IB HL+SL Chemistry Duck Jonas Meyer-Ohle, Nalin Mathur, Arihant Mehta, Jack Hollingworth, Adarsh Balaji http://www.holyhearthigh.ca/wp-content/uploads/2011/09/Chemistry-Guide.

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FROM TOPIC 12 ONWARDS IS HL ONLY

Table of Contents Core Topic 1: Quantitative Chemistry 1.1 The mole concept and Avogadros constant 1.2 Formulas 1.3 Chemical Equations Practice problem 1.4 Mass and Gases Volume relationships in Chemical Reactions k=Pv 1.5 Solutions Topic 2: Atomic Structure 2.1 The atom 2.2 The Mass spectrometer 2.3 Electron Arrangement Topic 12: Atomic Structure 12.1 Electron Configuration Topic 3: Periodicity 3.1 The Periodic Table 3.2 Physical Properties 3.3 Chemical Properties Topic 13: Periodicity 13.1 Trends Across Period 3 13.2 First-Row D-Block Elements Topic 4: Bonding 4.1 Ionic Bonding 4.2 Covalent Bonding 4.3 Intermolecular Forces 4.4 Metallic Bonding 4.5 Physical Properties Topic 14: Bonding 14.1 Shapes of molecules and Ions 14.2 Hybridization 14.3 Delocalization of Electrons Topic 5: Energetics 5.1 Exothermic and Endothermic Reactions 5.2 Calculation of Enthalpy Change 5.3 Hess Law 5.4 Bond Enthalpies Topic 6: Kinetics 6.1 Rates of Reaction

6.2 Collision Theory Topic 7: Equilibrium 7.1 Dynamic Equilibrium 7.2 The Position of Equilibrium Topic 8: Acids and Bases 8.1 Theories of Acids and Bases 8.2 Properties of Acids and Bases 8.3 Strong and Weak Acids and Bases 8.4 The pH Scale Topic 9: Oxidation and Reduction 9.1 Introduction to Oxidation and Reduction 9.2 Redox Equations 9.3 Reactivity 9.4 Voltaic Cells 9.5 Electrolytic Cells Topic 10: Organic Chemistry 10.1 Introduction 10.2 Alkanes 10.3 Alkenes 10.4 Alcohols 10.5 Halogenoalkanes 10.6 Reaction Pathways Topic 11: Measurement and Data Processing 11.1 Uncertainty and Error in Measurement 11.2 Uncertainties in Calculated Results 11.3 Graphical Techniques Higher Level Topic 15: Energetics 15.1 Standard Enthalpy Changes of Reaction 15.2 Born-Haber Cycle 15.3 Entropy 15.4 Spontaneity Topic 16: Kinetics 16.1 Rate Expression 16.2 Reaction Mechanism 16.3 Activation Energy Topic 17: Equilibrium 17.1 Liquid-Vapour Equilibrium 17.2 The Equilibrium Law Topic 18: Acids and Bases 18.1 Calculations Involving Acids and Bases 18.2 Buffer Solutions 18.3 Salt Hydrolysis 18.4 Acid - Base Titrations 18.5 Indicators Topic 19: Oxidation and Reduction 19.1 Standard Electrode Potentials 19.2 Electrolysis

Topic 20: Organic Chemistry 20.1 Introduction 20.2 Nucleophilic Substitution Reactions 20.3 Elimination Reactions 20.4 Condensation Reactions 20.5 Reaction Pathways 20.6 Stereoisomerism Option

Core
Topic 1: Quantitative Chemistry (HL/SL)
1.1 The mole concept and Avogadros constant
- In one mole of a substance there are 6.02 X 1023 particles. This rule can be applied to all kinds of particles: Atoms, Molecules, Ions, Electrons. The amount of substance is measured in moles (mol). - Conversation between number of particles and the amount of substance. - To calculate the amount of moles from the number of particles use the formula: with x being the number of particles in the substance. - To calculate the number of particles from moles use the formula: with x being the number of moles.

1.2 Formulas
- Relative atomic mass (Ar) is the the ratio of the average mass per atom of the naturally occurring form of an element to one-twelfth the mass of an atom of carbon-12. This number for each element can be found underneath the element symbol. Eg. Oxygen has an A r of 16.0 - Relative molecular mass (Mr) is the mass of all atoms in a molecule. Eg. HCL has a M r of 1+35.5= 36.5 - The mass of one mole of a species (atoms, molecules, molecular fragments, ions) is equal to the relative atomic mass. The unit for molar mass is g mol-1. Eg. One mole of Oxygen is equal to the Ar and therefore 16.0 g mol1 . - Problems to do with moles, mass and molar mass: - Number of moles in 9 grams of beryllium: n = 9/9 n = 1 mol - Mass of 1.5 moles of copper: 1.5 = m/63.5 m = 1.5 x 63.5 m = 95.25 g - Empirical Formula - The simplest whole number ratio of atoms of different elements in a compound - Molecular Formula - The actual number of atoms of different elements covalently bonded in a molecule - Empirical Formula from percentage composition of other experimental data. - Write the elements present in the compound as a ratio - Write the percentage composition below each element - Divide the percentage by the relative atomic mass of the element, giving a molar ratio

- Divide each ratio by the smallest one to get a whole-number ratio - Express the ratios in the empirical formula

Eg. O and H:

- Percentage Composition by mass of a compound, given its formula, divide the relative atomic mass of each element present by the relative atomic of the compound and express the result as a percentage:

- Determine the molecular formula when given both the empirical formula and experimental data. - Empirical formula and the molar mass must be known - The molar mass of the empirical formula will be in direct proportion to the molar mass of the molecular formula.

- Eg. Empirical Formula of a hydrocarbon was CH and its molar mass was 26.04 g mol-1 Molecular Formula is C2H2

1.3 Chemical Equations

- Chemical Formulas are shorthand representations of compounds. Chemical reactions are represented by equations using the chemical formulas and symbols of the substances involved in the reaction.

- This reaction is not balanced due to the law of conservation - The law of conservation states that matter can neither be created or destroyed, it can only be changed from one form into another. For chemical equations this means there must be the same number of every type of atom on both sides of the equation.

- Now that we have a balanced equation we can determine the molar ratio. 1 mole of CH 4 reacts with 2 moles of Oxygen to form 1 mole of carbon dioxide and 2 moles of water. the ratio is 1:2:1:2. - Chemical Equations also need to have state symbols. - (g) - Gas - (l) - Liquid - (s) - Solid - (aq) - Aqueous (In solution) These symbols represent the state of each substance at room temperature, unless otherwise specified.

Practice problem 75.075g of formaldehyde (CH2O) is fully combusted. The liquid from the reaction was reacted with sodium. State the sodium compound formed and calculate its mass. ANSWER :(NaOH, 100g)

1.4 Mass and Gases Volume relationships in Chemical Reactions

- Theoretical yield can be calculated from chemical equations - A balanced equation establishes the connection between the mass (/moles) of a known substance to the moles (/mass) of an unknown substance.

1. Write a balanced chemical equation 2. List the given data with units and a symbol. a. eg. n = 0.2 mol b. m = 4.72 g

3. Convert the data for the known quantity to moles using 4. Find the molar ratio between the known and unknown quantities and calculate the number of moles of the unknown. 5. Convert back to the relevant units.

- If there is more than one reactant, the limiting reactant needs to be identified. Find the moles of both reactants, use the molar ratio from the equation to determine which will be completely consumed.

This limiting reagent is the one used in the calculation. Practice problem 111.21g of diethyl ether (C4H10O) is combusted in 100 dm^3 of oxygen. The CO2 produced is passed through lime water. What mass of CaCO3 is formed? (all calculations at RTP) ANSWER : (272.6g)

- Percentage Yield = - Eg. 2Al + O2 2AlO - 2.7 Grams of Al react with excess Oxygen - In an experiment 3.7 grams of Aluminium Oxide are formed. - n(Al) = 2.7/27 - n(Al) = 0.100 mol - 2:2 Ratio - n(AlO) = 0.100 mol - m(AlO) = 0.1 x 43 = 4.3g 7

- Percentage Yield = (3.7/4.3) x 100 = 86% - Avogadros law and calculating reacting volumes of gases - Equal volumes of gases at the same temperature and pressure contain equal numbers of particles. - V= Kn V= Volume K= Constant n= moles - Eg. V1 = 50.0 dm3 V2 = x n1 = 0.003 mol n2 = 0.00375 mol - Avogadros Law = V1/n1 = V2/n2 - x = (50.0/0.003) x 0.00375 - x = 62.5 cm3 - Molar volume at standard temperature and pressure in calculations - V= nRT/p - V is the volume (dm3) - n is the number of moles (mol) - R is the Ideal Gas constant (8.31 Joules mol-1 kelvin-1) - T is the temperature in kelvin (K) - p is the Pressure in KiloPascals (kPa) - eg. 1.00 mol of an ideal gas at 273k and 101.3 kPa. - V= (1.00 x 8.31 x 273)/101.3 = 22.4 dm3 Standard Temperature = 273k (0 C) Standard Pressure = 101.3 kPa (1 Atmosphere) - Solve problems involving the relationship between temperature, pressure and volume for a fixed mass of an ideal gas

This can be simplified to: Due to the amount of gas being usually fixed. This equation can be used to solve for any of the six quantities if the other five are known. Make sure that all the units are appropriate and equal on both sides. Eg.

