (b)

Name of Shape: TrigonalPlanar PredictedBondAngle: 120

Name of Shape: Tetrahedral PredictedBondAngle: 109

C F 4 : covalent bonding between two non-metals; e oppositely charged ions.

shared to complete valence shells. Electrostatic attraction between

MgCl1 /KBr: ionic bonding between metal and non-metal.

(c)

Ionic bond forms from strong attraction between cations and anions. There are no mobile ions or e therefore they do not conduct as solids. In solution, ions are free to conduct. In molten state an increase in energy allows ions to become mobile and therefore conduct mobile ions. At melting point a lot of energy is needed to separate ions due to the strong attraction.

(d)

HCN is a polar molecule as dipoles created by unequal sharing (polar bonds) do not cancel due to the unsymmetrical shape of the molecule. CF4 contains polar bonds but due to symmetry, dipoles cancel and the molecule is non-polar.

74

Answers - Structure and Bonding (AS90308) (Question p 16) (SFEE)

QUESTION E I G H T E E N (a) Substance CaCl 2 NH 3 K (b) (i)

Physical property High melting points Crystalline solid Colourless gas Low boiling point Conducts electricity

Bonding type Ionic Covalent (molecular) Metallic

Other example NaC 1, PbI2 CO,, O Zn, Al

Diamond - each C covalently bonded to 4 atoms and graphite (3 C atoms) are different structures of the same element (allotropes). Isotopes 1 2 Cand 14C have the same atomic number and different mass number due to different number of neutrons. NH j and CH1 both contain polar covalent bonds, e" are attracted more to N and C atoms setting up a partial charge but since CH4 is symmetrical, the partial dipoles cancel and overall CH4 is a non-polar molecule. NH j is asymmetrical in shape and therefore a polar molecule.

(ii)

(iii)

An ion is an atom (or group of covalently bonded atoms) which have gained or lost e". An ionic bond is formed by the electrostatic attraction of oppositely charged ions.

QUESTION NINETEEN

(Question pi 6)

(SFEE)

(i)

CO 2 i o i i c i : O*

(ii)

CH 3 Cl .Hx
H

'

f t

Shape: Linear

* '
H

BondAngle: 1097109.5 (iii) PH3

h : P:
X

Shape: Trigonal Pyramidal (b) (i) One of the following points is required: (ii) Covalent; Ionic.

One of the following points is required:

X2Y;

XY2

Answers - Structure and Bonding (AS90308) (c) (i) MgO ionic compound has a high melting point due to a strong electrostatic bond H 2 O is molecular and melting involves breaking a weaker intermolecular bond. (ii)

75

SiO, is a giant covalent lattice/covalent solid and has a high melting point, due to strong intermolecular forces. CO 2 are discrete molecules with weak Van der Waals forces between them.

(iii)

CH j COOH weak acid dissociates poorly. It exists as molecules and therefore does not conduct. With dilution the acid dissociation increases and the free ions in solution increase conductivity.

QUESTION T W E N T Y

(Question pi 7)

Carbon dioxide is a covalent, molecular substance and so contains discrete molecules with weak van der Waals forces between them. Very little energy is required to break these bonds and so sublimation occurs at low temperatures. As it exists as non-polar molecules, it therefore does not conduct electricity. The weak van der Waals forces are directional and easily broken so the solid line is brittle. Silicon dioxide is a covalent network solid. The electrons are all used to make covalent bonds and are not able to move freely to conduct electricity. The covalent bonds between molecules are strong and so require a lot of energy to be broken. Therefore, SiO2 has a high boiling point and is very hard.

QUESTION TWENTY-ONE (a) (i) (ii) (iii)

(Question pi 7)

(SFEE)

Sulfur is a covalent molecular substance. The weak Van der Waals forces between the molecules are easily broken. Diamond is a covalent network substance with strong covalent bonds in all directions. To break diamond, these covalent bonds must be broken. Water is a polar solvent. The molecules in petrol are non-polar and cannot disrupt the strong intermolecular forces between water molecules. A strong attractive force (electrostatic) between oppositely charged ions in a crystal structure (lattice). A strong attractive force between two atoms created by the electron pair they are sharing.

(b)

(i) (ii)

QUESTION T W E N T Y - T W O (a) C2H2

H - C = C - H

(Question pi 7)

(SFEE)

H J J C * * C * H

OR CH 3 Cl

I
H - C

W
Cl

Hjc OR

; c

I
H

Answers - Structure and Bonding (AS90308) 76 (b) (c) Chloromethane. Increases it. Molecular polarity increases the strength of the intermolecular forces. temperatures are required to separate the molecules). (i) (ii) (iii) (e) (f) bent/v-shaped; trigonal pyramid; linear. (Higher

(d)

The two bond dipoles cancel each other out (due to its symmetrical shape). Could include one of the following: CaCO 3 ; NaNO3; NH Cl.
4

QUESTION TWENTY-THREE (a)

(Questionpi8)

(SFEE)

One of the following points is required: . Li; Na; K.

(b) (C) (d)

Cl. Fe. One of the following points is required: Si; C.

(e) (0

F. One of the following points is required: Na; Mg; Al.

(g)

Br.

QUESTION TWENTY-FOUR

(Question pi8)

(SFEE)

Two of the following points are required: any metallic property( s); will have soluble compounds; forms a + 1 ion.

Answers - Structure and Bonding (AS90308) QUESTION TWENTY-FIVE (a) (i) (Question pi 8)

77

(SFEE)

The following points are required: magnesium oxide is an ionic solid; all the ions are held together by strong ionic forces needing high temperatures to separate.

(ii)

Copper metal is held together by non-directional attractive forces between an array of positive ions and a "sea" of electrons. Its shape can be changed without disruption of the forces. Oxygen is a covalent molecular substance. The attractive forces between the molecules are weak (Van der Waals) and so it has a very low boiling point. Silicon dioxide is a covalent network solid. The electrons are all used to make covalent bonds and are not able to move freely. CO 2 The bond dipoles are equal and opposite and cancel each other out.

(iii) (iv)

(b)

(i) (ii)

(c)

(i) H-P-H

, p ;
*
X

OR (ii) (iii) (iv) Trigonal pyramidal. Water. Covalent bonds are intramolecular forces that are strong. Van der Waals forces are intermolecular forces that are weak. (d) (i) (ii) H In solid sodium chloride the ions are held in fixed positions, but in molten sodium chloride they are free to migrate (are mobile).

O / N

dissolved ions

78

Answers - Structure and Bonding (AS90308) (Question pl9) (SFEE)

QUESTION TWENTY-SIX (a)

Neon consists of separate atoms with very weak attractions between atoms. Carbon atoms are strongly bonded to each other - covalent bonds. (i) O

(b)

O (ii) (iii) (iv) Ionic. Molecular.

One of the following points is required: copper; iron.

(v)

One of the following points is required: sodium chloride; potassium chloride; magnesium oxide; magnesium chloride.

(vi) (vii) (viii)

Low. Low. One of the following points is required: liquid; molten; aqueous; dissolved.

(c) (d)

Conduct electricity - because of free moving electrons. (i) V-shaped or bent.

H
x

Is-H

I S - H

OR ()

^S (iii) (iv) Yellow.

Sulfur has much larger molecules (M/gmol 1 : (Ss)=256, (H, )=2). Larger molecules usually need more energy to separate them.

Answers - Structural Formulae and Reactions (AS90309)

79

STRUCTURAL FORMULAE AND REACTIONS OF COMPOUNDS (AS90309)

We have chosen not to identify each 'answer' as 'achieved', 'merit' or 'excellence'. Students who wish to do so can determine the 'level' by referring back to the standard specified at the beginning of the 'question' chapter. QUESTION ONE (Question p2l) IUPAC name

Structural formula (a) OH CH 3 CH 2 CHCH 3 (b) CH3CHCH2C I Cl // O

Butan-2-ol

3-chlorobutanoic acid \ OH

(c)

C H

CH3

Methyl propanoate

V
O

(d)

Cl

CCH2CH2Cl

2,4-dichlorobut-1 -ene

// CH2

QUESTION T W O (a) (i) (ii) (iii) (b) 1. 2. 3. 4. 5. 6. 5 1 2

(Question p21)

(SFEE)

ethyl propanoate. butan-2-ol (or 2-butanol). 2-methyl butane. ethanoic acid. 3-chloroprop-l-ene. but-2-yne (or 2-butyne)

Answers - Structural Formulae and Reactions (AS90309) 80 QUESTION T H R E E (a) (Question p22)

(b)

A B

Primary Secondary (Question p22)

QUESTION FOUR (a) (b) (c) (d) Primary Oxidation

Fizzing would be observed as a gas is produced. Compound B is an alkene and will undergo an addition reaction to form a 2,3-dibromobutane (). The orange/brown Br2 solution will therefore turn colourless. Compound D is an alkane. Under UV light, it will undergo a substitution reaction to form an alkylhalide 2 2 2 (1-bromobutane). The orange/brown colour of Br 2 will slowly turn colourless as the substitution reaction is a very slow process. The gas released is HBr which is an acidic gas and can be detected by placing damp blue litmus paper at the mouth of the test tube. The litmus paper should turn red.

