S347 Metals and Life

Are you ready for S347?

Contents
1 Introduction 2 Suggested prior study 3 Key concepts for S347 3.1 Atomic structure and the Periodic Table 3.2 Molecules and chemical bonding 3.3 Chemical reactions 3.4 The solid state crystal lattices 3.5 Chemical implications of the second law of thermodynamics 3.6 Spectroscopy 3.7 Biological concepts 3.8 Suggested further reading 4 Mathematical skills 5 Other skills 5.1 Basic study skills 5.2 Writing skills 6 Self-assessment questions 7 Answers to the self-assessment questions 1 2 2 2 3 3 3 4 4 5 5 5 5 5 6 6 11

Introduction

If you are intending to study S347, you will want to make sure that you have the necessary background knowledge and skills to be able to enjoy the course fully and to give yourself the best possible chance of completing it successfully. Please read through these notes carefully, and work through the self-assessment questions given in Section 6. You will find this a useful exercise, even if you have already studied other Open University Science courses and have completed the recommended prior courses for S347. Working through these questions will serve as a reminder of some of the facts, skills and conceptual knowledge, which is assumed you will bring with you from earlier courses. If you are coming to S347 without having studied the recommended prior courses, then it is essential that you establish whether or not your background and experience give you a sound basis on which to tackle the work. If you find that you have difficulty in answering a significant number of the self-assessment questions, you are advised not to study S347 without first completing the study of the recommended prerequisite courses. We advise you to seek further help and advice on the recommended prior courses
Copyright 2009 The Open University WEB 01420 5 1.1

from a Science Staff Tutor at your Regional/National Centre, especially if, after working through these notes, you are not sure about whether or not S347 is the right course for you. At the end of Section 3 we have suggested sources of further reading that would help you to fill any gaps in your knowledge, or revise any areas of weakness.

Suggested prior study

The main recommended prior course is the Open University Level 2 chemistry course S205 The Molecular World. (Alternatively, the former courses S247 Inorganic Chemistry: Concepts and Case Studies and S246 Organic Chemistry are acceptable.) If you have studied S205, it is likely that you have also studied a Level 1 Science Course (S104 or S103). Many concepts from the biology and chemistry parts of that course are developed further in S347.

Key concepts for S347

S205 includes a study of the chemistry of the typical (main-Group) elements. S347 continues a study of the chemistry of the elements by looking at the varied and versatile chemistry of the transition elements, in particular the crucial role they play in living systems. Some of the same concepts are used, and many new ones are introduced. Topics covered in S347 include the chemistry of the transition metals, focusing on the synthesis, stereochemistry, oxidation states, bonding, magnetic properties and thermodynamics of both simple compounds and of complexes. The course looks in particular at the essential role that metals play in life, looking closely at how organisms acquire metals and how they are transported and stored. This is extended to include some of the key biological processes that include metals, as well as topics in medicinal coordination chemistry, and techniques required to study transition metals and biologically important metal coordination complexes. The key concepts given below have been introduced in S205 or in S104 (or S103): a basic understanding of these concepts is essential for S347. Many of them are briefly described again and developed further in the S347 course materials. Self-assessment questions amplifying and illustrating a selection of this list of topics are given in Section 6. You should be able to establish the level of understanding needed to study this Course by working through them. The answers to the questions are given in Section 7.

3.1 Atomic structure and the Periodic Table

The electronic configuration of the elements. Atomic orbitals: s, p, d and f. Electron spin. The Periodic Table: the names of the elements. Trends in bonding, covalent and ionic radii, electronegativity and ionisation energies. Radioactivity, half-life, chain-reaction, - and -radiation. (SAQ 1)

3.2 Molecules and chemical bonding

Covalent bonding by sharing electron pairs: single, double and triple bonds. Ionic bonding by electron transfer. Lewis structures and resonance structures of molecules and ions. Multicentre bonding for example diborane, B2H6. Coordinate (dative) bonding and coordination compounds. Ligands and simple metal complexes monodentate, bidentate, tridentate, tetradentate and hexadentate ligands. The shapes of molecules valence-shell electron-pair repulsion theory. Centre of symmetry. Chirality. Molecular orbitals: bonding and antibonding, and . The relationship between the overlap of atomic orbitals and the separation of the bonding and antibonding orbitals. Molecular-orbital energy-level diagrams of diatomic molecules and simple polyatomic molecules (e.g. H2O). The properties of metals and of non metals. The nomenclature of simple organic molecules. (SAQs 27)