- Analyzing graphs related to the ideal gas equation - Boyles Law - Studied the relationship between pressure and volume. - The pressure exerted by a given mass of gas at a constant temperature is inversely proportional to the volume occupied by the gas.

k=Pv P1V1 = P2V2 This relationship applies if temperature and the amount of gas are constant and all units are consistent and appropriate. Eg. P1 = 101.3 kPa (1 atm) P2 = 130.5 kPa V1 = 1.5 dm3 V2 = x V2 = (P1V1)/P2 = (101.3 x 1.5)/ 130.5 = 1.16 dm3 1.5 Solutions 1.51 - Distinguish between the terms solute, solvent, solution and concentration (g dm-3 and mol dm-3) Solute - Substance which has been dissolved. Solvent - The substance in which the solute was dissolved Solution - Made up of solute and solvent. Called aqueous if the solvent is water. Concentration - Expression of how much solute there is dissolved in the solution. 1.5.2 - Solve problems involving concentration, amount of solute and volume of solutio - Eg. Sucrose (C12H22O11) solution - m = 30.0g - V = 200 cm3 - n = m/M 30.0/ 342.34 = 0.0876 mol C 12H22O11 c = n/V 0.0876 mol/ 0.200 dm3 = 0.438 ml dm-1

- Calculating concentrations of components of solutions - Concentration of individual ions in solution is proportional to the chemical formula. - If there is no chemical reaction when two or more solutions are mixed, the concentration of each individual ion can be calculated by determining the total amount of that ion present and dividing by the final volume of the solution. Eg. m(Al2[SO4]3) = 342.1 g - V = 150 dm3 - n m/M 342.1/342.1 = 1 mol Al(SO4)3 - c n/V 1/150 = 0.067 mol dm-3 Al(SO4)3 - c(Al3+) = 2 x 0.0067 = 0.0134 mol dm3 - c(SO42-) = 3 x 0.0067 = 0.02 mol dm3 - Dilution of Solutions

Units must be constant on both sides. - Limiting Reagent with Solutions - Write down balanced equation. - Write down all values such as concentration, volume and mass of solute. - Calculate moles of both solutions. Find the solution which is in excess. Use the limiting reagent in your calculation. - Find the molar ratio and calculate the mass of the product created.

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Back titrations A sample of chalk weighing 0.135g was reacted with 40.00cm3 of 1moldm^-3 hydrochloric acid (an excess). After the reaction was complete the solution was transferred to a 250cm3 volumetric flask and made up to the mark with distilled water. 25.00cm3 portions of this solution were then titrated against 0.15moldm^-3 sodium hydroxide using. An average of 25cm3 of the sodium hydroxide was required to neutralized the solution Calculate the percentage purity of the chalk. The general method for back titrations is as follows 1) Calculate the moles of substance in the aliquot (which is the HCl in the above example) by using the titration values. HCl+NaOH -> NaCl + H2O n(NaOH) = cv = 0.15 x 25/1000 = 0.00375mol The molar ratio is 1:1 therefore n(NaOH) = n(HCl) = 0.00375mol 2) Using the calculated value, find the total number of moles in the full solution Since the aliquot was 25cm^3, and the total volume of the solution was 250cm^3, we have to multiply the calculated amount by 10. (you may have to multiply by a different number depending on the volume of the solution and the aliquot eg. if a 20cm^3 aliquot was taken and 160cm^3 of solution was made you would have to multiply by 8) n(HCl) in aliquot x 10 = n(HCl) in solution = 0.00375 x 10 =0.0375 mol 3) Find the original number of moles first added to the solution. n(HCl) first added = cv = 1 x 40/1000 = 0.04 mol 4) Now minus the number of moles in the solution from the number of mols first added to the solution to find the moles reacted with the solute. 0.04-0.0375=0.0025 mol of HCl reacted with CaCO3

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5) Find the number of mols of the solute CaCO3 + 2HCl -> CaCl2 + H2O + CO2 We see the ratio is 1:2. (n(CaCO3) = 0.5n(HCl) Therefore we have to divide the n(HCl) by 2 to get the moles of CaCO3 n(HCl) / 2 = n(CaCO3) = 0.0025 / 2 = 0.00125 mol 6) Find the mass of the moles of the solute and find the percentage of mass it would take m(CaCO3) = nM = 0.00125 x 100 = 0.125g percentage purity of CaCO3 = (0.125/0.135) x 100 = 92.6% (3sf)

Note : step 6 was specific to the practice problem, a back titration may ask you to do something different with the calculated value. However the first 5 steps will apply to nearly all back titration questions.

Topic 2: Atomic Structure (HL/SL)

2.1 The atom
2.1.1 State the position of protons, neutrons and electrons in the atom - Atoms are made up of a nucleus containing positively charged protons and neutral neutrons with negative charged electrons moving around the nucleus in shells

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2.1.2 State the relative masses and relative charges of proton, neutrons and electrons Relative Mass Proton Neutron Electron 1 1 5 x 10-4 Relative Charge 1 0 -1

2.1.3 Define the terms mass number (A), atomic number (Z) and isotopes of an element - Mass Number (A) = Sum of protons and neutrons in the nucleus - Atomic Number (Z) = Number of protons in the nucleus. (Equal to the number of electrons) - Isotopes of an element - Atoms of the same element with the same number of protons but with a different number of neutrons 2.1.4 Deduce the symbol for an isotope given its mass number and atomic number - Nuclide notation, shows the mass number, atomic number and symbol to represent a particular isotope

2.1.5 Calculate the number of protons, neutrons and electrons in atoms and ions from the mass number, atomic number and charge - Protons - Find the atomic number - Neutrons - The difference between the mass number and the atomic number - Electrons - If the atom is electrically neutral, find the atomic number. - If not Find the atomic number and then subtract the charge. 2.1.6 Compare the properties of the isotopes of an element - Chemical Properties will remain the same due to the valence electrons being the same in every isotope of an element - Physical properties depend on the nuclei and therefore properties such as density, rate of diffusion, melting and boiling points will change - The mass will also change 2.1.7 Discuss the uses of radioisotopes Radioisotopes are often used in radiotherapy, in which they damage the DNA of cancer cells, preventing them from undergoing cell division. - Iodine-131 is used to treat thyroid cancer and diagnose whether a thyroid gland is functioning normally

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- Iodine-125 is used to treat prostate cancer and brain tumors - Cobalt-60 has been used for over 10 years to treat different kinds of cancer, and it is recently being used to suppress the bodys reaction to transplanted human organs - A constant percentage of Carbon-14 is present in living plants and animals because it is being continually replaced when animals absorb nutrients. However in dead tissue, these processes do not happen and the carbon-14 undergoes beta decay. By comparing the percentage of carbon-14 in a dead organic substance with that in living tissue, and knowing the half life of carbon, the estimated age of a fossil can be found. This is known as Radiocarbon dating.

2.2 The Mass spectrometer

2.2.1 Describe and explain the operation of a mass spectrometer - Mass spectrometers consist of a number of components which perform particular functions. - The principle behind it is that the movement of charged particles will be affected more/less as the pass through the magnetic field due to the mass/ charge ( ) ratio - There are 6 main stages of the operation: 1. Vaporization - The sample is heated and vaporized and passed through into an evacuated tube. This separates the particles 2. Ionization - Atoms/ molecules are then bombarded by a stream of high energy electrons, knocking electrons off the particles resulting ions with 1+ charge 3. Acceleration - Positively charged ions are then accelerated along the tube by means of the attraction to negatively charged plates. The ions pass through slits which control velocity (Direction) of their motion. 4. Deflection - The ions are then passed into a very strong magnetic field, deflecting the ions in a curved path.A lighter ion will be deflected more than a heavier one. Deflection of the ions depends on the mass/ charge ratio 5. Detection - The ions are detected electronically by a device that measures both the location and the number of particles that collide with it. 6. Recording - The percentage abundance of the isotopes is recorded as a graph called a spectrum.

A peak is produced in the spectrum for each isotope. The peaks along the horizontal axis indicate the ratio: - The number of peaks recorded indicate the number of isotopes and their isotopic masses. The height of the peak indicates the abundance. - Percentage abundance is then calculated for the calculation of relative atomic mass. This is found by dividing the height of the particular peak by the sum of all the peaks.

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2.2.2 Describe how the mass spectrometer may be used to determine relative atomic mass using the 12C scale - To generate the relative scale of atomic masses, carbon 12 isotope is assigned a relative mass of 12 units exactly. - The lightest of all elements (H) was found to have deflected 12 times further than carbon 12, while the magnesium-24 isotope deflects half as far. - This is why hydrogen's relative mass is close to 1 and magnesiums is approximately 24. 2.2.3 Calculate non-integer relative atomic masses and abundance of isotopes from given data - The relative atomic mass of an element is the weighted mean of all its natural occurring isotopes on the scale in which the carbon 12 isotope is 12 units exactly. Symbol = Ar

- Ir is the relative isotopic mass. - Eg. Cl-35 and Cl-37 - Ir(Cl-35) = 34.97 Ir(Cl-37) = 36.97 - Abundance(Cl-35) = 75.78% Abundance(Cl-37) = 24.22%

2.3 Electron Arrangement

2.3.1 Describe the electromagnetic spectrum - Electromagnetic waves can travel through space and matter. - Wavelength is the distance between two successive crests. - Velocity of travel, c, is related to its wavelength, and its frequency, f. - The frequency is the number of waves passing a given point per second.