(e)

A structural isomer is a molecule that has the same molecular formula as another, but a different structural arrangement of atoms (e.g. molecules B & F are structural isomers as are C & E).

(f)
H H I / H-C C H H I / H-C C
H

v 4
cis isomer

C C-H H7

trans isomer

Answers - Structural Formulae and Reactions (AS90309)

81

Compound A: alcohol (primary). Add acidified potassium permanganate dropwise. Colour will change from purple to colourless, [or, K 2 Cr 2 O 7 ZH t - orange -> green change. ] Compound C: aldehyde. Add silver nitrate solution (Tollens reagent). A silver mirror will be produced on the inside of the test-tube. Compound E: carboxylic acid. Add water and test with litmus. Blue litmus is turned red. Add water - A and E will dissolve; C will not.

Compound

Name of functional group

Systematic name of the compound

c h

c h / c o h \

carboxylic acid J

propanoic acid

W
3 2

ester

methyl ethanoate

C H

Cthcch3

alcohol

2-methyl propan-2-ol

( o h )

( ^ ^ = ^

C H

alkene
3

4-methyl pent-l-ene

Answers - Structural Formulae and Reactions (AS90309) 82 QUESTION FIVE (a) Compound A Structural Formula Name Propan-l-ol (Question p24) (SFEE)

CH 3 CH 1 CH 2 OH

CH2
B

CHj

CH

/ /

Propene

OH

C
CH3 CH CH3

Propan-2-ol

O D

Propanone
CH 3
/ < 4

CH 3

E H I H - C I H I H H I C 'Ot // C \ ^ H

Propanoic Acid

O F

/
CH2

O C H

C H

- C H

Propyl Propanoate
3

/
CH3

(b) (c)

The colour changes from orange to green. One of the following points is required: hydration; addition.

(d)

A is soluble in water; B is insoluble in water.

Answers - Structural Formulae and Reactions (AS90309) QUESTION SIX (Question p25) Compound A Structural Formula
H \ C = C
4

83

Name Propene

H /

. /

B
H H

Propan-l-ol

C - H

I
H - C

I
C

I
H H

I
H

C
H

Propan-2-ol
H

I
H - C

I
C

I
C - H

I
H H

I
H

D
H H

Propanoic acid I
H - C
1

I
C
1

//
C

\ n

\
H

Propyl propanoate

\ \

^H H H H

i
C O C

l
C

l
C - H

//
o'

I
H

I
H

I
H

84

Answers - Structural Formulae and Reactions (AS90309) (Question p26) C % +A1 38.40 38.40 12 = 3.2 H 4.80 48.80 1 = 4.8 M
1.6

QUESTION SEVEN (a)

(SFEE) Cl 56.8 56.8 35.5 = 1.6 L6

1.6

12
+ smallest 1.6 =2 Empirical formula: C 2 H 3 Cl (b) (c)

=3

=1

M(C 2 H 3 CI) = 62.5. So Molecular Formula = C 4 H 6 Cl 2 . (Need to do (a) and (b) in order to answer(c))
Cl

C-C

^H 3

CH 3 \ C = C / Cl

CH 3
/ \ Cl

/
CH 3 Cl Cl

\ Cl

Cl / = C Cl H

\
H

\ A

^H

"
QUESTION EIGHT (a) (b) (Questionp26)

(SFEE)

A compound that has double or triple bonds between carbon atoms. (i) (ii) CH 2 = CH - CH = CH - CH 3 + 2H 2 One of the following catalysts is required: Ni; Pt; Pd. CH CH CH C H C H

One of the following conditions is required: (c) high temperature; high pressure. 5CO. + 4 H , 0

CH 2 = CH - CH = C H - C H 3 + 7 0 .

Answers - Structural Formulae and Reactions (AS90309) QUESTION NINE (a) (Question p26)

85

CH3 H CH3

-
H H H H
(b) (i)
H H H

H - C

I
H

I C I
H

I
H

C - H

(ii) H H H H H H

I
and

I I
H

I I

I I

H-C C C-H

I H I I
m

H-C C C-H

,A-HH

.A-H

(iii)

The left-hand structural formula [CH 3 CH(OH)CH 3 ] will be produced in the larger amount. The carbon 'richest' in hydrogen atoms gets 'richer' in them (Markovnikov Rule) and therefore in this case the OH adds to the 'poorer' carbon. (Question p27) / 0 (SFEE)

QUESTION TEN (a)

3CH3(CH2)i6 C ONa One of the following points is required: (b) sodium stearate; sodium octadecanoate.

One of the following points is required: glycerol: cosmetics; lubricant; explosives.

Product B: soap for washing.

Answers - Structural Formulae and Reactions (AS90309) 86 (c) (i) (ii) (iii) (iv)
H H H H H H

Water/H 2 0. Bromine water - acrolein will decolourise, (orange - colourless). Acrolein is a polar molecule with stronger forces between its molecules than the non-polar but-l-ene.

I _

I _
C

I _
C

I _
C

I _

I _
COOH

"I
H

I
H

I
COOH

I
H

COOH

QUESTION ELEVEN

(Question p28) Section of the polymer Monomer molecule

(a)

Polypropylene

IL
x^x

CHI CH CH

CHI CH

CHI CH

CH1 \

I
CH,

L
CH,

L
CH,

L
CH,

(b)

Polyvinyl chloride (PVC)

CHI CH CH CH1 CH CH1 CH CH2

IL

I
CL

L
CL

L
CL

L
CL

QUESTION TWELVE (a)

(Questionp28)

(SFEE)

One of the following points is required:

CnH,2n+i)0H;
CH(2n+2)0.

(b)
H H H H I l l l H - C C C I l l l H H H H H H H H I l l l H - C - C C I l l l 1 H H H 0 1 H H H H I I I H - C - C C I I I
h

C - H

O-H

O-H

H-C-H I H

Butan-l-ol

Butan-2-ol

2-methylpropan-l-ol [or show as 2-methvlpropan-2-ol]

Answers - Structural Formulae and Reactions (AS90309)

87

"
H H (d)

H
H
'

-H
- ) CH3CH2OH

H2O(I) + CH2 = CH2

QUESTION THIRTEEN (a) (b) Ethyl Propanoate. Alcohol - ethanol;

(Questionp28)

(SFEE)

Carboxylic acid - propanoic acid. (c) Molecule Property: Alcohol Solubility Cr 2 O 7 2 TH + Soluble in H 2 O Colour change from orange to green Carboxylic Acid pH bicarbonate carbonate <7 gas been given off, i.e. bubbles. or Ester Smell

Test Results:

Sweet

QUESTION FOURTEEN (a) (i)

(Question p29)

(SFEE)

C = 2,3 dibromopentane; D = pentan-2-ol. (or 2 pentanol).

(ii) (iii)

C n H 2n One possible answer is:

H H H H H I I I I I I I I I H - C C -- C C C I I I I I I I I I I H H H H H

-O-H

pentan-l-ol (iv)
v

AdddiluteH SO or H 1 PO, and heat.

2 4 3 4

'

(v)

One of the following points is required: substitution; bromination; ,'^ i > CH 3 CH 2 CHBiCHBiCH 5 +2HBr.

(vi)

halogenation. CH 3 CH,CH 2 CH 2 CH+2Br,

88 (b) (c) (d)

Answers - Structural Formulae and Reactions (AS90309) Ability of C atoms to join / bond together in long chains. 2,4. Two of the following points are required: liquid at room temperature; non-conductive; colourless; immiscible.