3.3 Chemical reactions

Chemical equations. Molar quantities. Oxidationreduction (redox) equations. Standard electrode potentials. Oxidation states (oxidation numbers). Equilibrium and equilibrium constant. Acids and bases pH, strong and weak, and their reactions. (SAQs 79)

3.4 The solid state crystal lattices

Close-packing of spheres (cubic close-packing and hexagonal close-packing). Octahedral and tetrahedral holes in close-packed lattices. The body-centred cubic lattice and the structures of metals. Unit cells. Ionic solids the sodium chloride, caesium chloride, fluorite and corundum lattices. Ionic radius. Defects in crystals Schottky and Frenkel defects. (SAQ 10)

3.5 Chemical implications of the second law of thermodynamics

The second law of thermodynamics: for a natural (a spontaneous) process in an isolated system, S total > 0 . The definition of G (the free energy change or the Gibbs function):

G = H T S
The criterion G < 0 for a spontaneous reaction (at constant temperature and pressure).
Standard molar enthalpies ( H m ), entropies ( S m ) and free energies ( G m ).

The standard molar enthalpy change for a chemical reaction:

H m (reaction) = H f (products) H f (reactants)

The standard molar change in entropy for a chemical reaction ( S m ):

S m (reaction) = S m (products) S m (reactants)

The standard molar free energy change for a chemical reaction:

G m (reaction) = G f (products) G f (reactants)

The relationship of the standard molar free energy change ( G m ) to the equilibrium constant (K):

G m = 2.303 RT log K
The relationship of the standard molar free energy change ( G m ) to the standard redox potential E :

G m = nFE
(F = 96 485 Cmol1) (SAQs 11 13)

3.6 Spectroscopy
The electromagnetic spectrum. Wavelength (), frequency () and wavenumber (). The relationships E = h (where E is the energy of a photon), = c, and = 1/. The rotational and vibrational spectra of simple molecules. Infrared and Raman spectra. Molecular structure the effect of symmetry on group frequencies. Nuclear magnetic resonance spectroscopy. Mass spectrometry. (SAQs 14 18)

3.7 Biological concepts

The three fundamental attributes of living things; metabolism, growth and reproduction. The fundamental similarities between all organisms at the cellular and biochemical level. The differences between eukaryotic and prokaryotic cells. The biochemical building blocks of living things and the relationship between structure of a variety of biological molecules and the functions they carry out in the cell/organism. The importance to the cell/organism of metabolic processes including photosynthesis, glucose oxidation and protein synthesis. To recognise that enzymes are proteins that catalyse biochemical reactions, and all organisms rely on enzymic reactions for their survival. The basic structure of nucleic acids.

(SAQs 19 25)

3.8 Suggested further reading

S205 The Molecular World (The Open University). This is the major recommended prerequisite for this Course. If you have not studied S205, you should contact your Regional Enquiry Service, and they will be able to tell you where you can see reference copies of the Books. There are also many good general inorganic textbooks, for example: P. Atkins, T. Overton, J. Rourke, M. Weller, Armstrong, Inorganic Chemistry, (2006), Fourth Ed, Oxford University Press. C. Housecroft and A. G. Sharpe, Inorganic Chemistry, (2007), Prentice Hall.

Mathematical skills

Only basic mathematical skills are needed, such as the ability to carry out simple calculations, plot graphs and obtain information from them, and to calculate chemical formulae from experimental analytical data.
Useful reading: A. Northedge, J Thomas, A Lane and A Peasgood, (1997), The Sciences Good Study Guide, The Open University.

This contains a maths reference section.

Other skills

5.1 Basic study skills

To organise time for study, learning to pace study, effective reading: to extract relevant information and data from scientific texts, diagrams and accounts.
Useful reading: The Sciences Good Study Guide.

5.2 Writing skills

To write coherently and structure arguments, and to present a scientific account with appropriate diagrams.
Useful reading: The Sciences Good Study Guide.