- Electromagnetic waves are a form of energy. - The energy of this radiation is related to its frequency and Plancks constant

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- The value of Plancks constant is 6.63 x 10-34 Js-1 - A smaller wavelength has a higher frequency and therefore possesses more energy. - Electromagnetic waves can have a wavelength from low-energy radio waves to very high-energy gamma radiation. - Visible light is only a very narrow part of this spectrum.

- As energy increases, so does the frequency. - Red light has lower energy than violet light. - Ultraviolet light is more damaging to our skin due to high energy being more dangerous than low energy. - Sunlight contains all the wavelengths of visible light - When it passes through a prism, the different wavelengths are refracted at different angles, breaking up light into its components.

2.3.2 Distinguish between a continuous spectrum and a line spectrum - Line Spectrum - A representation of light and appears as a series of discrete, coloured lines on a black background - Continuous Spectrum - A spectrum of light in which there are no gaps, so that each region blends directly into the next. 2.3.3 Explain how the lines in the emission spectrum of hydrogen are related to electron energy levels. - Emissions spectra are the emissions of light from atoms that have been provided with energy. - Bohr suggested that when atoms are provided with large amounts of energy, the electrons can

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change energy levels. - The electrons jump to levels further from the nucleus than usual. This atom is said to be excited. - When the atom moves back to ground state, the energy is released as light. - The electrons will make specific jumps, depending on the ground states involved, so the light released has a specific wavelength. - The lines of light (emissions) look like coloured lines on a black background. - Studying these emissions is called emission spectroscopy.

Another Diagram:

2.3.4 Deduce the electron arrangement for ions up to Z=20 - The electron arrangement or configuration for an atom or ion is written showing the electrons in order from closest to the nucleus, outwards. - Each electron shell can hold a maximum of 2n2 electrons (n being the shell number) - The electron shells are also known as energy levels. The shells nearer the nucleus are lower in energy compared to the ones further out. - The shells are numbered from the nucleus (1, 2, 3) - The electron(s) in the outer shell of the atoms are called the valence electrons. - The lowest energy state of an atom is when all of the electrons are as close to the nucleus as possible. - This is known as its ground state. Eg. Z= 18 = 2,8,8 - Atoms may also be represented diagrammatically. - Protons, neutrons and electrons are shown.

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Topic 12: Atomic Structure(HL ONLY)

12.1 Electron Configuration

12.1.1 Explain how evidence from first ionization energies across periods accounts for the existence of main energy levels and sub-levels in atoms Definition: The first ionization energy is the minimum energy per mole required to remove electrons from one mole of isolated gaseous atoms to form one mole of gaseous unipositive ions under standard thermodynamic conditions. So basically, the energy required to take an electron off an atom Factors that affect ionization energy
1. 2. 3. Size of atom nuclear charge shielding effect

If you plot a graph of the first ionization energies of all the elements, you can identify clear trends. We will focus on the first three periods of the periodic table.

- There is a large drop in first ionization energy when going from one period to the next , e.g from He to Li, Ne to Na, or from Ar to K. This is because another electron shell has been added. The first electron is now further away from the nucleus, which means that the attraction of the positive nucleus for the negatively charged electron falls. Moreover, the valence electrons are being shielded from the attraction of the nucleus by the positively charged nucleus. In general, the shielding effect is most effective when the electron are close to the nucleus. So the electrons in the first shell (H, He), where there is high electron density, have a stronger shielding effect than the electrons in the second shell (Li, Be, B) - There is a general increase in ionization energy across each period . This is due to the increase in nuclear charge. When the nuclear charge becomes more positive, its attraction on all the electrons increases. As you can see, in period 1, as we go from H to He, the ionization energy increases. In period two, as you go from Li all the way to Ne, the ionization energy increases. And in period 3, as

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you go from Na to Ar, the ionization energy increases. - There is a dip from Be to B and from Mg to Al. This is a result of a change in sub-shell. When ionizing B (1s2s2p), it loses a 2p electron whereas Be (1s2s) loses a 2s electron. 2p orbitals are higher in energy than 2s orbitals, so it takes less energy to remove an electron from a 2p orbital than a 2s orbital. Also, an electron in the 2p orbital is more effectively shielded by the inner electrons than an electron in the 2s orbital. This is shown in the picture below

- There is a dip from N to O and from P to S. This occurs because in N (1s2s2px2py2pz) and P (1s2s2p 3s3px3py3pz) there are three valence electrons are in three separate orbitals, whereas in O (1s2s2px2py2pz) and S (1s2s2p 3s3px3py3pz) there are two electrons in the same 2px and the same 3px orbital. These two electrons experience a lot of repulsion so it is easier to remove one of these electrons than an unpaired electron from a half filled 2pz or 3pz orbital. 12.1.2 Explain how successive ionization energy data is related to the electron configuration of an atom The first ionization energy is the minimum energy required to remove a mole of electrons from a mole of gaseous atoms to form a mole of unipositive ions. The second ionization energy is the minimum energy required to remove a mole of electrons from a mole of gaseous unipositive ions to form a mole of dipositive ions. The third ionization energy is the minimum energy required to remove a mole of electrons from a mole of gaseous dipositive ions to form a mole of tripositive ions. And so on. - Successive ionization energies always increase because the electrons are being removed from increasingly positive ions and so the electrostatic forces are greater. The second ionization energy is always larger than the first because more energy is required to remove an electron from a unipositive ion than a neutrally charged atom. Similarly, the third ionization energy is always larger than the second and first.

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Successive Ionization energies of Potassium (2,8,8,1) - Jumps in the successive ionization energies correspond to removing electrons from inner shells whose electrons are progressively located nearer to the nucleus.

12.1.3 State the relative energies of s, p, d, and f orbitals in a single energy level and (12.1.4) State the maximum number of orbitals in a given energy level

Note that the 4s subshell has a lower energy than the 3d subshell, and hence electrons fill the 4s subshell before they occupy the 3d subshell. That is why K and Ca fill their 4s subshell before their 3d subshell. This is further expanded on in 12.1.6.

12.1.5 Draw the shape of an s orbital and shape of the px py pz orbitals

The three p orbitals are degenerate, this means that they all have the same energy.

12.1.6 Apply the aufbau principle, Hunds rule and the Pauli exclusion principle to write electron configurations for atoms and ions up to Z = 54

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Pauli exclusion principle - Each orbital can hold up to a maximum of two electrons. Aufbau principle - Electrons enter and occupy an empty orbital with the lowest energy. Hunds rule - Within a subshell, electrons experience repulsion and hence enter two different orbitals of the same energy.

Examples of electron configurations that are wrong

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We need to know these up till Xe (54) Note: The electron configurations for Cr and Cu are somewhat unexpected because they do not obey the Aufbau principle. The electron configuration for Cr is [Ar] 4s1 3d5, instead of [Ar] 4s2 3d4 as expected. And the electron configuration for Cu is [Ar] 4s1 3d10, rather than [Ar] 4s2 3d9 as expected. This is because a half-filled (in the case of Cr) or completely filled (in the case of Cu) 3d sub-shell is a particularly stable configuration. So the electron from the 4s subshell is transferred into one of the empty 3d orbitals. This is shown in the picture below.

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- When ionizing atoms, the last electron added is removed first. For example, O is [He] 2s2 2p4, so the O+ ion will be [He] 2s2 2p3 - In the case of d-block elements however, the electrons from the 4s subshell are removed before the electrons from the 3d subshell.

Topic 3: Periodicity (HL/SL)

3.1 The Periodic Table
3.1.1 Describe the arrangement of elements in the periodic table in the order of increasing atomic

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number The elements are arranged in order of increasing atomic number which leads to repeatable patterns in elemental properties 3.1.2 Distinguish between the terms group and period A period is a horizontal row of elements on the periodic table From left to right, a period starts with reactive metals to reactive non metals, ending in a noble gas A group is a vertical column of elements on the periodic table There are 8 groups in the table, the last one is referred to as group 0. The transition metals have similar properties down a group AND across a period.

3.1.3 Apply the relationship between the electron arrangement of elements and their position in the periodic table up to Z=20 All the elements in the same period have the same number of electron shells Groups display similar properties because of the same number of valence electrons

3.1.4 Apply the relationship between the number of electrons in the highest occupied energy level for an element and its position in the periodic table The number of electrons in an elements highest energy level is its valency. If the valency is 1, the element would go in group 1. If it is 7 it would go in group 7.

3.2 Physical Properties

3.2.1 Define the terms first ionization energy and electronegativity - First Ionization Energy = Energy required to form one mole of unipositive(+1 charge) ions in the gas phase from one mole of gaseous atoms (STP Conditions, 273K / 1 atm) - Electronegativity = Measures the tendency (power) of an atom to attract the electrons in a covalent bond. Measured by the Pauling scale. F = 4.0 Cs/Fr = 0.7

3.2.2 Describe and explain the trends in atomic radii, ionic radii, first ionizations energies, electronegativities and melting points for the alkali metals (Li Cs) and the halogens (F I) Atomic radius The atomic radius increases down the groups because the outermost electrons occupy a higher energy and the outer electrons are shielded by a greater number of inner electrons.

