Chemistry Core Concepts 2E

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Chemistry Core Concepts Brief contents Contents About The Authors 1 The nature of matter Chemical enquiry 1.1 Why study chemistry? Your degree Your career Your everyday life 1.2 Introduction to matter Classifying matter Interconverting matter 1.3 Atomic theory Law of conservation of mass Law of definite proportions From observation to theory 1.4 The structure of the atom Atomic mass 1.5 The periodic table of the elements The modern periodic table Naming the elements SUMMARY WHY STUDY CHEMISTRY? INTRODUCTION TO MATTER ATOMIC THEORY THE STRUCTURE OF THE ATOM THE PERIODIC TABLE OF THE ELEMENTS CHEMICAL ENQUIRY REVISITED KEY CONCEPTS AND EQUATIONS KEY TERMS REVIEW PROBLEMS ACKNOWLEDGEMENTS 2 The language of chemistry Chemical enquiry 2.1 Representations in chemistry Chemical formulae Structural formulae Three-dimensional structures Mechanistic arrows in chemical reactions 2.2 Nomenclature Naming inorganic compounds Naming organic compounds SUMMARY REPRESENTATIONS IN CHEMISTRY NOMENCLATURE CHEMICAL ENQUIRY REVISITED KEY CONCEPTS AND EQUATIONS KEY TERMS REVIEW PROBLEMS ACKNOWLEDGEMENTS 3 Measurement and chemical calculations Chemical enquiry 3.1 Fundamental skills Arithmetic operations Algebraic equations Graphical representations of data Expression of large and small numbers Exponents and logarithms 3.2 Units SI units Non-SI units Dimensional analysis 3.3 Measurement Precision and accuracy Significant figures Uncertainties SUMMARY FUNDAMENTAL SKILLS UNITS MEASUREMENT CHEMICAL ENQUIRY REVISITED KEY CONCEPTS AND EQUATIONS KEY TERMS REVIEW PROBLEMS ACKNOWLEDGEMENTS 4 Chemical reactions and stoichiometry Chemical enquiry 4.1 Chemical and physical change 4.2 Chemical equations Specifying states of matter 4.3 Balancing chemical equations 4.4 The mole 4.5 Empirical formulae Mole ratios from chemical formulae Determination of chemical formulae Determination of empirical formulae 4.6 Stoichiometry, limiting reagents and percentage yield Mole ratios in chemical reactions Limiting reagents Percentage yield 4.7 Solution stoichiometry The concentration of solutions Applications of solution stoichiometry Stoichiometry of solutions containing ions SUMMARY CHEMICAL AND PHYSICAL CHANGE CHEMICAL EQUATIONS BALANCING CHEMICAL EQUATIONS THE MOLE EMPIRICAL FORMULAE STOICHIOMETRY, LIMITING REAGENTS AND PERCENTAGE YIELD SOLUTION STOICHIOMETRY CHEMICAL ENQUIRY REVISITED KEY CONCEPTS AND EQUATIONS KEY TERMS REVIEW PROBLEMS ACKNOWLEDGEMENTS 5 Atomic energy levels Chemical enquiry 5.1 Characteristics of light Waves Wave-like properties of light Particle properties of light Absorption and emission spectra Atomic spectra Quantisation of energy Energy level diagrams 5.2 Properties of electrons 5.3 Quantisation and quantum numbers Principal quantum number (n) Azimuthal quantum number (l) Magnetic quantum number (ml) Spin quantum number (ms) The Pauli exclusion principle 5.4 Atomic orbital electron distributions and energies Orbital electron distributions Orbital energies 5.5 Structure of the periodic table The Aufbau principle and order of orbital filling Valence electrons 5.6 Electron configurations Electron–electron repulsion Orbitals with nearly equal energies Configurations of ions Magnetic properties of atoms Excited states 5.7 Periodicity of atomic properties Atomic radii Ionisation energy SUMMARY CHARACTERISTICS OF LIGHT PROPERTIES OF ELECTRONS QUANTISATION AND QUANTUM NUMBERS ATOMIC ORBITAL ELECTRON