Self-assessment questions

SAQ 1
This question refers to the Periodic Table. (a) Give the electronic configurations of the elements in Group 14 (IV): C, Si, Ge, Sn and Pb. (b) Are the elements in Group 14 (IV) metals or non-metals? (c) In which Group do the atoms have the largest covalent radius of any in their Period? (d) In which Period do the atoms have the largest covalent radius in any of their Group? (e) In which Group do the atoms have the largest electronegativity in their Period? (f) In which Period do the atoms have the highest electronegativity in their Period? (g) Which element(s) in the 2nd period have/has a first ionisation energy lower than the element that precedes it/them?

SAQ 2
Draw Lewis structures and structural formulae for the following species: note if resonance structures are needed. (a) (b) (c) (d) (e) Silicon tetrafluoride, SiF4; nitrogen trifluoride, NiF3; sulfur hexafluoride, SF6; the sulfite ion, SO32; diborane, B2H6.

SAQ 3
Draw structural formulae and explain the structures of: (a) The tetraammino copper(II) complex ion ([Cu(NH3)4]2+); (b) The bis-ethylenediamine copper(II) complex ion [Cu (ethylenediamine)2]2+; ethylenediamine is NH2CH2CH2NH2.

SAQ 4
The molecular orbital energy-level diagram for the dinitrogen molecule, N2 (derived from the N 2s and 2p levels only) is shown in Figure 1.

Figure 1 The molecular orbital energy-level diagram for dinitrogen, N2.

Account for the appearance of the molecular-orbital diagram in terms of the overlap of the 2s and 2p energy levels. What is the bond order of the N2 molecule? Why is it acceptable to consider only the 2s and 2p energy levels? Carbon monoxide (CO) is isoelectronic with dinitrogen. Explain how their molecular-orbital energy-level diagrams will differ.

SAQ 5
(a) What are the important differences between the type of bonding present in isolated molecules and that present in solids? (b) What type of bonding is predominant in: (i) sodium chloride, (ii) diamond, (iii) lithium metal?

SAQ 6
State some of the properties of metals and non-metals.

SAQ 7
(a) Calculate the oxidation numbers of the metal atoms in the species: Cr2O72, VO2+, CrO2 and CrO42, and of Cl in OCl.

(b)

Write balanced equations for the reactions: (i) between dichromate ions (Cr2O72) and vanadium(III) (V3+) ions in acidic aqueous solution, when VO2+ ions and chromium(III) ions are produced; (ii) between sodium hypochlorite (NaOCl) and CrO2 ions in basic aqueous solution (OH), when CrO42 and chloride ions are produced.

(c)

Describe the redox changes involved for the reactions in part (b).

SAQ 8
Potassium permanganate in acid solution oxidises thallium(I) to thallium(III) if excess fluoride ions are present. 20.00 cm3 of a solution of 0.025 molar (mol dm3) KMnO4 reacts with 10 cm3 of 0.1 molar thallium(I) solution. Calculate the number of moles of thallium(I) that react with one mole of permanganate, and hence the oxidation number of the manganese in the product. Write a balanced equation for the reaction (in the products, the manganese is a six-coordinate fluoride complex and the oxygen appears in water).

SAQ 9
Acetic acid is a weak acid with a dissociation constant (Ka) in aqueous solution of 1.8 105 mol dm3. What is the concentration of H+ ions in a 0.01 molar solution? What is the pH of this solution? Assume that [H+] << 0.01 mol dm3.

SAQ 10
(a) Calculate the number of atoms in the unit cell of a face-centred cubic lattice of a metal. (b) Calculate the number of tetrahedral holes and the number of octahedral holes in the unit cell of a face-centred cubic lattice of a metal. (c) Describe the structures of the crystalline lattices (i) to (iii) in terms of the filling of holes in a close-packed lattice. (i) NaCl, (ii) CaF2, (iii) -alumina (Al2O3)

SAQ 11
For the water gas reaction: C(graphite)(s) + H2O(g) = CO(g) + H2(g)
1 1 1 H m = 131.3 kJ mol and S m = 133.9 J K mol

(a) (b)

Does the reaction take place using steam at 100 C? Does the reverse reaction take place at 100 C?