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Covalent bonds - the atomic radius is half of the distance in between the nuclei. Metallic bonds - the atomic radius is half of the distance in between the nuclei in a metallic lattice Noble gases - the atomic radius is measured from individual atoms. Ionic radius The ionic radius increase down the groups with the same valency because 1)the outermost electrons occupy a higher energy level, and are further away from the nucleus reducing the force of the nucleus on the outer electrons. 2) the increased shielding of the outer electrons because of the larger number of inner electrons. First ionization energy The first ionization energy decreases down the group 1)the outermost electrons occupy a higher energy level, and are further away from the nucleus reducing the force of the nucleus on the outer electrons. 2) the increased shielding of the outer electrons because of the larger number of inner electrons. Electronegativity Electronegativity decreases down the group. This is because of an increasing atomic radius increases the distance between the outer bonding electrons and the nucleus, reducing the attraction between the two. The fact that nuclear charge increases down the group is opposed by the increased shielding of outer electrons. Melting point Group 1 The melting point decreases down the group because of the larger atomic radius, which reduces the strength of the attraction between the nuclei and the delocalized electrons in the metal lattice. Group 7 The melting point increases down the group because of the increased strength of the dispersion forces(attraction between temporary and induced dipoles) because of the larger electron cloud. 3.2.3 Describe and explain the trends in atomic radii, ionic radii, first ionization energies and electronegativities for elements across period 3 Atomic radius Decreases along the period Explanation - Electrons are added to the same shell, which only slightly increases shielding, while protons are added to the nucleus which outdoes the slight increase in shielding, making the overall pull on electrons greater and reducing the radius of the atom Ionic radius Decreases from Na+ -> Al3+ Silicon does not form ions but calculated values show the Si 4+ cation is smaller than the Al3+ and the Si4- is larger than the P3Increases from Al3+ to P3- then decreases from P3- -> ClAr doesnt form ions

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Explanation Na+ -> Al3+ cations are isoelectronic species, meaning their electronic configuration is the same, and since the nuclear charge increases across the period, the electrons are pulled closer. The increase from Al3+ to P3- is because the phosphorus anion has an additional electron shell which increases the shielding effect and increases the ionic radius P3- -> Cl- are isoelectronic, since nuclear charge increases across the period the ionic radius reduces.

First ionization energy Increases across the period The increase in nuclear charge counterbalances the slight increase in shielding to give atoms whose outer electrons are closer to the nucleus making them harder to remove.

3.2.4 Compare the relative electronegativity values of two or more elements based on their positions in the periodic table The general trend in electronegativity is it increases across a period and decreases down a group. The EN increases from left to right because of increasing nuclear charge countering the slight increase in shielding, pulling any bonding electrons closer to the nucleus The EN decreases from up to down because the bonding electrons are placed in higher energy levels, which reduces the attraction between the electrons and the nucleus.

3.3 Chemical Properties

3.3.1 Discuss the similarities and differences in the chemical properties of elements in the same group Alkali Metals with Water Alkali metals are very reactive and react violently with water. Due to this property they must be stored under oil. Reactivity increases down the alkali group. This increase in reactivity down the group is caused by decreasing electrostatic attraction to the outer shells. Electrons can be removed easier from the group. Alkali metals are good reducing agents because they donate electrons. Alkali metals with water produce an alkaline solution Na2O(s) + H2O(l) 2NaOH(aq) Alkali Metals with Halogens The reaction between alkali metals and halogens is very violent as alkalis are good reducing agents and halogens are good oxidising agents. In the reaction a salt is produced 2Na(s) + Cl2 (g) 2NaCl(s) Halogens and Halide ions Reactivity increases up the halogen group because charge density increases as the atom size decreases. With that the ability to gain electrons increases (Electronegativity). Fluorine is the most reactive halogen and element with the highest electronegativity (FONCl)

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Larger halide ions lose electrons more easily due to electron shielding and greater distance between the nucleus and valence shells decreasing electrostatic attraction. Cl2 (g) + 2I- (aq) 2Cl-(aq) + I2 (s) 3.3.2 Discuss the changes in nature, from ionic to covalent and from basic to acidic, of the oxides across period 3

All elements across period 3 react with oxygen to form various types of compounds. - Metals will react to form ionic compounds - Non-metals react to form covalent molecules - Decreases in pH from left to right. - Aluminium oxides are amphoteric as they can act as a base or an acid.

Topic 13: Periodicity (HL)

13.1 Trends Across Period 3
13.1.1 Explain the physical states (under standard conditions) and electrical conductivity (in the molten state) of the chlorides and oxides of the elements in period 3 in term of their bonding and structure

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State NaCl and MgCl2 are ionic therefore they are ionic lattices at STP. Making them solids at STP as ionic compounds have high melting points. AlCl3 exists in sheets but is covalent, and forms a dimer, Al 2Cl6, when it is in gas and liquid states. The covalent bonding is what makes the melting and boiling points much lower than the NaCl and MgCl 2 SiCl4 , SCl2 and Cl2 are all molecular covalent which means the only forces holding them together are the dispersion forces. PCl5 is a bit more interesting, it actually forms an ionic lattice of (PCl 4)+ and (PCl6)- ions which is why it has a high boiling and melting point even though the bonding between in the individual molecules is covalent. Conductivity NaCl and MgCl2 are ionically bonded, and when aqueous are good conductors of electricity as they dissociate into their respective ions. NaCl dissociates into Na + and Cl-. MgCl2 dissociates into an Mg2+ ion and two Cl-ions. These ions can carry a charge across a potential difference and thereby conduct an electric charge. When or in the solid state however, they do not conduct electricity because there are no free ions or electrons to carry a charge. The MgCl2 has a lower boiling point that the NaCl because it shows slightly more covalent character, so when you are heating the MgCl2 you are forming MgCl2 molecules rather than individual Mg 2+ and Clions. These molecules then dissociate into the individual ions, but all it has to do to form a liquid is to form those aforementioned molecules. AlCl3, SiCl4, PCl5, PCl3, S2Cl2 and Cl2 all do not conduct electricity. Again, this is because there are no ions or electrons that can carry a charge across a potential difference.

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State Na2O, MgO and Al2O3 are all ionic and are therefore solids at STP because breaking the ionic lattice requires a large amount of energy. SiO2 exists as a covalent network which explains the high melting point because covalent bonds need to be broken before it can be considered a liquid. P4O6 P5O10 are large simple molecules which gives the dispersion forces enough strength to keep it as a solid at STP SO2 SO3 Cl2O Cl2O7 are all simple covalent meaning the dispersion forces arent strong enough to keep the molecules as solids at STP Conductivity Ionic - yes SiO2 partial if heated, the oxygen is mobile enough to show partial conduction. Covalent - no

13.1.2 Describe the reactions of chlorine and the chlorides referred to in 13.1.1 with water NaCl NaCl(s) Na+(aq) + Cl-(aq) NaCl Dissolves in water to form a neutral solution. MgCl2 2+ MgCl2(s) + H2O(l) Mg (aq) + 2Cl (aq) MgCl forms a slightly acidic solution. AlCl3 AlCl3(s) + 3H2O(l) Al(OH)3(s) + 3HCl(g) Forms a highly acidic solution. Forms acid fumes. The aluminium (III) ion is a small ion with a high charge density allowing it to polarize the electron cloud of one oxygen in a water molecule. This creates a cleavage in the HO-H bond in water and H+ is released. This process is called deprotonation. The extra H+ reacts with H 2O and forms H3O+. Therefore, this solution is acidic while other aluminium compounds in solutions are basic (amphoteric properties). SiCl4

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SiCl4(l) + 2H2O(l) 4HCl(g) + SiO2(s) Forms a highly acidic solution. PCl3 PCl3(l) + 3H2O(l) H3PO3(aq) + 3HCl(g) HCl dissolves in water to form a highly acidic solution PCl5 PCl5(s) + 4H2O(l) 5HCl(g) + H3PO4(aq) Forms a highly acidic solution S2Cl2 S2Cl2(l) + 3H2O(l) 2HCl(aq) + H2S(g) + H2SO3(aq) Cl2 Cl2(g) + H2O(l) HOCl(aq) + HCl(aq) Forms chlorine water

13.2 First-Row D-Block Elements

13.2.1 List the characteristic properties of transition elements Similar electronic configuration, first ionization energy and atomic radii Since the first row of d block elements all add electrons to either the 3d or 4s subshell, the atomic radius doesnt change be a large amount across from Sc to Zn. The small decrease in atomic radius is because the electrons are added to the inner 3d subshell, which increases shielding of the 4s electrons, enough to negate most of the effect of the increase in nuclear charge. This also explains the small fluctuations in first ionization energy, since it is the 4s electrons which are liberated. Physical Properties Good conductors of heat and electricity High melting points Malleability High tensile strength (ability to hold large loads without breaking) Ductility Lustrous (most) Dense Sonorous The delocalized electrons (coming from 3d AND 4s) explain the properties. The large number of delocalized electrons per atom allows for the strength of the metallic bond. The smaller atomic radius partly accounts for the high density.

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Chemical Properties Variable oxidation states in compounds Forms many complex ions Form colored compounds Act as catalysts

13.2.2 Explain why Sc and Zn are not considered to be transition elements Scandium and Zinc only have one oxidation state in the compounds, scandium has a +3 and zinc a +2. Their ions do not have a partially filled 3d subshell, Sc 3d subshell is completely empty and Zn 3d subshell is completely full. 13.2.3 Explain the existence of variable oxidation number in ions of transition elements The successive ionization energies for a single transition metal increase gradually when removing the 4s and the 3d electrons, meaning there is no large jump in ionization energy when removing electrons from those specific shells. When all the electrons from those shells are removed however, the jump of the ionization energy is large and therefore the cation of the higher charge cannot be formed. Lets take an example of Ti The first 4 electrons are removed from the 4s first then the 3d. These ionization energies increase gradually, however once you have removed the 4th electron, there is a large jump in ionization energy to removed the 5th, meaning it doesnt form a 5+ cation. Important points -all transition metals show oxidation states of 2+ and 3+ -from Sc to Cr the 3+ state is more stable, but for later elements the 2+ is more stable -From left to right of the period until Mn , there is an increase in the oxidation state which always increase in increments of +1. Meaning Ti can form +2 to +4, V can form +2 to +5 and so on. Manganese has the maximum at +7. From Mn there is a reduction in the oxidation states in increments of -1. -Oxidation states above +3 show covalent character -Compounds with high oxidation states are usually oxidizing agents.