DISTRIBUTIONS AND ENERGIES STRUCTURE OF THE PERIODIC TABLE ELECTRON CONFIGURATIONS PERIODICITY OF ATOMIC PROPERTIES CHEMICAL ENQUIRY REVISITED KEY CONCEPTS AND EQUATIONS KEY TERMS REVIEW PROBLEMS ACKNOWLEDGEMENTS 6 Chemical bonding and molecular structure Chemical enquiry 6.1 Fundamentals of bonding Bond length and bond energy Unequal electron sharing 6.2 Ionic bonding 6.3 Lewis structures The conventions Building Lewis structures Resonance structures 6.4 Valence-shell-electron-pair repulsion (VSEPR) theory Two sets of electron pairs: linear geometry Three sets of electron pairs: trigonal planar geometry Four sets of electron pairs: tetrahedral geometry Five sets of electron pairs: trigonal bipyramidal geometry Six sets of electron pairs: octahedral geometry 6.5 Properties of covalent bonds Dipole moments Bond length Bond energy Summary of molecular shapes 6.6 Valence bond theory Orbital overlap Conventions of the orbital overlap model Hybridisation of atomic orbitals Multiple bonds SUMMARY FUNDAMENTALS OF BONDING IONIC BONDING LEWIS STRUCTURES VALENCE-SHELL-ELECTRON-PAIR REPULSION (VSEPR) THEORY PROPERTIES OF COVALENT BONDS VALENCE BOND THEORY CHEMICAL ENQUIRY REVISITED KEY CONCEPTS AND EQUATIONS KEY TERMS REVIEW PROBLEMS ACKNOWLEDGEMENTS 7 States of matter Chemical enquiry 7.1 The states of matter 7.2 Intermolecular forces Dispersion forces Dipolar forces Hydrogen bonds Binary hydrogen compounds 7.3 Gases Pressure (p) The gas laws The ideal gas equation Determination of molar mass Determination of gas density 7.4 Gas mixtures Daltons law of partial pressures Describing gas mixtures 7.5 Gas stoichiometry Summary of mole conversions 7.6 Liquids Properties of liquids Vapour pressure 7.7 Solids Magnitudes of forces Molecular solids Network solids Metallic solids Ionic solids Amorphous solids 7.8 Phase changes Supercritical fluids Phase diagrams SUMMARY THE STATES OF MATTER INTERMOLECULAR FORCES GASES GAS MIXTURES GAS STOICHIOMETRY LIQUIDS SOLIDS PHASE CHANGES CHEMICAL ENQUIRY REVISITED KEY CONCEPTS AND EQUATIONS KEY TERMS REVIEW PROBLEMS ACKNOWLEDGEMENTS 8 Chemical thermodynamics Chemical enquiry 8.1 Introduction to chemical thermodynamics Heat and temperature System, surroundings and universe Units 𝚫X: the change in X 8.2 The first law of thermodynamics Heat capacity The determination of heat 8.3 Enthalpy Standard enthalpy change Hesss law Standard enthalpy of formation Standard enthalpy of combustion Bond enthalpies 8.4 Entropy Entropy and probability Entropy and entropy change Factors that affect entropy 8.5 Gibbs energy and reaction spontaneity The sign of DG SUMMARY INTRODUCTION TO CHEMICAL THERMODYNAMICS THE FIRST LAW OF THERMODYNAMICS ENTHALPY ENTROPY GIBBS ENERGY AND REACTION SPONTANEITY CHEMICAL ENQUIRY REVISITED KEY CONCEPTS AND EQUATIONS KEY TERMS REVIEW PROBLEMS ACKNOWLEDGEMENTS 9 Chemical equilibria Chemical enquiry 9.1 Chemical equilibrium 9.2 The equilibrium constant, K, and the reaction quotient, Q Reactions at equilibrium Reactions not at equilibrium Equilibria involving gases The relationship between Kp and Kc Manipulating equilibrium constant expressions The magnitude of the equilibrium constant Equilibrium constant expressions for heterogeneous systems 9.3 Equilibrium and Gibbs energy The relationship between 𝚫rGө and K 9.4 How systems at equilibrium respond to change Le Châteliers principle Adding or removing a product or reactant Changing the pressure in gaseous reactions Changing the temperature of a reaction mixture Addition of a catalyst 