(c) What is the minimum temperature at which the water gas reaction will occur?

SAQ 12
Use the thermodynamic data given below to determine whether: (a) (b) sodium chloride will dissolve in water at room temperature (25 C), and diamond will react with oxygen at 100 C. NaCl(s) Na+(aq) Cl(aq) C(diamond) O2(g) CO2(g)
1 H f / kJmol

411.2

240.1

167.2

1.9 2.4

393.5

S / J K mol 1

72.1

59.0

56.5

205.1 213.7

SAQ 13
For the reaction of aluminium metal with an acid, Al(s) + 3H+(aq) = Al3+(aq) +
3 2

H2(g)

1 G m = 485 kJ mol

(a) Give this equation in the usual form for a standard redox potential and calculate the value of E (Al3+|Al). (b) Does the value you have obtained suggest that aluminium is a powerful or weak oxidising or reducing agent?

SAQ 14
Convert the frequency 1 1013 Hz (Hz = 1 s1) into its equivalent in (a) kilojoules per mole, (b) metres and (c) wavenumbers (cm1). (Planck constant, h = 6.626 1034 J s; Avogadro constant, NA = 6.022 1023 mol1; speed of light, c = 3.0 108 m s1.)

SAQ 15
Two of the absorptions in spectra of the molecule OCS are at 1.216 1010 Hz and 2.580 1013 Hz. (a) (b) What wavelengths and wavenumbers correspond to these frequencies? In what regions of the electromagnetic spectrum do these frequencies lie?

(c) What type of molecular energy change is likely to be responsible for each of these absorptions?

SAQ 16
Which of the following molecules will have a vibration that is active in (a) the infrared spectrum, (b) the Raman spectrum? N2, HF, HCl, Br2 and NO

SAQ 17
The 13C n.m.r. spectrum in Figure 2 was obtained from a compound of formula C7H14O. Values of between 0 and 55 p.p.m. correlate to aliphatic carbons, and values in the range 175225 p.p.m. correlate to aldehyde or ketone groups. The

labels d, t and q on the spectrum refer to doublets, triplets and quartets produced by coupling to the hydrogen atoms attached to each particular carbon atom. Identify the structure of the unknown compound.

Figure 2 The 13C n.m.r. spectrum of an unknown compound.

SAQ 18
What features distinguish a prokaryotic cell from a eukaryotic cell?

SAQ 19
Certain molecules found in cells often have hydrophilic and hydrophobic regions within their structure. Comment on how such a molecule would interact with water.

SAQ 20
Proteins are formed from the polymerisation of what kind of molecule?

SAQ 21
By means of a diagram, describe the generalised structure of an amino acid

SAQ 22
What is a peptide bond and how is it formed? Use a diagram in your answer.

SAQ 23
Which of the following statements about metabolism are true? (a) The conversion of ADP + Pi to ATP is coupled to energy-requiring reactions in the cell. (b) ATP is a carrier of chemical energy. (c) All the ATP produced in the cell by catabolic pathways is used in biosynthetic pathways. (d) Energy derived from the oxidation of glucose is packaged as ATP and used within minutes.

SAQ 24
State two reasons why photosynthesis is a vital process for life on Earth.

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SAQ 25
What is meant by the active site of an enzyme?

Answers to the self-assessment questions

SAQ 1 Answer
(a) C: Si: Ge: Sn: Pb: 1s22s22p2 1s22s22p63s23p2 1s22s22p63s23p63d104s24p2 1s22s22p63s23p63d104s24p64d105s25p2 1s22s22p63s23p63d104s24p64d104f145s25p65d106s26p2