13.2.4 Define the term ligand A species that forms a dative covalent bond with a metal ion The coordination number of the metal ion is the number of dative bonds formed by the ligands.

13.2.5 Describe and explain the formation of complexes of d-block elements

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The high charge density of the d-block elements attracts the lone pair of electrons of the ligand which forms a complex ion. All ligands have a lone pair that can form a dative covalent bond.

Naming Complex Ions Ligand H2O NH3 OHClF

-

Coded by Aqua Ammine Hydroxo Chloro Fluoro Cyano

CN-

Number of Ligands 1 2 3 4 5 6

Prefix Mono Di Tri Tetra Penta Hexa

Add the oxidation state after the metal. eg. copper(II) To find the oxidation state, look at the complex. (CuCl4)2The chloro ligand has a charge of 1-, and since there are 4 of them the total charge is 4-. This means the copper must be adding a charge of 2+ to give the overall complex a charge of 2-. Meaning the oxidation state of copper is 2+ and the complex is tetrachlorocuprate(II) 13.2.6 Explain why some complexes of d-block elements are coloured The partially filled 3d subshell allows transition metals to absorb a part of the spectrum of white light, meaning what isnt absorbed forms the color of the solution. The theory used to explain this is crystal field theory.

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When there is an octahedral complex, the ligands are bonded along the x axis from the positive and negative end, the y axis from the positive and negative end, and the z axis from the positive and negative end. The d subshells that lie along these axes will experiences greater repulsion from the electrons from the ligands as they are on the same axes. The other subshells will feel less repulsion. Meaning that the subshells on the axes will be higher in energy because of the increased repulsion and the subshells not along the axes will have a lower energy. This disparity in the amount of energy means that a photon can hit an electron in the complex, which will then jump up in energy because there is a place to jump to, in this case, the partially filled subshell which falls along the x,y or z axes. When this drops back down to ground state a photon is released, meaning the compound will be colored.

13.2.7 State examples of the catalytic action of transition elements and their compounds Examples of transition metals being used as catalysts Iron This catalyzes the haber process N2 (g) + 3H2 -> 2NH3 (g) (the reaction is reversible) Nickel Converts alkanes to alkenes Breaks the double bond between carbons which then have single hydrogens attached to them Palladium and Platinum Used in catalytic converters to remove harmful gases in the exhaust 2CO(g) + 2NO(g) -> 2CO2(g) + N2 (g) Examples of transition metal compounds being used as catalysts MnO2 in decomposition of H2O2 H2O2 (aq) -> H2O (l) + O2 (g) V2O5 in the contact process 2SO2 (g) + O2 (g) -> 2SO3 (g) (the reaction is reversible) All these catalysts are heterogeneous which means that they are in a different state from the reactants. (eg if reactant is liquid the catalyst is a solid) The next few are homogeneous catalysts, meaning they are in the same state as the reactants. Fe2+ in heme

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The iron atom is surrounded with 4 nitrogen atoms and it forms weak bonds to the O 2, which break easily when the oxygen needs to be released Co3+ in vitamin B12 Part of the vitamin has an complex of cobalt that is octahedral but only 5 sites are full, leaving the last one for biological activity.

13.2.8 Outline the economic significance in the Contact and Haber processes The contact process and the haber process produce chemicals with important industrial applications, catalysis of these processes increases the rate of products produced. Heterogeneous catalysts are preferred in industry because they can simply be filtered out of the mixture, as they would be the only solid there.

Topic 4: Bonding (SL/HL)

4.1 Ionic Bonding
4.1.1 Describe the ionic bond as the electrostatic attraction between oppositely charged ions. Ionic bonding is when one or more electrons are completely transferred from the valence shell of one atom to another atoms valence shell. This forms a positively charged ion (cation) and a negatively charged ion (anion), the ionic bond is the electrostatic attraction between the negative and the positive ion. 4.1.2 Describe how ions can be formed as a result of electron transfer Ionic bonding usually happens in a reaction between a metal and a non-metal. When the non-metal gains the valence electron or electrons of the metal and the ions start to attract is when the ionic bond is formed If we look at magnesiums and oxygens electronic configuration Mg : 1s2 2s2 2p6 3s2 (for SL 2,8,2) O : 1s2 2s2 2p4 (for SL 2,6)

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The magnesium has 2 electrons in its valence shell, and if it loses these electrons it will have a configuration isoelectronic to Ne. The oxygen has 6 electrons in its valence shell, if it gains 2 more it will have a configuration isoelectronic to Ne. So when these 2 form an ionic bond, the magnesium loses 2 electrons and the oxygen gains these 2 electrons

4.1.3 Deduce which ions will be formed when elements in groups 1 2 and 3(13) lose electrons 4.1.4 Deduce which ions will form when elements in group 5 6 and 7 (15 16 17) gain electrons

4.1.5 State that transition elements can form more than one ion Group number Ions formed Example 1 2 3(13) Transition Metals +, 2+ , 3+ Fe 2+, Fe 3+ 5(15) 6(16) 7(17)

1+ Na +

2+ Mg 2+

3+ Al 3+

3N 3-

2O 2-

1F-

4.1.6. Predict whether a compound of two elements would be ionic from the position of the

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elements in the periodic table of from their electronegativity values. The electronegativity values must have a large enough difference for the bonding to be ionic. The most covalent bond would be one between 2 of the same atom, for example in a O2 molecule the electronegativity values are the same. This means the bond is not polar and the electrons are shared equally. General rule is that a electronegativity value of GREATER than 1.8 will result in an ionic bond.

4.1.7 State the formula of common polyatomic ions formed by non metals in periods 2 and 3. Nitrate Hydroxide Hydrogen Carbonate Carbonate Sulfate Phosphate Ammonium NO3 OH HCO3 CO3 2SO4 2PO4 3NH4 +

4.1.8. Describe the lattice structure of ionic compounds The forces of electrostatic attraction between ions make them surround themselves with ions of the opposite charge. Therefore it will form a predictable 3D crystalline structure called an ionic lattice. The higher the charges on the constituent ions the stronger and more stable the compound would be. The ionic lattice is also called a giant structure. The coordination number is how many ions will surround another of the opposite charge. For example the coordination number of NaCl the coordination number is 6, each Na+ is surrounded by 6 Cl - . Covalent character in ionic bonds Polarizing power of the cation - The extent to which a cation can attract the electron cloud of an anion It depends on - its size, the smaller the ion the closer its charge is to the anions valence electrons - the less the distance the more force it can exert on them - therefore the smaller the ion the higher the polarizing power - its charge - the larger the charge of the ion the greater force it can exert on the electrons Both of the above factors determine the charge density of the cation, the greater the charge density of the ion the more it can attract the anions and the greater the degree of covalence in the ionic bond Polarizability of an anion - the ease with which its electron density can be pulled toward the positive ion

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It depends on - the amount of electrons, - the more electrons there are the less control the nuclear charge will have on them - the distance of the electrons from the nucleus - the further the electrons are from the nucleus the more polarizable the ion The more polarizing and the more polarizable the ions involved, the more covalent the ionic bond will be,

4.2 Covalent Bonding

4.2.1. Describe the covalent bond as the electrostatic attraction between a pair of electrons and positively charged nuclei. Covalent bonds are the electrostatic attraction between a pair of electrons and positively charged nuclei. 4.2.2 Describe how the covalent bond is formed as a result of electron sharing (including dative covalent bonds) A covalent bond is when 2 atoms each donate one electron to the bond, dative bonding is when one atom donates both electrons to the bond. 4.2.3. Deduce the lewis structures of molecules and ions for up to four electron pairs on each atom Step 1 Step 2 Step 3 atoms Step 4 - Calculate the number of valence electrons in the molecule - Draw the skeletal structure of the molecule - Use pairs of crosses or dots, or a single line to show one single bond between each of the

- Add electrons pairs to complete the octets around the atoms (exceptions include hydrogen which has a maximum of 2, boron and beryllium which can have incomplete octets, and elements in the 3rd period which can expand their octects Step 5 - If the octets are not filled, form double or triple bonds to complete them Step 6 - Check the number of electrons in the final structure is equal to that calculated in step 1. Lets try this for NO2 Total number of electrons = 18

But we see nitrogen has an incomplete octet, and the way to fill it is to throw over a pair of electrons from the oxygen to form a double bond with the nitrogen.

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Now we recheck to see if we have 18 valence electrons in the molecule, we have 2 on the nitrogen, 6 in bonds, and 10 around the oxygens. 2+6+10=18 4.2.4 State and explain the relationship between the number of bonds, bond length and bond strength Double bonds are stronger than single bonds and triple bonds are stronger than double bonds (relative to the same atom). This is because there are more electrons shared between the two nuclei.