(e)
H

(i)
. "
1

H + H-O-H

//

Oi

H - C - C Oi 1

"

H - C - C 1 H

H
I O H-C-

\ M

I I I C-C-Ot
H H

H
(i) (f) Ester.

Polyester is formed by alternating carboxylic acids and alcohols (i.e. esters). involves the removal of the H2O molecule.

Condensation

QUESTION FIFTEEN (a)

(Questionp29)

(0
OH CH

CHCH

I H-CI
H

H I
-C

H I
C

//
O - C

(ii)
HCI CH 3 CH 2

H H H I I I
H - C C C - H 1 1 I H H

d,

(iii)
CH 3 OH

+ H.O / H"
CH 1 CH,

I
CH3CCH3

I
CH,

Answers - Structural Formulae and Reactions (AS90309)

89

(iv) H
1

H
1

H
1

H +Cr2O72VH*
4

H - O - C C C - H I I I H H H

H H I I C C C-H
1 1

// A'
(b) (i) (ii) (iii) (iv) (c) Ester Haloalkane Alcohol Carboxylic acid.

C1H1

CH1

CL

/ 4
H1C CH IIJC

/ I + 2HC1
H!C
N

Limonene
H'C \ H
/

\ X C I
CH, H
X

H H
^
H

CH1

/
HIC CHI H,C J

C
H I

CL

QUESTION SIXTEEN (a) B = CO2; C = H 2 O; D = CH 2 CH 2 . (b)

(Question p30)

(SFEE)

The following structural formulae are required:

H H O H - C - C

I
H - C - C H

//

I
H

And (c) (i) (ii)

H

Polythene,

I . -CI H

I I C I I

H - -

I I C I I
H

I I I

I I I

H C H

- C H

C H

I I I I

Answers - Structural Formulae and Reactions (AS90309) 90 (d) Ethanol is a polar molecule and so can dissolve in water which is a polar solvent. OR, the - O H bonds allow for H bonds to adjacent molecules and H 2 O making ethanol very soluble in water.

QUESTION SEVENTEEN Compound X

(Question p31) Structural formula

H H I l H - C C I I H H H H l l C C I I H H H l

Name
butan-l-ol

0 "

H H I I H - C I I H H

H I C I H

!^t //
C \ ^ H
m

butanoic

acid

Z
H H H H I I I // H H - C C C C \ I I I \ ^ c H H H ^ N

butyl

butanoate

V
\

4 H C ^ V - ^ \ H H h

W //
H-C \ H

C C I
H

V ?
' H

but-1 -ene

C-H

V
? I H - C I H H l C l H l C l H l H H l C - H H

1-chlorobutane

V'

H H H H I l l l H - C C C I l l l H I1 H

2-chlorobutane C - H H

Note: V' is produced in greater amounts than V. V and V' can be reversed in table above.

Answers - Structural Formulae and Reactions (AS90309) QUESTION E I G H T E E N (a)

H
H - C

91

(Question p31) Secondary: H !

O - H H - C

(SFEE) Tertiary:
H

Primary:

I I C I I
H

H I

H H I I l
C

- C

C
H

C - H
H

H -{- H H
I
H - C

0 1
H

I I c-

I 1 1 H 0 1 H

(b) (c)

14. The following points are required: react each with bromine water; cyclohexene causes brown colour to turn colourless immediately; cyclohexane produces no colour change.

(d)

Add blue litmus/indicator to each and colour change to red (or appropriate for indicator chosen) identifies the ethanoic acid. Add the remaining two chemicals to water - the one that dissolves is ethanol, leaving ethyl ethanoate as the remaining one. A fruity smell is the Ester.

QUESTION NINETEEN (a)

(Question p32)

butan-l-ol and but-2-ene. Test: Observations: Explanation: Add to bromine solution. But-2-ene will decolourise the solution; there will be no change in the solution's colour with the addition of butan-l-ol. The but-2-ene reacts with the bromine solution (addition reaction) to produce 2,3dibromobutane. The alcohol does not react with the bromine solution.

(b)

butanoic acid and methylbutanoate. Test: Observations: Explanation: Blue litmus paper. Blue litmus paper will turn red with butonoic acid; there will be no change with methylbutanoate. The COOH group means that 2 2 is acidic and so will turn blue litmus paper red. There will be no change with methylbutanoate.

QUESTION TWENTY (a) (b) (c)

(Question p32)

(SFEE)

A compound containing the elements hydrogen and carbon only. CH2n+2Name - propane. Molecular formula C 3 H 8 .

92 (d)

Answers - Structural Formulae and Reactions (AS90309) Two of the following structures are required: H I
H - C H H H H H H I I I I I I I H - C - - C C C -- C C - H I I I I I I I H H H H H H

H l
C

H i
C
1

H i

H i
C C - H

W - H "
H

Hexane H H I
H-C

2-methyl pentane

H i l
C
H

H i l
C

H H i i l
C
H

H C - H
H

"?-

H C-H

H-C C

H - i - H

3-methyl pentane

2,3 dimethyl butane

H H -{- H H
I I I
H - C

I l l l H 1 H H H-C-H I
H

C - H

2,2 dimethyl butane

QUESTION TWENTY-ONE (a)

(Question p32)

(SFEE)

(b)

(i)
H

H-CBr

-C-H Br

(ii) (c)

Addition.

The brown/orange colour of bromine would have gone colourless.

Answers - Structural Formulae and Reactions (AS90309) QUESTION TWENTY-TWO (Question p32)

93

(SFEE)

H H - C

H C

//

O _

i
(b) (c) HLa+H^O v
4

-
H30*(aq)+La'(aq)

One of the following points is required: alcohol; hydroxyl; hydroxy.

QUESTION TWENTY-THREE (a)

(Question p33)

(SFEE)

One of the following points is required: sodium ethanoate; sodium acetate; sodium salicylate; sodium hydroxybenzoate.

(b)

Cyclohexene: does not dissolve in aqueous solutions; two miscible layers; decolourises orange aqueous bromine.

Ethanoic acid: fizzes; gas released with Na,C0 3 (aq).

Ethanol: unreactive sample; dissolves only.

QUESTION TWENTY-FOUR (a) (i) (ii) (iii) (iv) (v) (b) (i) Methane; Ethane; Propane; C3H8; C4H10.

(Question p33)

(SFEE)

Characteristic groups of atoms an properties.

bonds which gives the molecule its characteristic

Answers - Structural Formulae and Reactions (AS90309) 94 (ii) Two of the following points are required: double carbon to carbon bond; -COOH/carboxyl group; -OH/hydroxyl group; -COO-ester linkage/group.

QUESTION TWENTY-FIVE (a)

Cl

(Question p33)

Cl

Cis-1,2-dichloroethene (b)
Cl

Trans-1,2-dichloroethene

Cl
This isomer cannot exist in cis-trans isomers because both chlorine atoms are attached to the same carbon. For geometric isomers to exist, there must be two different 'groups' on each carbon of the double bond. In (a) above we had a hydrogen atom and a chlorine atom attached to each carbon, but in this isomer we have the same 'groups' attached to each carbon.

QUESTION TWENTY-SIX (a)

(Question p34)

(SFEE)

The following points are required: NaOH; CH, (OCOR)CH(OCOR')CH 2 (OCOR"); R/R'/R'' = C17H35 or suitable alternative.

(b)

One of the following points is required: potash; potassium hydroxide; sodium carbonate; potassium carbonate.

(c)

One of the following points is required: saponification; hydrolysis.

Answers - Structural Formulae and Reactions (AS90309) (d) One of the following points is required: (e) (f) Brine. One of the following points is required: cosmetics; paint; foodstuffs. raise temperature; boils reaction mixture.

95

QUESTION TWENTY-SEVEN

(Question p34)

| 2 ), 6 3

Il CHOC(CH 2 )I 6 CH 3 + 3NaOH

Il > 3CH 3 (CH 2 )i 6 CONa + Compound M

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

(b) (c)

alcohol (3 of them). The term unsaturated means that the compound contains at least one non-single bond. Therefore the compound has at least one double or triple bond present. Firstly, each of the fats would need to be homogenised and added to a non-polar solvent such as cyclohexane. Add excess bromine solution to each of the fat-containing solutions. The bromine solution is originally orange/brown coloured. Bromine reacts with carbon double bonds by an addition reaction. The more double bonds that there are in the fat-containing solution, the faster the solution will lose its colour. Therefore the degree of unsaturation can be determined by observing the degree of decolourisation of the orange/brown colour, or the amount of time taken for each solution to become colourless.