(b) Tin and lead are metals; carbon and silicon are non-metals. Germanium shows both metallic and non-metallic properties. (c) Group 1 (I) (Li, Na, K, Rb and Cs). Across a Period, the contribution to the covalent radius due to the increasing nuclear charge dominates over the increase in size caused by adding outer electrons. (d) 6th Period (Cs to Rn). The increase in size as a result of adding the outer electrons predominates (Note Covalent radii are not known for many elements of the 7th Period, and are likely to be reduced by the lanthanide contraction.) (e) Group 17 (VII) (F, Cl, Br, I and At). Electronegativity is a measure of the power of an atom to attract electrons to itself when entering into chemical combination. This is most affected by the increasing nuclear charge across the Period. (f) The 2nd Period (Li, Be, B, C, N, O, F). The small size predominates over the increase in the nuclear charge on moving down a Group. (g) Boron and oxygen. The first ionisation energy of boron (801 kJ mol1) is less than that of beryllium (899 kJ mol1) because the electron being removed in beryllium is from the filled s orbital (Be Be+ + e is 1s22s2 1s22s2). The 2p orbital is less likely to be found close to the nucleus than the 2s, and therefore the electron can be removed more easily. The first ionisation energy of oxygen (1 314 kJ mol1) is less than that of nitrogen (1 402 kJ mol1) because the electron being removed from nitrogen is from a half-filled p orbital (p3 p2), whereas that being removed from oxygen is from a p orbital with two electrons (p4 p3). The electron being removed from oxygen is paired with another electron and is more easily removed than an electron in nitrogen where no electrons are paired, but all three have parallel spins.

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SAQ 2 Answer
F F Si F F

F FN F

F F

F S F F S F

F
F

O S O O

H B H

H H B H H

(a)

For SO32 there are three resonance hybrids:

O

Notice the two different depictions of the structure of SO32 a Lewis structure and three structural formulae for the resonance hybrids. In B2H6 each bridging atom is bonded to the two boron atoms by a three-centre two-electron bond.

SAQ 3 Answer
NH3 H3N (a) Cu NH3 NH3 (b)
2+

In both (a) and (b) the N\Cu bond is a coordinate bond. Ammonia is a monodentate ligand, whereas ethylenediamine is a bidentate ligand.

SAQ 4 Answer
With reference to the molecular orbital energy-level diagram for dinitrogen shown in Figure 1: the N 2s orbitals overlap to give 2sg and 2su molecular orbitals; the N 2pz orbitals overlap to give 2pg and 2pu molecular orbitals; the N 2px and N 2py orbitals overlap to give two degenerate pairs of molecular orbitals: 2pu and 2pg the 2sg and 2su (bonding and antibonding) orbitals and the 2pu and 2pu (bonding) orbitals are filled, and the 2pg and 2pu orbitals are empty. The bond order is (8 2)/2 = 6/2 = 3; and so N2 has a triple bond.

F F Si F F F

F N F F F

F F

H B H

H B H

H H

(b)

(c)

(d)

(e)

S O

S O

S O

H2C H2C

H2 N Cu N H2

H2 N N H2

2+

CH2 CH2

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We need consider only the 2s and 2p energy levels, because the 1s levels are much lower in energy and are not involved in bonding. Carbon monoxide differs from dinitrogen in that the 2s and 2p atomic orbitals on carbon and oxygen differ in energy. The atomic ionisation energies are C(2s) 26.6 1019 J, C(2p) 18.0 1019 J, O(2s) 45.6 1019 J and O(2p) 21.8 1019 J. These are to be compared with N(2s) 32.6 1019 J and N(2p) 23.3 1019 J. The molecular orbital diagram for CO is shown in Figure 3.

Figure 3 Orbital energy-level diagram for CO

The most significant effect is that the O 2p orbital falls between that of the C 2s and the C 2p. Because of this, the O 2p orbital of orientation interacts not only with the C 2p orbital but also with the C 2s orbital. Hence the 2p bonding molecular orbital is formed from not just the O 2p and C 2p orbitals, but also from the C 2s; similarly the 2su antibonding molecular orbital is not just formed from C 2s and O 2s orbitals, but also from the O 2p orbitals. This results in the energy of the 2p bonding molecular orbital being higher than in dinitrogen, and the energy of the 2su antibonding molecular orbital being lower than in dinitrogen. In CO the 2s bonding molecular orbital (5) is higher in energy than the 2p molecular orbitals (1). The net result is that the O 2p atomic orbitals contribute more to the bonding molecular orbitals than do the C 2s and C 2p atomic orbitals. Also in the N2 molecule, three of the six electrons come from each N atom. In CO four electrons are from the O atom and two from the C atom. Note also that N2 has a centre of symmetry, whereas CO does not. That is why the N2 molecular orbitals have subscript labels g or u, but those of CO do not.