Therefore the bond strengths increase and bond lengths decrease the higher the bond order. Bond type C-C C=C CC Bond enthalpy kJmol^-1 348 612 837 Bond length nm 0.154 0.134 0.120

4.2.5. Predict whether a compound of two elements would be covalent from the position of the elements in the periodic table or from their electronegativity values. In general non-metals form covalent compounds with each other. The rule is that a electronegativity difference of less than 1.8 will result in a covalent bond. 4.2.6. predict the relative polarity of bonds from electronegativity values Polarities of covalent bonds can be determined from the electronegativity values. The larger the difference in electronegativity, the more unequal the sharing of electrons and therefore the more polar the bond. Element Electronegativity F 4.0 O 3.5 N 3.0 Cl 3.0 C 2.5 H 2.1

From this we can deduce that a C-O and C-Cl bonds are polar but the C-O bond is more polar. A C-O bond has a difference of 1.0 while a C-Cl bond has a difference of 0.5. The N-Cl bond is non-polar

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because the electronegativity value is the same. The C-H bond has a difference of 0.4, which shows it has very low polarity (we effectively consider it non-polar) 4.2.7. Predict the shape and bond angles for species with four, three and two negative charge centres on the central atom using the valence shell electron pair repulsion theory (VSEPR) VSEPR theory states electron pairs around the central atom repel each other bonding pairs and lone pairs of electrons arrange themselves as far apart as possible Bonding and lone pairs are called negative charge centers BP-BP < LP - BP < LP - LP is the order of the strength of repulsion BP - bonding pair LP - lone pair This states that BP BP repulsion is the weakest and LP LP repulsion is the strongest. The molecule or polyatomic ion will present the shape that gives the least repulsion between electrons, both bonding and lone pairs, The shape of a molecule is therefore determined by the electron pairs rather than the atoms themselves.

Two electron pairs -Think about BeCl2, there are 2 negative charge centers around the Be atom, these pairs of electrons will seperate as far as possible so the repulsion is minimized. -This makes the molecule adopt a linear shape, as the furthest possible distance the electron pairs can put between themselves is by staying at 180 degrees from each other. ----Shape is linear Three electron pairs -If there are three negative charge centers the furthest apart they can get is at 120 degrees from each other. -Think of BF3, there is going to be 1 bond forming with each fluorine therefore there are going to be 3 negative charge centers. This will create a trigonal planar arrangement of charge centers.

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Four electron pairs -This is when there are 4 negative charge centers around a central atom. -The angle at which the electron repulsion is minimized is 109.5 in a tetrahedral shape -Examples include CH4 and CCl4. We have 3 possible combinations of lone pairs and bonding pairs for 4 charge clouds. 4 bp - 0lp 3bp - 1lp 2bp - 2lp 1bp - 3lp (we dont really consider this because the molecule will just be linear)

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Molecule H2O NH3 CH4

#lone pairs 2 1 0

#bonding pairs 2 3 4

Bond angles and shape 104.5 Bent 107 Trigonal pyramidal 109.5 Tetrahedral

It is important to note that the shape of the molecule refers to the orientation of the atoms rather than the charge clouds. Meaning if you have 2 lone pairs and 2 bonding pairs, yes you have 4 charge clouds but the molecule is NOT tetrahedral. It is bent. We see that as you increase the number of lone pairs the bond angle decreases (the bond angles refer to the H-O-H bond in water, H-N-H bond in ammonia, H-C-H bond in methane). This is because the lone-pairs have a GREATER repulsion than bonding pairs. This makes the bond angles between the atoms smaller because they repulse them MORE. This is why the bond angle in H2O is less than NH3, because there are 2 lone pairs repelling the bonding pairs rather than just one. This squishes the bond angle more than the NH3 which only feels the effect of one bonding pair Multiple bonds VSEPR considers double and triple bonds as one charge center. Meaning they have the SAME effect as a single bond.

Lets take this ethene molecule, the shape around the carbons is still trigonal planar, because the double bond is still one charge center. It wouldnt even matter if it was a triple bond, the shape would still be trigonal planar.

4.2.8. Predict whether or not a molecule is polar from its molecular shape and bond polarities. Diatomic molecules of the same element will have no polarity as their electronegativity values are exactly the same. Their bonding will also not be polar, as the bond is shared between atoms of the same electronegativity value. This is called a non-polar covalent bond. When atoms of different electronegativities bond, the electrons will be more strongly attracted to the atom with the more electronegative bond. This makes the distribution of the bonding electrons asymmetric. Lets take the example of HCl Chlorine is more electronegative than hydrogen, therefore the electrons in the bond will be attracted to the Cl atom. Making the Cl atom gain a partial negative charge and the H atom gain a partial positive charge

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The HCl molecule is therefore described as polar and the bond is described as polar covalent The polarity of a bond depends on the electronegativity of the constituent atoms. The larger the electronegativity difference, the more polar the bond, if the electronegativity difference becomes too large the bond will become ionic

The separation of charge is called the polarization. When opposite electrical charges are seperated by distance in a molecule, a dipole is established. The magnitude of the dipole is measured by the dipole moment Polarities of molecules HCl H2O NH3 Benzene CH4 HCCl3 CCl4 CO2 Bromobenzene Polar Polar Polar non-polar non-polar Polar non polar non-polar Polar

The polarity depends on the electronegativity value of the atoms AND how the atoms are arranged. Lets take the example of the CO2, the electronegativity values are different but the molecule is nonpolar. This is because the shape is linear, and the charges cancel out making the overall molecule non polar. However the bonds are polar covalent because there still is a difference in electronegativity. 4.2.9. Describe and compare the structure and bonding in the three allotropes of carbon (diamond graphite C60 fullerene) Giant covalent lattices are usually 3D structures of atoms covalently bonded together. Allotropes - two or more crystalline forms of the same element in which the atoms/molecules are bonded differently

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Graphite - each carbon atom is covalently bonded to 3 other carbon atoms forming 2D layers of carbon arranged in hexagons. -There is no bonding between the layers but there are vanderwaals forces because of the large suface area. -There is slight metallic bonding because of the delocalized electron per carbon atom, this accounts for the fact that graphite is a conductor on the plane of the crystal when a voltage is applied

Fullerenes -60 carbon atoms are covalently bonded to each other -all sp2 hybridized -forms a structure with 60 vertices and 32 faces. Diamond -carbon atoms in a giant covalent structure with each atom bonded to 4 others.

4.2.10. Describe the structure of and boding in silicon and silicon dioxide SiO2 -exists as a giant covalent structure -It is bonded in a tetrahedral manner in SiO4 groups which are in turn held together by Si-O-Si bonds -It is transparent, hard, and has a high melting and boiling point. Si -Each silicon atom is bonded to 4 other silicon atoms like in diamond. -It is softer than diamond because of the longer bonds - pure Si is an insulator

4.3 Intermolecular Forces

4.3.1 Describe the types of intermolecular forces and explain how they arise from the structural features of molecules Van Der Waals forces -these are caused by temporary dipoles -temporary dipoles are formed by random movements of electrons , which can be asymmetrically distributed over a molecule at a certain instant.

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-Like we see in helium above -The unequal distribution of electrons will create an instantaneous dipole, which will repel electrons of a neighbouring atom -This will create an attraction between these 2 atoms. Factors that influence VDW force -molecular size -molecular shape We see the VDW force getting larger for the halogens because the size of the molecules are increasing. The higher the number of electrons in the molecule the stronger the instantaneous and induced dipoles are going to be. If we think of pentane in these forms

2,2 dimethylpropane

pentane

The normal pentane molecule will have a larger surface area for interaction therefore have a higher boiling point. The isomer of pentane will have a lower boiling point because of the lower surface area of the VDW forces. Dipole Dipole forces In a polar molecule the positive end will attract the negative end of another dipole, this electrostatic attraction is the dipole dipole force. In a polar molecule there will be a permanent dipole, because a polar molecule will always have a dipole moment. They only work if the molecules are packed close together (in solid or liquid states), and are weak compared to ionic or covalent bonds. The strength of this force depends on the dipole moment. The larger the dipole moment the larger the force. Hydrogen bonding 44

HB is a strong permanent dipole-dipole attraction between molecules with a hydrogen atom covalently bonded to a O F or N atom. The requirements for a hydrogen bond are that the hydrogen has a partial positive charge, which will be electrostatically attracted to a lone pair of electrons on the electronegative atom (O, F or N)

This shows the hydrogen bonding in ammonia. Each ammonia molecule can only form one hydrogen bond because it only has one lone pair of electrons.

This shows the hydrogen bonding in hydrogen fluoride. The bonding is stronger here than in ammonia because fluorine is smaller and more electronegative than nitrogen, making the hydrogen bond stronger

4.3.2 Describe and explain how intermolecular forces affect the boiling points of substances Strengths of intermolecular forces When comparing intermolecular forces 2 generalizations must be made -When you have molecules with similar mass, the dipole dipole forces are more significant. The most polar molecule will have the higher boiling point -When you have molecules with very different masses, the VDW forces are more significant. The molecule with the highest relative molecular mass will have the higher boiling point.

-this shows the boiling points of group 4 5 6 7 hydrides. -The high boiling points for water ammonia and hydrogen fluoride are attributed the hydrogen bonds

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Hydrogen bonds effect on physical properties -boiling points on NH3 H2O HF and some other molecules -solubitlity of covalent molecules in water -density of water and ice -viscosity of liquids

4.4 Metallic Bonding

4.4 .1 Describe the metallic bond as the electrostatic attraction between a lattice of positive ions and delocalized electrons In a metal, the valence electrons are not constrained to a single atom but are free to flow through the lattice. These electrons are delocalized Metallic bonding is the electrostatic attraction of the positive cation lattice and the delocalized electrons

4.4.2 Explain the electrical conductivity and malleability of metals -Metals are ductile, malleable, conduct electricity and conduct heat Why metals are ductile and malleable - If enough force is applied to a metal, the layers of metal cations will slide over each other -The solid will not break because the free electrons are still holding it together -this means the metallic bond is not disrupted even when a force is applied - Meaning that metals can be drawn into wires (ductile) and made into thin sheets (malleable) without breaking Why metals conduct heat and electricity -When a voltage is applied to the metal, the delocalized electrons will flow from the negative to the positive electrode, this flow of electrons constitutes an electric current. -The delocalized electrons can conduct heat by carrying kinetic energy from the hot to the cold part of the metallic lattice. -both properties are attributed to the delocalized electrons.