9.5 Equilibrium calculations Calculating Kc from equilibrium concentrations Calculating equilibrium concentrations from initial concentrations SUMMARY CHEMICAL EQUILIBRIUM THE EQUILIBRIUM CONSTANT, K, AND THE REACTION QUOTIENT, Q EQUILIBRIUM AND GIBBS ENERGY HOW SYSTEMS AT EQUILIBRIUM RESPOND TO CHANGE EQUILIBRIUM CALCULATIONS Chemical enquiry revisited KEY CONCEPTS AND EQUATIONS KEY TERMS REVIEW PROBLEMS ACKNOWLEDGEMENTS 10 Solutions and solubility Chemical enquiry 10.1 Introduction to solutions and solubility 10.2 Gaseous solutions 10.3 Liquid solutions Gas–liquid solutions Liquid–liquid solutions Liquid–solid solutions 10.4 Quantification of solubility: the solubility product The relationship between Ksp and solubility The common ion effect 10.5 Colligative properties of solutions Expressing the concentration of a solution Quantifying colligative properties SUMMARY INTRODUCTION TO SOLUTIONS AND SOLUBILITY GASEOUS SOLUTIONS LIQUID SOLUTIONS QUANTIFICATION OF SOLUBILITY: THE SOLUBILITY PRODUCT COLLIGATIVE PROPERTIES OF SOLUTIONS CHEMICAL ENQUIRY REVISITED KEY CONCEPTS AND EQUATIONS KEY TERMS REVIEW PROBLEMS ACKNOWLEDGEMENTS 11 Acids and bases Chemical enquiry 11.1 The Brønsted–Lowry definition of acids and bases Conjugate acid–base pairs 11.2 Acid–base reactions in water The autoprotolysis of water The concept of pH The strength of acids and bases 11.3 Strong acids and bases pH calculations in solutions of strong acids and bases 11.4 Weak acids and bases pH calculations in solutions of weak acids 11.5 The molecular basis of acid strength Binary acids Inductive effects 11.6 Buffer solutions pH calculations in buffer solutions 11.7 Acid–base titrations Strong acid – strong base and strong base – strong acid titrations Weak acid – strong base and weak base – strong acid titrations Acid–base indicators SUMMARY THE BRØNSTED–LOWRY DEFINITION OF ACIDS AND BASES ACID–BASE REACTIONS IN WATER STRONG ACIDS AND BASES WEAK ACIDS AND BASES THE MOLECULAR BASIS OF ACID STRENGTH BUFFER SOLUTIONS ACID–BASE TITRATIONS CHEMICAL ENQUIRY REVISITED KEY CONCEPTS AND EQUATIONS KEY TERMS REVIEW PROBLEMS ACKNOWLEDGEMENTS 12 Oxidation and reduction Chemical enquiry 12.1 Oxidation and reduction Oxidation numbers 12.2 Balancing net ionic equations for redox reactions Redox reactions in acidic and basic solutions 12.3 Galvanic cells Setting up a galvanic cell Processes in galvanic cells 12.4 Reduction potentials Cell and standard cell potentials Reduction and standard reduction potentials Spontaneous and nonspontaneous reactions 12.5 Corrosion 12.6 Electrolysis What is electrolysis? Comparison of electrolytic and galvanic cells Electrolysis in aqueous solutions 12.7 Batteries The lead storage battery Dry cell batteries Modern high-performance batteries Fuel cells SUMMARY OXIDATION AND REDUCTION BALANCING NET IONIC EQUATIONS FOR REDOX REACTIONS GALVANIC CELLS REDUCTION POTENTIALS CORROSION ELECTROLYSIS BATTERIES CHEMICAL ENQUIRY REVISITED KEY CONCEPTS AND EQUATIONS KEY TERMS REVIEW PROBLEMS ACKNOWLEDGEMENTS 13 Reaction kinetics Chemical enquiry 13.1 Reaction rates 13.2 Factors that affect reaction rates Chemical nature of the reactants Physical nature of the reactants Concentrations of the reactants Temperature of the system Presence of catalysts 13.3 Overview of rate laws First-order rate laws Second-order rate laws Zero-order rate laws 13.4 Temperature dependence of chemical reactions 13.5 Reaction mechanisms and catalysis Catalysts Enzyme kinetics SUMMARY REACTION RATES FACTORS THAT