SAQ 5 Answer
(a) In an isolated molecule the electrons are in well-separated discrete energy levels. In a solid the levels can be regarded as energy bands. The relative energies of bands containing electrons and empty bands, and their full or partial occupation by electrons, determine the type of solid metal, non-metal, semiconductor, ionic or covalent. (b) (i) Sodium chloride: ionic bonding; (ii) diamond: covalent bonding; (iii) lithium metal; metallic bonding.

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SAQ 6 Answer
Metals are the elements at the left-hand side of the Periodic Table and non-metals are those on the right-hand side. The most important property of a metal atom is that it will lose electrons to form a cation (positive ion) in aqueous solution, and that of a non-metal atom that it will gain electrons to form an anion (negative ion) in aqueous solution. This property is reflected in the standard redox potentials (a measure of the ease of electron gain), which are negative for metals (in general) and positive for non-metals. The bonding in metallic solids is delocalised metallic bonding. The bonding in non-metallic elements is covalent. Solid metals conduct heat and electricity; they are ductile and malleable. Solid non-metals are insulators.

SAQ 7 Answer
(a) Chromium +6 in Cr2O72; vanadium +4 in VO2+; chromium +3 in CrO2; chromium +6 in CrO42; chlorine +1 in ClO. (b) H2O(l) (c) (i) Chromium is reduced from an oxidation state of +6 to +3; vanadium is oxidised from oxidation state +3 to +4. (ii) Chlorine is reduced from an oxidation state of +1 to 1; chromium is oxidised from oxidation state +3 to +6. (i) Cr2O72(aq) + 2H+(aq) +6V3+(aq)+ = 2Cr3+(aq) + 6VO2+(aq) + H2O(l) (ii) 3ClO(aq) + 2CrO2(aq) + 2OH(aq) = 3Cl(aq) + 2CrO42(aq) +

SAQ 8 Answer
The number of moles of MnO4 is 0.025 mol dm 3 20 dm3 . 1 000

(since 1dm3 = 1 000 cm3 )

The number of moles of Tl+ is 0.1 mol dm 3 10 dm3 = 1 10 3 1 000

Therefore, the ratio of Tl+: MnO4 = 1 103: 5 104 = 0.001 : 0.000 5 = 2 : 1. The thallium changes oxidation state by +2. If two moles of thallium(I) are needed to reduce 1 mole of MnO4, then the oxidation state of the manganese must change by 2 2 = 4. In MnO4 the manganese is in oxidation state +7, therefore in the product it is + (7 4) = +3. The reaction is represented by the equation MnO4 + 2Tl+(aq) + 6F(aq) + 8H+(aq) = MnF63(aq) + 2Tl3+(aq) + 4H2O(l)

SAQ 9 Answer
The acid dissociation constant for acetic acid (HAc) is given by the expression

Ka =

[H + (aq)][Ac (aq)] [HAc]

The concentrations of H+ and Ac are equal (say x). Therefore

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1.8 105 mol dm3 =

x2 0.01 mol dm 3 x

As x is very small, (0.01 x) 0.01. Therefore x2 = 1.8 105 mol dm3 0.01 mol dm3 = 1.8 107 mol2 dm6 Hence, x = 4.24 104 mol dm3. The pH of the solution is given by pH = log (4.24 104) = 3.37

SAQ 10 Answer
(a) In a face-centred cubic (cubic close-packed, ccp) lattice there is an atom at each of the eight corners of a cube and an atom in each of the six faces. An atom at the corner of a cube is shared by eight cubes (eight cubes meet at a of an atom at each corner. As there corner); therefore each unit cell contains 1 8 are eight corners, the total number of atoms at corners is 8
1 8

= 1.

An atom at the centre of a face of a cube is shared by two cubes (two cubes meet of an atom in each face. As there at a face); therefore each unit cell contains 1 2 are six faces, the total number of atoms in faces is 6
1 2

= 3.