(d)

QUESTION TWENTY-EIGHT (a) (i) (ii) Free fatty acids.

(Questionp35)

(SFEE)

One of the following points is required: soaps; sodium salt of fatty acid; RCOONa.

Answers - Structural Formulae and Reactions (AS90309) 96 (iii) One of the follow ing points is required: easily vaporises; low boiling point. One of the following points is required: steam increases temperature; low boiling point impurities evaporate. One of the following points is required: hydrogenation; reduction. Two of the following points are required: vitamins; water; emulsifiers; citric acid; mineral salts; salt; flavourings; colour (beta-carotene). One of the following points is required: long chain carboxylic acid; organic acid with a large CH or alkyl group. C 17 H 35 COOH (or)
H H H H I I C I I H H I I I H H I I C I I H H I ! C I I H H I I C I I H H I I I I H

I
H - C -

I
-C

I
C-

//

I
H

I
H

I
H

(") (c) (i) (ii)

Containing more than one carbon to carbon double bond / multiple bond. Blue to orange/yellow/red/pink. One of the following points is required: soluble starches contain fewer glucose units than insoluble starch. insoluble starch has more branching in its structure.

Answers - Chemical Reactivity (AS90310)

97

CHEMICAL REACTIVITY (AS90310)

We have chosen not to identify each 'answer' as 'achieved', 'merit' or 'excellence'. Students who wish to do so can determine the 'level' by referring back to the standard specified at the beginning of the 'question' chapter. QUESTION ONE (Question p37) (a) (i) (ii) Reactants. Since forward reaction is endothermic, reactants must be of lower energy, therefore energetically more stable. (SFEE)

(b)

M ( N H 4 N 0 3 ) = 80 __m _ 20 80 = 0.25mol

(c)

1 mole needs 25kJ Therefore 0.25 mol needs 0.25 1 x 25

= 6.25kJ ... (d) n 0.25 == V 0.1 = 2.5molL 1 QUESTION TWO (Question p37) (a) (b) To ensure that all the HCl has reacted or that the reaction goes to completion. (i) (ii) (iii) (c) (d) D. E. A. (SFEE)

A catalyst offers an alternative pathway of lower activation energy. The following points are required: temperature; surface area. (Question p38)

QUESTION THREE (a) Change I: Change 2: Change 3: Change 4:

Increase Decrease Increase Remain the same

98 (b)

Answers - Chemical Reactivity (AS90310) Change 1: As temperature is increased, the average kinetic energy of the particles is increased. More particles have sufficient energy to overcome the reaction's activation energy, collide and react. Therefore there are more successful collisions per second and more product forms per second. The reaction rate has increased. Change 2: The concentration of acid has been decreased so there are less acid particles present in the lOOmL. There will be fewer collisions per second and less product forming per second. The reaction rate has decreased.

QUESTION FOUR (Question p38) (a)

(SFEE)

If any change is made to a system at equilibrium, the equilibrium will shift in the direction to oppose/minimise the change. 4. 2A(g)+2B<g) ^ C(g)+2D(g>. AH is negative,

(b)

(c)

r _ [C][D] 2 [A] 2 [B] 2 (i) Move to RHS/products favoured. If concentration of B was increased, the equilibrium will respond by using up some of the extra added B, thus moving to RHS. (ii) Move to RHS/products favoured. If we cool the system down, the equilibrium will shift in exothermic direction to produce more heat, therefore forward direction favoured.

(d)

QUESTION FIVE (Question p39) (a) 178g of H 2 S 2 O 7 produces 196g of H 2 SO 4 89 Therefore 8.9g of H,S,O 7 produces x l 9 6 = 9 . 8 g l l , S 0 4 178 (b) PH = -Iog [H 3 O + ] = -log (0.2) = 0.7 (c) (i) (ii) NaOH+HCl * NaCl+H,0

(SFEE)

/i(NaOH) = cx V = 5.5x0.025 = 0.1375moles

/!(HCl) = C x V = 3 . 0 x 0 . 0 5

(iii)

= 0.15moles

Answers - Chemical Reactivity (AS90310) (iv) (1) in the final mixture = 0.15 - 0.13 75 = 0.0125moles n 0.0125 c(HCl) in the final mixture = = V 0.075 = 0.167molL"' PH = -IogtH 3 CN

99

= -log(0.167) = 0.78

QUESTION SIX (Question p40) [SO 3 ] 2 [S02]2[02]

(SFEE)

(a)

Kc

(b)

A catalyst provides an alternative pathway which has a lower activation energy, therefore more particles colliding will have sufficient E a to react. A catalyst is not used up in the reaction. No effect. One of the following points is required: catalysts speed up forward and reverse reactions equally; catalysts only speed up the time to achieve equilibrium.

(c)

(d)

Two of the following points are required: increase [SO2 ] and/or [O, ] according to Le Chatelier, equilibrium will shift to use up additional reactants producing more product SO 3 ; remove [SO3 ]. A decrease in [SO3 ] will shift equilibrium to produce more, therefore

increasing production of [SO3 ]; increase in pressure shifts equilibrium to the side with less volume (i.e. least number of gaseous particles) therefore producing more [SO3 ]; In exothermic reactions, heat is produced and therefore decreasing the temperature favours the forward reaction producing more [SO ].

(e)

Kc = 2300 is very large, therefore [SO3 ] is much greater than [SO, ].

1OO Answers - Chemical Reactivity (AS90310) QUESTION SEVEN (a) (Question p40) (SFEE)

2 S 0 j ( g ) products

Reaction co-ordinate

(b)

2mol SO j from Imol 0 . M(SO 3 )= 32+ (16x3) = 80gmol l 160gS0 3 from 1 mol O, 0.16kg => ImolO 2

0.16 = 9.375 x IO6 mol

(c)

Imol SO 3 (80g) liberates IOOkJ 0.08kg SO 3 =^lOOkJ l.SxlO^kg^

1 5 x 1 d

0.08

^-

1 0 0

= -1.87xl09kJ

QUESTION E I G H T (a) (b) (c) (d) (e) exothermic endothermic exothermic exothermic endothermic

(Question p40)

Answers - Chemical Reactivity (AS90310) QUESTION NINE (a) (Question p4Ij is negative). AH

101

In exothermic reactions heat is produced (i.e. H -^products"^rcacunts(i.e. heat is lost).

is negative where

Negative AH means that reactants have more energy than products

(b) (c)

6.12 m o l x - 5 5 0 0 k J m o r ' = -33660 kJ. Therefore, 33660 kJ is released. 1 mol H 2 gives 286 kJ, so for 33660 kJ we need n= 117.89= = 117.69 moles OfH 2 (2 dp).

286

m
M

(2x1)

m = 117.69xf2xl) = 235g (3sf)

QUESTION TEN (Question p41) (a) (b) Sx-ArH = S mol x98.2 = 491 kJ n= - M ^ 7 = 0.03125 mol

(2xl6)gmol

The given equation shows Vi mol O 2 being formed so the energy released when 0.03125 mol O 2 is 0.03125 0.5 (c) , ,_. x98.2 = 6.1375 = 6.14 kJ (3sf)

98.2 kJ from 1 mol H 2 O 2 . 600 kJ from = 6.11 mol H 2 O 2 . 98.2 n= M m = 6.11x34 = 208 g

QUESTION ELEVEN (a) (b)

(Question p41)

(SFEE)

An acid is defined as a proton donor. HCl dissociates completely in solution giving off its proton to form H j O" (low pH) whereas ethanoic acid does not dissociate fully existing mainly as molecules - less FT given off; higher pH.

(c)

pH = -log [FT ] = -log (0.14) = 0.85.