AFFECT REACTION RATES OVERVIEW OF RATE LAWS TEMPERATURE DEPENDENCE OF CHEMICAL REACTIONS REACTION MECHANISMS AND CATALYSIS CHEMICAL ENQUIRY REVISITED KEY CONCEPTS AND EQUATIONS KEY TERMS REVIEW PROBLEMS ACKNOWLEDGEMENTS 14 Organic chemistry 1 Chemical enquiry 14.1 Introduction to hydrocarbons 14.2 Alkanes Conformation of alkanes Cycloalkanes Conformations of cycloalkanes Physical properties of alkanes 14.3 Alkenes and alkynes Shapes of alkenes and alkynes Nomenclature of alkenes and alkynes Physical properties of alkenes and alkynes 14.4 Reactions of alkanes 14.5 Reactions of alkenes Electrophilic addition reactions 14.6 Aromatic compounds The structure of benzene SUMMARY INTRODUCTION TO HYDROCARBONS ALKANES ALKENES AND ALKYNES REACTIONS OF ALKANES REACTIONS OF ALKENES AROMATIC COMPOUNDS CHEMICAL ENQUIRY REVISITED KEY CONCEPTS AND EQUATIONS KEY TERMS REVIEW PROBLEMS ACKNOWLEDGEMENTS 15 Organic chemistry 2 Chemical enquiry 15.1 Chirality Stereoisomers Enantiomerism Naming stereocentres Molecules with more than one stereocentre Molecules with two stereocentres Chirality in the biological world 15.2 Alcohols Physical properties Preparation of alcohols 15.3 Reactions of alcohols Acidity of alcohols Basicity of alcohols Reaction with active metals Conversion to haloalkanes Acid-catalysed dehydration to alkenes Oxidation of primary and secondary alcohols Ester formation 15.4 Amines Physical properties Preparation of amines 15.5 Reactions of amines Basicity of amines Reaction with acids Amide formation 15.6 Carboxylic acids and derivatives Carboxylic acids Acid halides Acid anhydrides Esters of carboxylic acids Amides of carboxylic acids 15.7 Nomenclature of carboxylic acids and derivatives Carboxylic acids Acid halides Acid anhydrides Esters and lactones Amides and lactams SUMMARY CHIRALITY ALCOHOLS REACTIONS OF ALCOHOLS AMINES REACTIONS OF AMINES CARBOXYLIC ACIDS NOMENCLATURE OF CARBOXYLIC ACIDS CHEMICAL ENQUIRY REVISITED KEY CONCEPTS AND EQUATIONS KEY TERMS REVIEW PROBLEMS ACKNOWLEDGEMENTS 16 Biochemistry Chemical enquiry 16.1 Carbohydrates Monosaccharides The cyclic structure of monosaccharides Disaccharides and oligosaccharides Polysaccharides 16.2 Lipids and triglycerides Fatty acids Physical properties of triglycerides Soaps and detergents 16.3 Amino acids Chirality Protein-derived amino acids Acid–base properties of amino acids 16.4 Peptides, polypeptides and proteins The structure of polypeptides and proteins Protein structure Enzymes Denaturing proteins 16.5 Nucleosides and nucleotides 16.6 The chemistry of DNA Primary structure: the covalent backbone Secondary structure: the double helix Tertiary structure: supercoiled DNA DNA replication Ribonucleic acid (RNA) Ribosomal RNA Transfer RNA Messenger RNA SUMMARY CARBOHYDRATES LIPIDS AND TRIGLYCERIDES AMINO ACIDS PEPTIDES, POLYPEPTIDES AND PROTEINS NUCLEOSIDES AND NUCLEOTIDES THE CHEMISTRY OF DNA CHEMICAL ENQUIRY REVISITED KEY CONCEPTS AND EQUATIONS KEY TERMS REVIEW PROBLEMS ACKNOWLEDGEMENTS Appendices Appendix A Thermodynamic data for selected elements, compounds and ions (25°C) Appendix B Average bond enthalpies (25°C) Appendix C Solubility products (25°C) Appendix D Cumulative formation constants of complexes (25°C) Appendix E Acidity and basicity constants for weak acids and bases (25°C) Appendix F Standard reduction potentials (25°C) Appendix G Ionisation energies and electron affinities of the first 36 elements at 25°C Appendix H Table of molar masses and the periodic table of the elements INDEX EULA