Therefore the total number of atoms in the unit cell is 1 + 3 = 4. (b) There is a tetrahedral hole between each corner atom and the atoms in the centres of the three adjacent faces. As there are eight corner atoms, there are eight such tetrahedral holes and they are all within the unit cell. Therefore the number of tetrahedral holes is eight. There is an octahedral hole at the centre of a face-centred cube, where the six atoms in the six faces meet. There is also an octahedral hole in the centre of each of the twelve edges of the cube. This is where two atoms at corners and two in adjacent faces meet two other atoms in faces of adjacent unit cells. These holes are shared by four unit cells (four cubes meet at an edge), so the total number of holes in edges is 12 1 = 3 . The total number of octahedral holes in the unit 4 cell is therefore 1 + 3 = 4. (c) (i) NaCl is a cubic close-packed (ccp) array of Cl ions with Na+ ions in all the octahedral holes. It would also be true to describe it as a ccp array of Na+ ions with Cl ions in all the octahedral holes, although the Cl ions are much larger than the Na+ ions. The convention is to describe the array in terms of the largest ion (here Cl). (ii) CaF2 is a ccp array of Ca2+ ions, with F ions in all of the tetrahedral holes. Note that here it is the cations (Ca2+) forming the close-packed array. (iii) -Alumina (Al2O3) is a hexagonal close-parked (hcp) array of O2 ions, with Al3+ ions in two-thirds of the octahedral holes.

SAQ 11 Answer
(a) For a reaction to be thermodynamically feasible, G H (= m m T S m ) should be negative.
Assuming that H m and S m are independent of T, G m at 100 C is given by

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1 1 G m = [131.3 (373 133.9)/1 000] kJ mol = 81.35 kJ mol

This is positive, so the reaction will not take place. (Note the factor of 1 000; this 1 1 is needed because S m is given in J K mol .)
1 G (b) m for the reverse reaction will be 81.35 kJ mol . This is negative, so the reaction is thermodynamically possible, but will only occur in practice if it is also kinetically favourable.

(c)

is, when H m = S m . Hence this occurs at a temperature

The reaction becomes thermodynamically possible when G m = 0, that

T=

H m S m
131.3 1 000 J mol 1 = 980.6 K 133.9 J mol 1 K 1

Hence T =

SAQ 12 Answer
(a) (i) The reaction is NaCl(s) = Na+(aq) + Cl(aq). G m can be calculated using the equation
G m = H m T S m again assuming H m and S m to be independent of T.

Now:
H m (reaction) = H f (products) H f (reactants)

= [240.1 167.2 (411.2)] kJ mol 1 = +3.9 kJ mol1

and
S m (reaction) = S m (products) S m (reactants)

= [59.0 + 56.5 72.1] kJ mol 1 = +43.4 JK 1 mol 1

1 At 25C (= 298 K), G m = H T S = [3.9 (298 43.4)/1 000] kJ mol

= 9.0 kJ mol 1

G m is negative, so the reaction is thermodynamically favourable at

25 C (= 298 K) (b) The reaction is C(diamond)(s) + O2(g) = CO2(g)
H m (reaction) = H f (products) H f (reactants)

= [393.5 1.9 0] kJ mol1 = 395.4 kJ mol1

and
S m (reaction) = S m (products) S m (reactants)

= [213.7 2.4 205.1] J K 1 mol 1 = 6.2 J K 1 mol1

At 100 C (=373 K), G = H T S = [395.4 (373 6.2)/1 000] kJ mol1 = 397.7 kJ mol 1

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This is a large negative value, so the reaction is thermodynamically very favourable. In fact, it does not occur, which means that diamond is kinetically stable in oxygen at 100 C.

SAQ 13 Answer
Standard redox potentials are reduction potentials by definition, so the equation 1 must be transposed from right to left. For this reaction G m = 485 kJ mol . To obtain the equation in the usual form, you must recognise that H2(g) = H+ + e (where e = an electron). Therefore the equation becomes: Al3+(aq) + 3H+(aq) + 3e = Al(s) + 3H+(aq). Eliminating the H+ from both sides of the equation gives Al3+(aq) + 3e = Al(s). Now G m = nF E . Therefore 485 103 J mol1 = (3 96 485 C mol1) E ; that is, E = 1.68 V (1 V = 1 J C1) (b) This is a high negative potential (cf. E (Zn2+| Zn) = 0.76 V and E (Mg2+ | Mg) = 2.36 V), so aluminium is expected to be a powerful reducing agent.