102

Answers - Chemical Reactivity (AS90310) (Question p41)

QUESTION TWELVE (a) (b)

HY is the stronger acid. The two acids have the same concentration. pH is a measure of the H 3 O + concentration. A lower pH means more H 3 O + ions are present since pH = -log[H 3 0 + ]. HY has a lower pH than HX, so its solution contains more H3O* ions. This means that it dissociates more in solution HY than HX, so HY is the stronger acid. There are a number of possible answers. Two possible tests are as follows: Add magnesium ribbon or calcium carbonate to the two solutions. In both solutions the magnesium will react, as seen by the fizzing, but the magnesium will fizz more violently in the stronger acid, and will stop reacting in the stronger acid first (because it reacts quicker). Titrate the two acids against NaOH and measure the pH at the equilibrium point. The pH for the titration with the stronger acid will be lower than for the titration with the weaker acid. Test the conductivity of each acid HY. The stronger acid will be a better conductor.

(c)

QUESTION THIRTEEN (a)

(Question p42)

HCl+ H 2 O -> H 3 0 + ( a q i + C r ( a q ) CH 3 CH 2 COOH + H 2 O ^ CH 3 CH 2 COO

(aq) (4)

+ n 33 O H u

(aq)

(b)

The hydrochloric acid has a high acidity and high conductivity because in aqueous solution it completely dissociates The propanoic acid, however, is a weak acid - it only partially dissociates resulting in an equilibrium. Propanoic acid has a lower concentration of H 3 O + and therefore has a lower acidity. Propanoic acid has a lower concentration of ions in general so therefore has a lower conductivity than the hydrochloric acid solution.

QUESTION FOURTEEN (a) (b) CaCO+2HC1 Acid - H 1 O + ; Conjugate Base - II1O OR: Acid - H 1 CO 3 ;

(Question p42)

(SFEE)

* CaCI,+C0 2 +H,0 .

Conjugate Base - HCO 3 . (c) M(CaCO 3 )= 40 + 12 + (16x3) = IOOgmol -i

103 (d)

Answers - Chemical Reactivity (AS90310) 2 x 0.045 = 0.09 moles HCl needed to react with 0.045 moles of CaCO 3 . " cr\ -1 0.09 mol = => 0.50molL = V V(L) V = 0.180 L

(e)

One of the following points is required: sodium carbonate is more soluble (i.e. Na" does not form a precipitate); calcium carbonate is insoluble (i.e. Ca2+ reacts with some anions to form a precipitate).

QUESTION FIFTEEN (a)

(Question p42)

(SFEE)

The following two points are required: Solution A - should be sodium chloride or water. Solution D - should be ammonia.
NH/(aq)+OH-(aq)

(b)

NH3(aq)+H,0 V

(c) (d)

Water or sodium chloride (must be different to answer to first part of (a)) H2S04+2H,0 2H,0*(aq)+S0J2"(aq)

QUESTION SIXTEEN
(a) C02(g)+2H20 v

(Question p4i)
H30*(aq)+HC03-(aq);

(SFEE)

(b)

(i)

CH 3 C00H(aq)+H,0 [CH3COOHH3O*]

CH 3 C00-(aq)+H 3 0\aq)

(")

[CH 3 COOH]

QUESTION SEVENTEEN K = - J ^ [S02]2[02]

(Question p43)

(a)

rw (D)

e = , I n q ] 4 r. [NH 3l]4 r [O 2l5 ]

[CH 3 COO ][H*] [CH 3 COOH]

(C)

Kc =

104

Answers - Chemical Reactivity (AS90310) (Question p44) (SFEE)

QUESTION EIGHTEEN (a)

The wood powder presents an enormous surface area in contact with oxygen. This gives a high collision rate and a very fast reaction. The concentration of oxygen is greater in pure oxygen than in air. This produces a higher collision rate and a faster reaction. At room temperature the activation of energy is too high to overcome. The spark provides this energy and the reaction, once started is rapid.

(b)

(c)

QUESTION NINETEEN (a) (b)

(Question p44)

The time taken would reduce. The increased temperature means that the particles have more energy and move faster. This results in more collisions between particles. Both factors (more energy and more collisions) mean that more particles will collide with sufficient energy to form the product.

QUESTION TWENTY
Energy

(Question p44)
uncatalyscd path

(SFEE)

products

catalysed path

reactants

Reaction Coordinate

QUESTION TWENTY-ONE
(a) Fe3*(aq)+SCN"(aq) <

(Question p44)
" [FeSCN] 2 "(aq) [ AH is exothermic.]

(SFEE)

(b)

Solution turns a darker red. Addition of Fe 3t causes equilibrium to shift to the right.

QUESTION TWENTY-TWO (a) (b) Increases it. Increases it.

<Question p44)

(SFEE)

Answers - Chemical Reactivity (AS90310) QUESTION T W E N T Y - T H R E E (Question p45)

105

(SFEE)

The equilibrium would shift to the right. This would reduce the number of gaseous molecules present. QUESTION TWENTY-FOUR (a) (b) (C) (d) Strong. HCH-H2O - > H30+(aq)+CI (aq) [H 3 O"]= IxlO" 2 molL' 1 . I x 10~ 2 molL"'. (Question p45) (SFEE) (Question p45) (SFEE)

QUESTION TWENTY-FIVE (a) (b) (c) (d) (e) (f)

Decreasing the concentration of X decreases the rate of reaction. Carbon dioxide. Calcium hydroxide. Y. As the reactants are used up, their concentration decreases. The following two points are required: it lowers the activation energy; it is not 'used up' in the reaction. Increase. Particles move faster and collide more frequently and/or with greater energy. (Question p46) (SFEE)

(g)

(i) (ii)

QUESTION TWENTY-SIX (a) (b) (c) (d) Haber Process. High Pressure.

ArH value is negative - exothermic reaction. (i) (ii) No effect. Increases the amount of ammonia produced.

(e) (f)

56-59%. One of the following points is required: reaction is too slow; not enough particles have activation energy required.

106 (g)

Answers - Chemical Reactivity (AS90310) One of the following points is required: removing ammonia quickly; recycling unreacted hydrogen and nitrogen. N2 Mgmor
1

(h)

2NH 3 17 34

28 28

Reaction ratios

100% conversion of 28,000 kg of nitrogen, gives 34,000 kg of ammonia. 15% of 34,000 = 5100 kg.

QUESTION TWENTY-SEVEN 9RS (a) (i) (ii) = 142.5

(Questionp47)

(SFEE)

One of the following points is required: explosive combustion; car accidents; large volume for small distance; storage difficulties/dangers.

(iii)

Octane combustion 15% efficiency yields - 47.8x0.15 = 7.17kJg"' Same yield for methanol % efficiency = x 100 = 30.38 = 30.4% 23.6 OR x 15% = 30.4% 23.6 7.17 = 23.6 x % efficiency

(b)

(i)

The following are required: CO; SO,.

(ii) (iii)

CO2. CO.

QUESTION TWENTY-EIGHT (a) (i) Kc [CH,OH] [CO][H,]"

(Question p47)

(SFEE)

107 Answers - Chemical Reactivity (AS90310) (ii) The following points are required: Increase pressure - products have 1 mol compared to 3 mol for reactants and according to Le Chatelier's Principle increasing pressure will favour the side with lower number of gaseous moles; Increase [reactant] - system will act to minimise stress by using up reactants and [product] increases; Removal of product - system will oppose the change by shifting equilibrium to the right increasing the production of methanol; = - 3 6 0 kjmol" 1

(b)

(i) (ii)

2CH 3 0H+30 2 Exothermic.

* 2C0,+4H,0

(iv)

M(CH 3 OH)=32 % composition ^ x 1000=125kg

OR

0.032kg CH j OH from 4 x 10 3 kg H2 4 x 10"3 xIO 3 1000kg => 0.032 = 125kg

(c)

(i) (ii)

Increase temperature of acid=> increases kinetic energy of reactant allowing more effective collisions. Add a catalyst => (MnO 2 ) provides an alternative pathway requiring a lower activation energy therefore increasing the rate of decomposition.

QUESTION TWENTY-NINE (a) (b) NO 2

(Question p48)

The Kc value is so small and since it is the ratio of products to reactants this indicates that there are more reactants present than products. Therefore NO 2 is present in a greater concentration at equilibrium than N 2 O 4 .