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4.5 Physical Properties

4.5.1 Compar e and explain the propert ies of substan ces resultin g from differe nt types of bondin g

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Solubility Solubility of solids - There are 3 stages to the dissolution of solids -The lattice must be broken, the process is endothermic -The intermolecular forces in the liquid (VDW, hydrogen bonds, dipole dipole) must be disrupted, the process is also endothermic -New bonds formed between the molecules in the solid and the liquid (this is an exothermic process) -Generally a solid is more likely to dissolve if the whole process ends up being exothermic. -High solubility is more likely if - the attraction strength is greater between the liquid and solid than the solid and solid and the liquid and the liquid. General rule : Like dissolves like. Meaning : polar dissolves polar non polar dissolves non polar Solubility of liquids -Similar to solubility of solids. - a polar solvent will dissolve another polar liquid - such as water and ethanol - the oppositely charged ends of each molecule will form hydrogen bonds with each other -a polar solvent will not dissolve a non-polar liquid - like water and tetrachloromethane (CCl4) -the hydrogen bonds in water and the VDW forces in CCl4 are stronger than the force that will hold the H2O and CCl4 molecules together if they could dissolve -meaning it is not energetically favorable to do so and the liquids will not mix. Solubility of gases -most gases are only slightly soluble in water (noble gases, N2, O2 etc) -However some gases which are polar can dissolve in water

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-including HCl, it will react with water to form hydrochloric acid. -The positively charged hydrogen in the HCl molecule and the negatively charged oxygen in the water will attract and form a bond with the hydrogen. -the chlorine will gain both of the electrons from the covalent bond and a hydronium (H3O+) ion and a chlorine (Cl-) ion will form

Physical properties of ionic compounds Brittle - this is because the planes of ions can slide over each other, and if then a positive and a positive or a negative and a negative are then placed adjacently, the crystal will break because of the repulsion.

High melting and boiling points - the attraction of the oppositely charged ions is greater than the repulsion of the ions with the same charge -meaning it needs a large amount of energy to separate the ions. -leading to its hardness and high melting and boiling points Electrical conductivity - When solid the ions are not free to move and therefore cannot carry a charge. -When dissolved in water or molten the ions are free and therefore can carry a charge. Properties of simple molecular compounds Low melting/boiling points -the covalent bonds that hold individual molecules together are strong and difficult to break -however the VDW forces holding different molecules together are weak and only these need to be broken to melt/boil the compound Solubility in water - most compounds whose intermolecular forces are VDW forces tend to be scarcely soluble in water. 49

-including iodine -compounds which form hydrogen bonds tend to be very soluble in water -including amines and sugars -this is provided they have the ability to form multiple hydrogen bonds and have a low molar mass

Topic 14: Bonding (HL ONLY)

14.1 Shapes of molecules and Ions
14.1.1 Predict the shape and bond angles for species with five and six negative charge centers using VSEPR theory [REFER BACK TO TOPIC 4 FOR PREREQUISITE KNOWLEDGE] -The formation of species with five and six negative charge centres occurs when an atom expands its octet -Expansion of the octet occurs when an electron is promoted to a suitable low energy orbital to accommodate extra electrons. This will happen when the energy released from bond creation offsets the energy required to raise electrons energy levels. - For example in Phosphorus, a 3s electron is promoted to the 3d orbital to result in 5 unpaired electrons to form PCl5. -The base structure of a substance with five negative charge centres is trigonal bipyramidal (a trigonal planar shape with two more charge centres at 90 perpendicular to the plane). -When one or more pairs of electrons are a lone pair they will occupy a centre on the trigonal plane. -The base structure of a substance with six negative charge centres is octahedral (a square planar shape with two more charge centres at 90 perpendicular to the plane). -When one or more pairs of electrons are a lone pair they can occupy any centre as all bond angles are at 90. Two lone pairs will however locate themselves at opposite centres. -The table below summarises the structures and angles (Note the effect that lone pair-bonding pair repulsion has on structural angles)

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14.2 Hybridization
14.2.1 Describe Sigma and Pi bonds -When the atomic orbitals of two atoms (each with an unpaired electron) overlap, a molecular orbital is formed. This is know as a covalent bond. -The strength of the bond is related to the match in energy levels and degree of overlap of the atomic orbitals. -Dative covalent bonds also form by the overlapping of orbitals, however both electrons come from a single atom. -Sigma () bonds occur when axial (head-on) collisions of orbitals occur. -The bonds fall along the internuclear axis. -The shape of the molecule formed between atoms is determined by bond framework around the central atom -The different forms of bond are as below:

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-Pi () bonds occur when two parallel p orbitals overlap sideways. -This type of bond occurs in double and triple covalent bonds. -A double bond has one and one bond. -A triple bond has one and two bonds. -They require a bond to have formed, to bring the p orbitals in the proximity to overlap. -They result in poor shielding of the nuclei of atoms involved, and electrons being further from the nuclei (in comparison to bonds). -This means they are polarisable and hence chemically reactive. -They are weaker than bonds due to the smaller extent of orbital overlap. This is shown by bond enthalpy values for single, double and triple bonds -They form above and below the plane of atoms -They do not affect the shape of a molecule

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-The bonds and locations in ethene are shown as an example below -Note that the only 1 bond is present in ethene, and that a secondary bond (present in

ethyne) would be in a plane in front and behind the internuclear axis in this orientation. 14.2.2 Explain hybridization in terms of the mixing of atomic orbitals to form new orbitals for bonding -In hybridisation orbitals of the same atom overlap to form a set of hybrid atomic orbitals. -These orbitals have specific shapes and orientations, dependant on the orbitals being hybridised. -The number of hybridised orbitals formed is equal to the number of orbitals being hybridised. -All atoms (except hydrogen) are reasoned to undergo hybridisation prior to bonding. -Hybrid orbitals have electron density concentrated on one side of the nucleus, hence allowing for stronger bonding. -Hybrid orbitals repel each other, adopting a configuration for minimised repulsion. -Hybridisation frequently involves the excitation of electrons to move into higher orbital energy levels -NOTE: Hybridisation is a model, not an actual process.

-The three main types of hybridisation are as follows: -sp: a single s and p orbital overlap and merge to form 2 identical (in both shape and energy) sp hybridised orbitals, oriented at 180 to each other

-the energy of the hybrid orbital is intermediate between that of the lone s and p orbitals -sp2: an s and two p orbitals overlap and merge to form 3 identical (in both shape and energy) sp2 hybridised orbitals, whose major lobes orient towards the corners of an equilateral triangle -the energy of the hybrid orbital is intermediate between that of the lone s and p

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orbitals -sp3: an s and three p orbitals overlap and merge to form 4 identical (in both shape and energy)

sp3 hybridised orbitals, whose major lobes form a tetrahedral shape -A diagram summarising the formation of ethene is as below

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This table summarises hybrid orbitals and their relation to bonding in carbon

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14.2.3 Identify and explain the relationships between lewis structures -VSEPR theory can be applied to identify the hybridisation state of the central atom in a structure. -sp3 hybridisation can be used to describe bonding with 4 negative charge centres around the central atom -sp2 hybridisation can be used to describe bonding with 3 negative charge centres around the central atom -sp hybridisation can be used to describe bonding with 2 negative charge centres around the central atom -Following table summarises this in relation to structural shape

IMPORTANT FOR FIGURING OUT HYBRIDIZATION OF AN ATOM There is a shortcut to finding the hybridization of an atom It uses a simple arithmetic calculation called Steric number, referred to as SN SN= number of bond centers + number of lone pairs SN = 4 -> sp3 SN=3 -> sp2 SN= 2 -> sp

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SN=1

-> s

SN values can go higher such as SN 5 and 6 having sp3d and sp3d2 hybrid orbitals respectively but I dont think that is in the syllabus. Examples -> what is the hybridization of the nitrogen atom in ammonia? In ammonia (NH3) the nitrogen has a single lone pair, and is singly bonded to THREE hydrogen atoms. Therefore the SN = 3 bond centers + 1 lone pair =4 an SN of 4 gives us sp3 hybrid orbitals for nitrogen in NH3 -> what is the hybridization of carbon in cyanide? In cyanide (HCN) the carbon is triple bonded to the nitrogen and single bonded to the hydrogen Therefore the SN = 2 bond centers (1 for the nitrogen even though its triple bondec and 1 for the hydrogen) + 0 lone pairs SN = 2 Giving us sp hybrid orbitals for C in HCN Remember that even a double bond or triple bond counts as ONE bond center. Reasoning for this: When the second bond with the same atom forms, a pi bond forms. All a pi bond is, are p orbitals from different atoms forming a bond perpendicular to the internuclear axis. Meaning this P orbital, even though bonded to the other atom, doesnt involve itself in the i nitial sigma bond. Which is where all of the hybridization occurs.