SAQ 14 Answer
(a) The energy of one photon is given by the equation E = hv, therefore the energy per mole is:

E = hnN A = (6.626 10 34 J s) (1 10 3 s 1 ) (6.022 1023 mol 1 ) = 3 990.18 J mol 1 = 3.990 kJ mol 1

(b) (c)

= c / v = (3 108 m s 1)/(1 1013 s 1 ) = 3 105 m

= 1/ = 1/(3 105 m) = 1/(3 103 cm) = 333.33 cm 1

SAQ 15 Answer
(a)

= c/v and = 1/.

For 1.216 1010 Hz:

= (3 108 m s1)/(1.216 1010 103 s1) = 2.467 102 m,

And = 1/(2.467 cm) = 0.4054 cm1. For 2.580 1013 Hz: = (3 108 m s1)/(2.580 1013 Hz) = 1.163 105 m And = 1/(1.163 103 cm) = 859.8 cm1. (b) The absorption at 1.216 1010 Hz is in the microwave region, and that at 2.580 1013 Hz is in the infrared region. (c) The microwave transition is likely to be caused by a rotational change, and the infrared transition will be caused by a vibrational change in the molecule.

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SAQ 16 Answer
(a) Only those molecules in which the dipole moment changes during the vibration are infrared active: these are the heteronuclear molecules HF, HCl and NO. (b) Molecules that change their polarizability during vibration are active in the Raman spectrum. All diatomic molecules do this, so the vibrations of all the molecules are Raman active.

SAQ 17 Answer
There are seven peaks in the n.m.r. spectrum shown in Figure 1, so there must be seven non-equivalent carbon atoms present in the molecule. A peak at = 202 p.p.m. is indicative of an aldehyde or a ketone group. This peak is labelled as a doublet. Therefore the carbon atom producing this peak must have one attached hydrogen atom: that is, the functional group present is an aldehyde. The remaining six peaks all fall in the region occupied by aliphatic carbon atoms. Five of the peaks are labelled as triplets and one is labelled as a quartet. Therefore there must be five CH2 groups present and one CH3 group. The only way these seven groups can be put together to yield a molecule with satisfactory valencies is heptanal CH3CH2CH2CH2CH2CH2CHO. All the CH2 groups are non equivalent due to symmetry.

SAQ 18 Answer
The eukaryotic cell has a nucleus, and membrane bound organelles such as mitochondria, and chloroplasts. The prokaryotic cell lacks these, i.e. no clearly defined structures are visible under the microscope.

SAQ 19 Answer
The hydrophilic groups would interact with water, but the hydrophobic groups would interact with one another i.e. avoid water as far as possible, this determines the molecules three dimensional structure in water.

SAQ 20 Answer
Proteins are formed by polymerization of amino acids (a chain of amino acids is called a polypeptide).

SAQ 21 Answer
The generalised structure of an amino acid is shown below, where R is the variable side chain. The C carbon is linked to an amino group, a carboxylic acid group and a side chain.
H H R N C H C H O

SAQ 22 Answer
A peptide bond is the bond formed between two amino acid residues in a polypeptide. It is formed by the elimination of a water molecule between the amino group of one amino acid and the carboxyl group of another. The atoms within the box comprise the peptide group.
peptide bond H N H R CH O C N C O

H H peptide group

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SAQ 23 Answer
(a) False. The conversion of ADP + Pi to ADP is coupled to energy-releasing reactions. (b) True. ATP is a carrier of chemical energy in that it transfers energy between energy-releasing and energy-requiring reactions. (c) False. ATP is used in many processes other than biosynthesis, such as muscle contraction. (d) True. ATP is a short-lived energy store, typically being converted to ADP within a minute.

SAQ 24 Answer
Photosynthesis is essential for life on Earth because: it converts solar energy into chemical energy in sugars, which can be used to fuel all the energy-requiring processes of life it releases oxygen, which is required for respiration.

SAQ 25 Answer
The active site of an enzyme is the site at which a substrate binds and undergoes chemical modification.

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