108 (c)

Answers - Chemical Reactivity (AS90310) (i) You would expect to observe the gas system going browner. This occurs because increasing temperature adds energy to the system, favouring the endothermic reaction (the one that produces NO2Ig)) to absorb energy. Equilibrium shifts to the left and the gas system turns browner due to the excess N0 2 ( g ) produced. You would expect to observe the gas system to go darker brown. Addition OfNO 2 leads to increased NO 2 concentration and increased pressure. Equilibrium position will move to minimise this, and decrease pressure, by forming fewer molecules and use up some of the NO 2 . Note that some (but not all) NO 2 will react to form N2O-I. There will be more NO 2 in the new equilibrium mixture and it is observed as a darker brown.

(ii)

QUESTION THIRTY

(Question p48)

(a)

(i) (ii)

[FeSCN 2+ , ,] = ^J+ [Fe (aq) ][SCN- (aq) ]

The solution would become paler (less red). The equilibrium shifts left to replace the removed ions (and use up the excess FeSCN 2+ ).

(b)

(,)
(ii)

[N 2 ][H 2 ] 3 The amount of NH 3 in the system will increase. The increase in pressure shifts the equilibrium to the right (producing more NH 3 ), because this is the side with fewer moles of molecules (i.e. two versus four). At higher temperatures the system will move in the endothermic direction to use up the excess energy. At higher temperatures we have less NH 3 present so the system must favour the left-hand side (i.e. the reverse reaction is endothermic), so the reaction in which NH 3 is formed must be exothermic.

(iii)

QUESTION THIRTY-ONE (a) (b) It is acting as a base.

(Question p49)

A base is a proton acceptor. HCO3" accepts a proton from H 2 O to become H 2 CO 3 . It is therefore acting as a base. Also, because it produces OH" ions this indicates that it is a base and not an acid (which would produce H + or H 3 O + instead).

QUESTION THIRTY-TWO (a) 1. 2. 3. (b)

(Question p49)

Acid H 2 CO 3 ; base HCO3". Acid H 3 O + base H 2 O. Acid HCO 3 ; base CO32".

Equation 2 is acting as an acid because it is acting as a proton donor (it gives its proton to the H 2 O tO form H3O", aq)).

Answers - Chemical Reactivity (AS90310) QUESTION T H I R T Y - T H R E E (Question p49)

109

When NH 4 Cl dissolves in water the following reactions occur: NH4Clw then NH4*+H20 *
+ 4

NH 4 + (aqJ + Cr ( a q ) NH3+H3O*

i.e. the NH 4 ions produced on dissolving OfNH 4 Cl in water reacts with the water to produce H 3 O + ions. It is therefore going to produce an acidic solution (pH < 7) because of the H 3 O t ions produced. QUESTION THIRTY-FOUR Solution A (Question p49) [OH ] / mol L"1 0.0288 pH I o g f l x l 0 M 1 = 12.5(3 sf) [ 0.0288

[H 3 O + ] / mol L 1 lxlO" 1 4 0.0288 3.47x IO 1 3 (3 sf)

IO"5'24 =5.75x IO 6 (3 sf)

lxl0

" ' 4 - 1 . 7 4 x IO"9 (3 sf)

5.24

10

QUESTION THIRTY-FIVE (a) Solution

(Question p50)

Concentration of H 3 O + and OH" in solution Greaterthan IxlO ' m o l L 1 Lessthan lxlO 'molL"1 H3O+ OH' H3O+ OH

Na 2 CO 3 0.100 molL-1 HNO 3 0.100 molL-1 NaOH 0.100 molL"1 NH 4 Cl 0.100 molL"1 (b) pH = -log[H 3 0 + ] = -log(0.035) = 1.46 (3 sf) (c) 9.2 =-IogfH 3 O + ] [H 3 O + ] = IO"'2 [ H 3 0 + ] = 6 . 3 1 x l 0 1 0 molL"1 (3 sf)

OH H3O+ OH H3O+

= 1.58 x IO"5 molL"1 (3 sf)

110

Answers - Oxidation-Reduction Reactions (AS90311)

OXIDATION-REDUCTION REACTIONS (AS90311)

We have chosen not to identify each 'answer' as 'achieved', 'merit' or 'excellence'. Students who wish to do so can determine the 'level' by referring back to the standard specified at the beginning of the 'question' chapter. QUESTION ONE (a) (b) (Question p52) NH 2 Cl = -I NH,Cl = -1 (SFEE)

Oxidationstateofchlorine in: HOCl = + 1 Oxidation state of nitrogen in: NH 3 = -3

QUESTION T W O (i) (ii) (iii) (i) (ii) (b) (i) (ii) Mn 2 + H2O2 Br 2 SO 2 CO

(Question p52) +2 -1 O +4 +2

Species oxidised , Br - ; species reduced, H2O2. Br" is oxidised to form Br 2 which is orange. H 2 O 2 + 2H + + 2e" 2 H 2 0 2Br" Br2 + 2e"

H 2 O 2 + 2H~ + 2Br" -> Br2 + 2 H 2 0 (iii) 2(Fe 2+ - > F e 3 + + l e " ) Cl 2 + 2e"

2+

2Fe +Cl 2 -> 2Fe 3+ +2 The Fe 2+ ions, which are pale green, are oxidised to form Fe3* ions which are omage.

QUESTION T H R E E (a) (b) Fe(OH) 3 .

(Question p53)

(SFEE)

One of the following points is required: orange; brown; rusty.

(c)

Reduction. Oxidation state has decreased from O to - 1 . Chlorine atom gains an e".

(d)

Cl+2NaOH

* NaOCb-NaCKH 1 O .

Answers - Oxidation-Reduction Reactions (AS90311) QUESTIONEIGHTEEN(Question p60) (a) (b) (c) MnO4" + 8FT + 5e~ C2O42" Mn 2 t + 4 H , 0 .

111

(SFEE)

*2C0+2e". * 2Mn2* +8H 2 0 . > IOCO2 +

2

2MnO; + 16 + ) 8 ^ 5C,0 4 2 2MnO; + 16H* + 5 C , 0 "

4 2 4

XJ^.
2 2

* 2Mn " + 8H,0 + IOCO,.

QUESTION FIVE (Question p53J (a) The reductant is SO 2 because it is oxidised. It has gained oxygen or, equivalently, the oxidation number of S has increased from +4 to +6. Oxidation: Reduction: (c) SO 2 + 2 H 2 0 SO 4 2 " +4H* + 2e~

(b)

Cr 2 O 7 2 " +14H + +6e~ -> 2Cr 3+ + 7 H 2 0

3 S 0 2 + 6 H 2 0 + Cr 2 O 7 2 " + 14H + + 6e" -> 3S0 4 2 " +12H + + 6e" + 2Cr 3+ + 7 H 2 0 3 S 0 2 + Cr 2 O 7 2 " + 2H + -> 3S0 4 2 " + 2Cr 3+ + H 2 O

(d)

The solution would turn from orange (due to the Cr2O?*" ions) to green (due to the Cr 3+ ions produced).

QUESTION SIX (Question p54) (a) (i) (ii) (b) : -1

IO3": +5 IO 3 ' 21" I 2 + 2e~ 2I03"+12H++10e" -I2 + 6H20

Oxidant: Reductant:

(c)

I": IO3":

(d)

+ 23" + 1 2 + - > 6 I 2 + 6 H 2 0 51" + IO3" + 6 H + - > 3 I 2 + 3 H 2 0

112

Answers - Oxidation-Reduction Reactions (AS90311) (Question p54) (SFEE)

QUESTION SEVEN (a)

Product at positive anode Cone, sodium chloride solution Molten lead bromide Dilute sulfuric acid (b) (i) Chlorine Bromine Oxygen

Product at negative cathode Hydrogen Lead Hydrogen

One of the following points is required: 2H + + 2e~ - > H 2 / 2 H 2 0 + 2e" H 2 + 20H". * Br, + 2e".

(ii) (c)

2Br"

One of the following points is required: NaOH; sodium hydroxide; caustic soda.

QUESTION E I G H T C3Hg + 5 0 ,

(Question p54)

(SFEE)

* 3C0, + 4H,0

QUESTION NINE (a)

(Question p55)

(SFEE)

Spectator ions. Not directly involved in the reactor or the oxidation number does not change in the reaction.

(b)

Reduction half equation: Oxidation half equation: Balanced equation:

MnO 4 " + 8H + + 5e" -> Mn 2+ + 4 H 2 0 Fe 2+ Fe 3+ + e"

MnO 4 " + 8 H + +5Fe 2 + -> Mn 2 + + 4 H 2 0 + 5Fe 3+

(c)

(i) (ii)

+6. +4.
> C H 3 C H 2 C H I C O O H + 4H* + 4E"

(d)

CH3CH2CH2CH2OH + H2O

(e)
(f)

Cr2O72"+ 14FT + 6e
2Cr 2 0 7 2 ' + 16H* +

* ICxs* + 7H,0
3CHtiCH2CH2COOH+4Cr3' + 11H2O

^ ^ ^

Answers - Oxidation-Reduction Reactions (AS90311) QUESTIONEIGHTEEN(Question p60) (a) (b) A soluble or molten substance which is capable of carrying a charge. 2Cl"(aq) * Cl2(S) + 2e".

113

(SFEE)

QUESTION ELEVEN

(Questionp55)

(SFEE)

h
Nail (cathode)

C u anode

-CuSO4(J4)
-beaker

QUESTION TWELVE (a)

(Question p56)

(SFEE)

One of the following points is required: Mg gains 0 ; oxidation number of Mg increases. Ag S + 2e" 2Ag + S * Ag* + e" *S 2 ' > 2Ag* + S2"

(b)

(i) (ii) (iii)

(c)

Cr 2 O 7 2- - orange
3 +

Cr (d) (i)

- green. CH3CH2OH + H2O Cr2O7 " + 14H* + 6e'

2

* CH3COOH + 4H* + 4e " * 2Cr3* + 7H 2 0 > 3 C H 3 C 0 0 H +4Cr3* + 1IH 2 O

(ii) (iii) (e) (i)

3CH 3 CH,OH + 2Cr 2 0 7 2 " + 16H*

Al readily oxidises to Al 2 O 3 . Oxide layer is tightly held and electrolysis is necessary to remove it. Alumina/bauxite from Australia.

(ii)

(iv) (v)

Refer to above diagram. One of the following points is required: cans; aluminium window frames.

(vi) (vii)

Lightweight. One of the following points is required: conducts; malleable; ductile; shiny.

QUESTION THIRTEEN (a)

(Questionp57)

(SFEE)

One of the following points is required: nitrogen dioxide; NO2.

(b)

Copper (Il) ion/cupric. Cu2*.

(c) (d)

Cu

* Cu2* + 2e" > N O 2 + H2O

N0 3 ' + 2H+ + e

QUESTION FOURTEEN (a) (b)

(Question p57)

(SFEE)

The solution will turn blue. Oxidation - Cu Reduction - Ag*+e" * Cu2* +2e" * Ag > 2Ag + Cu2"(aq)

(c)

Cu + 2Ag"(aq)

115 Answers - Oxidation-Reduction Reactions (AS90311) (d) Ag-+1 N-+5

0--2
(e) Oxidant - Ag+ Reductant - Cu (f) Iodine.

QUESTION FIFTEEN

(Question p58)

(b)

Reaction One: Reaction Two:

2 H , 0 + 2e" - 2 0 H +H 2 2 -> Cl 2 + 2e"

(c)

Gas A is chlorine. The negative chloride ions are attracted to the positive electrode (the anode). Oxidation occurs at the anode; the chloride ions are oxidised to form chlorine gas.

QUESTION SIXTEEN (a)

(Question p58)

(SFEE)

graphite electrode

ft
mo*en magnesium chloride

116 (b) (c) (d) (e) (f)

Answers - Oxidation-Reduction Reactions (AS90311) Left Hand. Right Hand. 2 a+2e-

In the molten state the ions are able to move and conduct an electric current. They are inert.

QUESTION SEVENTEEN (a) (b) Fe2O3 + 3 C 0 Iron - +3. Oxygen - -2. (c)

(Question p59)

(SFEE)

* 2Fe + 3 C 0 2

One of the following points is required: endothermic; high activation energy.

(d)

The following two points are required: Fe 2 O 3 + 3 H2SO4 Fe + H, SO j

2 4

* Fe 2 (SO 4 ) 3 + 3 H 2 O; FeSO + H , .
4 2

(e)

(i) (ii) (iii) (iv) (v)

Mg Fe 2+ +2e"

> Mg2' + 2e" Fe * Mg2" + Fe

Mg + Fe " Magnesium.

The following two points are required: expense of magnesium - would need a lot of magnesium and a reactive metal is difficult to make. expense of sulfuric acid - would need to use large amounts of sulfuric acid. > 2HC1

(f) (g)

H2+Cl2

One of the following points is required: ZnO; CuO.

(h)

SiO2 or S O , . Acidic oxide will not react with an acid.

Answers - Oxidation-Reduction Reactions (AS90311) QUESTION E I G H T E E N (a) (b) (c) Purple. The H+ from the acid is necessary to remove the O atoms and form water. Fe24 * Fe3*+e" (Question p60)

117

(SFEE)

QUESTION NINETEEN (a) (i) (ii)

(Question p60)

(SFEE)

B.
One of the following points is required: KCl; CuSO
4

(iii) (iv)

A. Electrode A - Anode Electrode B - Cathode 2 Cl+2e" 2H 2 0+2e" > H+20H

(b)

(i) (ii)

(c) h

C u anode

6
(Question p61)

spoon (cathode)

, CuSO 4 l a q l -beaker

QUESTION TWENTY (a) (b)

(SFEE)

Unreacted Hydrogen gas. Oxidant - oxygen Reductant - hydrogen.

(c)

The following points are required: H 2 + 20H" 2 H 2 0 + 2e"; > O 2 + 2 H 2 0 + 4e" 4 0 H ' .

118 Answers - Oxidation-Reduction Reactions (AS90311) (d) (e) 2H 2 + O 2 2H20

One of the following points is required: chemical energy is converted directly into electrical energy, not chemical to heat to mechanical to electrical; little energy is lost as heat or noise.

(f)

Lead accumulator batteries are very heavy and weight is restricted on space missions.

QUESTION TWENTY-ONE (a)

(Question p61)

(SFEE)

Two of the following points are required: potassium permanganate; potassium dichromate; hydrogen peroxide.

(b)

Dilute sulfuric acid. Sulfate ions are stable or not oxidised.

QUESTION TWENTY-TWO (a)

(Question p62)

(SFEE)

One of the following points is required: aluminium oxide is an amphoteric oxide; aluminium oxide dissolves in aqueous sodium hydroxide. * Al > 0,+4e"

(b)

Cathode - Al3*+3e" Anode - 20 2 "

(c)

One of the following points is required: cryolite lowers the temperature needed for the process; acts as a solvent; lowers melting point.

QUESTION TWENTY-THREE (a)

(Question p62)

Reduces. The oxidation number of Mn in MnO4" is +7 and in Mn 2+ it is +2. This reduction in oxidation number means that it has been reduced. MnO4" is the oxidant. Fe 2+ is the reductant. Oxidation: Reduction:
Fe2*(aq)

(b) (c)

>

Fe3+(a4)

+ e~ M n 2 t w + 4H,0

Mn04~(aq,

+ 8H* + 5e"

(d)

5Fe 2 * + M n O 4 " +8H~ -> 5Fe 3 " + Mn 2 * + 4 H ; 0

119 (e)

Answers - Oxidation-Reduction Reactions (AS90311) The original solution is purple due to the MnO4" present. As the reaction occurs Mn2* is produced which is colourless, so the solution turns colourless. It may turn slightly orange due to Fe3* formation. Fe 2+ is very pale green so this hardly affects the observation.

Species to be mixed

Does a reaction occur? (yes/no)

If a reaction occurs, describe what would be observed.

If a reaction occurs, write a balanced equation for the reaction.

Cl 2 +2e" - 2
(i) C l 2 ( a q ) + B r (aq)

Yes

Colourless solution turns brown

C 1

2Br" Br2 +2e" >

2
( a q

+2Br' ( a q ) - Br2(]) +

2Cl"(aq)

(ii)

Cl'(aq) +

I2(aq)

No

QUESTION TWENTY-FOUR (a) (i) (ii) (b) +4 +6

(Question p63)

S02(aq)+2H20(1)-> SO42^4) +4H* +2e^(aq)

+ 2 e

' ->2()
SO
2 4

(C)

S 0 2 ( a q ) + 2H 2 0 ( 1 ) + I 2(aq)

^a,,

+ 4H + + 2I

(aq)

(d)

Turn from orange (due to Cr2O72") to green (due to Cr3* produced). reduction of the orange Cr2O?2" to produce green Cr 3 ' . (Question p63)

The alcohol causes the

QUESTION TWENTY-FIVE (a) (i)

120

Answers - Oxidation-Reduction Reactions (AS90311) (ii) Refer to diagram above (i.e. movement is from +ve to -ve). Show anions to anode; cations to cathode. 20 2 ' ((aq) ^ > 02(g + 4e~ aq) 2 ( | 13() +3e" - Al ls \ s )

(b)

(i) (ii)

(c)

C(s)+02(cl->C0 The carbon and oxygen react to produce carbon dioxide gas, so the carbon electrode gradually erodes away and must therefore be eventually replaced.

QUESTION TWENTY-SIX

(Question p64)

Ag Ag + + e (oxidation occurring at the silver metal electrode - the anode.) > Ag" + e" -> Ag (reduction occurring at the spoon - the cathode.) The cathode (spoon) attracts the cations (Ag + ) which accept an electron from the cathode to form silver which plates the spoon.

QUESTION TWENTY-SEVEN (a) (0 (") (iii) (b) (i) (ii) (c) +1 -1 0

(Question p64)

2Cl"(aq) - C l 2 ( g ) + 2 e "

20 + 4H + + 2e_

Cl 2 + 2 H 2 0

Reaction (i) is an oxidation reaction: the oxidation number of chlorine increases from - 1 to 0; two electrons are produced. Oxygen is being oxidised because its oxidation number increases from - 2 (in the NaOCl) to 0 (in O 2 ). Chlorine is being reduced since its oxidation number decreases from +1 (in NaOCl) to - 1 (in NaCl).

(d)

1 ^ _ 2 Z 00 < O ^ v ! C N Vl "" Os I- w Vl O v V O O S SD ^ 00 - Cl I 0 B ^ u Z ^ Vi m w C - to N cn

U 5 O O Tt * m V O O O w V " W C Cl 00 _ < N > ** O Cl C / " N m -- Vl S a O^ V O N TJ C N N Tt m - V) C Tt - ( J " V 00 w (N A ^ < * S O v m ^ Tfr 1) m 00 C N m -

O O1

> C^ t-1

s ; 5 d Lm 00 - ^ O Vl V O C N

/5 fZ S -J S H .
-J B Q

H W

<

N (N fN OI ^ C O O (N Cl - V 00 as ci ^ vo w O Os "" _ S * v 00 C Vl C ci Tt N N 0 1 vC X 00 ^ CJ C N " 00 w N Vi "" Cl so Tt 00 3 C N <= ot V Os w ci - < S O < & C N V Tt O I^- O v 2 3 vS O O 00 00 (N - /> Tt ^ C N ^ C N a O O v -. W 00 VI - "" C N Tt Tt * 5 V Os O w Tf Sc O N a V O O ^ Tf . Vl * O 2 I- Tt < N ^ ^ C Vl Tt O 1 N O Tt C N Vl V O (N Z 5^ N Tf ^ C C N Ul t 1 00 I- ^ C r^ I- Tt N C N Tt Tf

. O LJV rf f" C E I^ O V O Vl C N ) 1 Tt -. I^ = S O v Vi V O Os C N v O V O QC N ~ 00 w Vi O v C N

S W Os tu O v Tt Vl tr^ tN V O Vi Os C

S CJ Tt ) E C N CI ] VI < 5 V O Vi O v C N V O Os ^ < to N V O S ^ _ fc 5? V O I 5 - li^ C l ^ C N ~ Z r^ Cl (Tl O v C N 2 -J O O N Cl Tt Cv C O N V O L % a Tt - v ^ C O N V J= > C N CJ Cl 00 w Tt N Vi Os C O v Vi

CL.
tt

"

>

5 Cl ~ O O v. " 00 C "* - N

O v m N j V O n O - 1/3 Tt O ^ O < N C N Tt m T 00 I P U (N t QJ M 9 O c N S O w O^ OrI ^O-' O B ^ 00 C N Tt C C N N Tt C 00 C Vl 0 * E ^ B ._ Tt U Cl C id Vl " CJ N ^ Cl. N /, v (-4 Cl O - N Os Os m Vl I Cl 00 w C N

57 La* 138.9

O O

102 No 255.0 U C N (N

FEEDBACK FORM
We invite you to give us feedback about this book. We want the revision guide to be as useful as possible so your constructive comments are very welcome. Probably the easiest way to do this is to go to our website www.rur.co.nz and complete a feedback survey form. Alternatively, this form can be posted back to PO Box 19-939, Woolston, Christchurch or faxed to (03) 376 4545. Emailed comments are also welcomed at rur@clear.net.nz.
1. Please identify the level and title of this book, e.g. Level 2 Physics.

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ORDER FORM
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Really Useful Resources P.O. Box 19-939 Woolston CHRISTCHURCH

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(03) 377 4545 (03) 376 4545 rur@clear.net.nz

Website: http://www.rur.co.nz

"I wish to order the following 2005 Revision Guides." Please y ^ the appropriate title. The price to schools is $12.50 per CODV. Price to individuals is $15.00 per copy. These prices include the cost of freight and handling. Please allow 5 - 7 days for delivery. NCEA Level 3 Accounting NCEA Level 3 Economics NCEA Level 3 Calculus NCEA Level 3 Statistics and Modelling NCEA Level 3 English NCEA Level 3 Biology NCEA Level 3 Chemistry NCEA Level 3 Physics NCEA Level 3 Geography NCEA Level 3 History (New Zealand Topics) NCEA Level 3 History (England Topics) NCEA Level 3 Classical Studies (Roman Topics) NCEA Level 3 Classical Studies (Greek Topics) NCEA Level 2 Accounting NCEA Level 2 Economics Check out www.rur.co.nz. Orders and inquiries can now be made through the website. Schools should use a purchase order number, VISA/Mastercard is also acceptable (please include name, card number and expiry date). These titles are also available through Whitcoulls, Dymocks, Paper Plus, some Books and More stores and other good booksellers. _ _ _ _ NCEA Level 2 English NCEA Level 2 Mathematics NCEA Level 2 Biology NCEA Level 2 Chemistry NCEA Level 2 Physics NCEA Level 2 Geography NCEA Level 2 History NCEA Level 1 English NCEA Level 1 Mathematics NCEA Level 1 Science NCEA Level 1 Accounting NCEA Level 1 Economics NCEA Level 1 Geography NCEA Level 1 History

ORDER FORM
Date: Please make cheques payable to: Name: Address:.
Really Useful Resources P.O. Box 19-939 Woolston CHRISTCHURCH

Ph Fax Phone: email: E-mail:

(03) 377 4545 (03) 376 4545 rur@clear.net.nz

Website: http://www.rur.co.nz

"I wish to order the following 2005 Revision Guides." Please ^ the appropriate title. The price to schools is $12.50 per copy. Price to individuals is $15.00 per copy. Theseprices include the cost of freight and handling. Please allow 5 - 7 days for delivery. NCEA Level 3 Accounting NCEA Level 3 Economics NCEA Level 3 Calculus _ NCEA Level 3 Statistics and Modelling NCEA Level 3 English NCEA Level 3 Biology NCEA Level 3 Chemistry NCEA Level 3 Physics NCEA Level 3 Geography NCEA Level 3 History (New Zealand Topics) NCEA Level 3 History (England Topics) NCEA Level 3 Classical Studies (Roman Topics) NCEA Level 3 Classical Studies (Greek Topics) NCEA Level 2 Accounting NCEA Level 2 Economics Check out www.rur.co.nz. Orders and inquiries can now be made through the website. Schools should use a purchase order number. VISA/Mastercard is also acceptable (please include name, card number and expiry date). These titles are also available through Whitcoulls, Dymocks, Paper Plus, some Books and More stores and other good booksellers. NCEA Level 2 English NCEA Level 2 Mathematics NCEA Level 2 Biology NCEA Level 2 Chemistry NCEA Level 2 Physics NCEA Level 2 Geography NCEA Level 2 History NCEA Level 1 English NCEA Level 1 Mathematics NCEA Level 1 Science NCEA Level 1 Accounting NCEA Level 1 Economics NCEA Level 1 Geography NCEA Level 1 History