14.3 Delocalization of Electrons

14.3.1 Describe the delocalization of electrons and explain how this can account for the structures of some species -In some molecules and compound ions, lewis diagrams can be drawn with lone pair and bonds in different positions. -For example carbonate (CO32-) has three possible structures (assuming that the oxygen atoms

have not changed positions):

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-The carbonate is not correctly represented by any one of the three resonance structures, existing as a

resonance hybrid (a blend of all three) like below. -Each resonance structure contributes to the resonance hybrid, although the lower its energy, the more it will contribute. (In the example of carbonate all three structures are of equal energy and contribute equally). -The dotted line in the structure indicates a partial double bond character, and the - is dipole. -There is experimental proof of this, where the bond length is shown to be intermediate between that of a single and double bond. -A resonance hybrid is more stable than any of the resonance structures. -The energy difference between a resonance structure and hybrid is know as resonance energy. -For significant resonance stabilisation to occur structures must: -Have the same molecular shape -Not have a very high energy (obeying the octet and duplet rules were appropriate) -Contain the same number of electron pairs -Carry the same net charge

-Also to be considered: -In the case of ions the most stable resonance structures will place the negative charges on the more electronegative atoms, and positive charges on the less electronegative -The most important resonance structures are those where the most atoms possible obey the octet rule, have the maximum number of bonded electrons and which have the fewest charges. -The greater the number of resonance structures generally the greater the stability of the resonance hybrid. -An example of resonance in organic chemistry is the benzene molecule (C6H6)

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-It occurs in two major resonance structures known as Kekul structures. -The two resonance structures are symmetrical and make equal contributions to the resonance hybrid. -All carbon carbon bonds are equivalent, being intermediate between single and double bond strengths and lengths. -An alternative model to describing resonance stabilised structures is molecular orbital theory. -In this application of the theory the electron orbitals are delocalised, extending over three or more atoms. -Benzene can be explained under this theory, as each carbon atom will have a 2p z orbital, with lobes above and below the plane, which overlap to form a large electron orbital ring above and below the benzene ring plane. This is shown below. -This means that the six electrons are delocalised over the electron orbitals,

resulting in the partial double bonds. -All molecules and ions in which the bonding has multiple resonance structures can be explained in terms of the delocalised electron orbital, s uch as CO32-, where pz orbitals overlap to form a 4 centred delocalised orbital. -To ensure maximum overlap of pz orbitals the molecule or ion must be planar.

Additional Content: Bond Orders 59

-To calculate bond orders we must know the number of bonds in one resonance structure and the total number of resonance structures. Bond order = (number of bonds in one resonance structure)/(number of resonance structures) -For example, with the carbonate ion, the total number of bonds in one structure is 4 and there are 3 resonance structures meaning the bond order is 4/3 or 1.33.

Topic 5: Energetics
5.1 Exothermic and Endothermic Reactions 5.2 Calculation of Enthalpy Change 5.3 Hess Law 5.4 Bond Enthalpies

Topic 6: Kinetics

6.1 Rates of Reaction

6.1.1 Define the term rate of reaction. The increase in concentration of products or decrease in the concentration of reactants per unit time. RoR = increase in product concentration/time taken RoR = decrease in reactant concentration/time taken The units are moldm-3s-1

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Product concentration vs time taken on the left, and reactant concentration vs time taken on the right. Since both of the graphs are curves, the gradient changes across them. Therefore the rate of reaction changes as the time passes. To measure the rate at any particular point a tangent must be drawn at the point, and the gradient of the tangent must be measured. This gradient will be the rate of reaction at that point in time. Ex, if we want to measure the rate at 60 seconds, a tangent would be drawn on either the product or reactant curves at t=60 seconds. Note : The gradient in the reactant curve will always be negative, but the rate is always expressed as a positive value. To measure the initial rate the tangent must be drawn at t=0. 6.1.2 Describe suitable experimental procedures for measuring rates of reactions. 1) change in volume of gas produced If one of the products of a reaction is a gas the volume of gas released can be used to measure the rate. A gas syringe is probably the best instrument for this. If a gas syringe isnt available a inverted measuring cylinder can measure the gas release. This method can be problematic if the gas released is soluble in the water. To overcome the error caused by this warmer water could be used as gases are less soluble in warm water 2) Change in mass The change in mass could be measured if one of the products of the reaction is a gas. The conical flask (or whichever container) in which the reaction is taking place is put directly on a mass scale with cotton wool on the opening to prevent any solid or liquids from escaping. The mass change will correspond to the amount of gas released. However with reactions involving hydrogen, the hydrogen gas released may be too small a mass to give a significant overall change. 3) Change in transmission of light This can be used if ONE of the reactants OR products are colored. Or an indicator can be dropped in to give a colored compound that can be studied through the reaction. A colorimeter or a spectrophotometer can pass light (at specific wavelengths, usually in the visible region) through the solution and measure how much of the light is absorbed. As the colored compound increases in concentration, less light will be passed through and more will be absorbed. This gives a quantitative measurement of how far the reaction has progressed as you are measuring the concentration of a reactant or product through measuring the absorbance of the solution. An example would be the decomposition of hydrogen iodide into hydrogen and iodine.

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2HI (g) -> H2 (g) + I2 (g) Only the I2 is colored, meaning the absorbance of the gases can be measured in order to find the rate of the reaction For this reaction, a specific wavelength must be set in the colorimeter. Alternatively,a colored filter can be used, ensuring that the color of the filter is complementary to the color of the compound (ie .Since I2 is brown, green filter needs to be used which is about 546nm). The reaction is to be done in the cuvette of the colorimeter, and the absorbance value can be calculated as the concentration of the reactant in rate equation (in this case the HI) changes. Then, a concentration against absorbance graph can be plotted to understand the relationship between the concentration of the reaction and the rate equation.

4) Titrations A standard solution could be used to titrate against a ONE of the reactants OR products. Samples must be withdrawn at time intervals and then either titrated with or against. However during the titrations the sample will continue to react, in order to stop this a method known as quenching is used. A substance is introduced to effectively stop the reaction from progressing any more. Also, the substance is added to cold water to stop the reaction, or if the reaction is facilitated by acid (think KmnO4 Glucose), then alkaline can be added to neutralise the acid and thus stop the reaction at the specific times) An example of this would be the reaction between hydrogen and acidified potassium iodide, which gives I2. Sodium carbonate is used to quench the reaction by neutralizing any of the acid. This solution is then titrated against sodium thiosulphate. 5) Measuring conductivity The conductivity of a solution depends on the concentration of ions in it. If this changes as the reaction progresses measuring the conductivity can be used to follow its progress. This usually means putting electrodes in the solution, which are first calibrated with solutions of known conductivity. 6) Non-continuous methods of detecting change during a reaction : clock reactions Measure the time taken for a reaction to reach a fixed point, something observable that can be classified as an end point. Such as measuring how long it takes for a solution to become colored. 6.1.3 Analyse data from rate experiments ?

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6.2 Collision Theory

6.2.1 Describe the kinetic theory in terms of the movement of particles whose average energy is proportional to temperature in kelvins. All particles vibrate, rotate and translate and the velocity it does so is dependent on its energy. The average energy of all the particles in the substance is its temperature, which is generally measured in kelvin (K) The temperature of a substance in kelvin is proportional to the average kinetic energy of the particles in a substance. 6.2.2 Define the term activation energy, Ea. The minimum value of kinetic energy which particles must have before they are able to react. 6.2.3 Describe the collision theory For a reaction to occur the particles must collide. The energy of the collisions result in bonds between reactants breaking and new bonds forming between the products. The number of collisions that are successful will determine the rate, remember that not all collisions are successful. There are generally 2 factors which determine if the collision is successful or not, energy and geometry. Energy -the particles must have the activation energy in order to undergo a successful collision. This energy is to overcome the repulsion between the molecules, and breaking bonds in the reactants if necessary. -when adequate energy is supplied the transition state is made. allowing the products to be formed **PUT DIAGRAMS Geometry -The collisions may occur in a whole bunch of orientations, but not all of them will lead to a successful collisions. (Think enzymes and active sites) **PUT DIAGRAM

6.2.4 Predict and explain, using the collision theory, the qualitative effects of particle size, temperature, concentration and pressure on the rate of a reaction. Particle size / Surface area -Decreasing particle size will increase the rate of reaction as it will increase the surface area -More surface area leads to more effective collisions per unit time Temperature

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- As temperature of the particles increase, they have more energy - Thus, the particles have more energy to collide and hence the energy in collision increases, thus the number of particles with energy more than the activation energy increases - This means that more particles can effectively collide to produce successive collisions and hence the rate of reaction increases - Also, as temperature increases kinetic movement of the particles increase - This means that the particles are moving more and thus the frequency of collision also increase - However, the main point is the increase in energy as frequency also applies to concentration Concentration - As concentration increases the number of particles per unit volume increase - Hence, there will be more frequent collisions that occur and thus, the rate of reaction will increase Pressure -applicable for gases - As pressure increases the number of particles per unit volume increase - Hence, there will be more frequent collisions that occur and thus, the rate of reaction will increase Catalysts?

6.2.5 Sketch and explain qualitatively the MaxwellBoltzmann energy distribution curve for a fixed amount of gas at different temperatures and its consequences for changes in reaction rate.

The curve starts from the origin because there are no particles with no energy. The average kinetic energy is slightly to the right of the peak because there are technically more particles to the right of the peak than there are to the left, this would shift the mean to the right of the peak. The curve asymptotes towards the x axis as we move further along the curve as there is no theoretical limit to the amount of energy a particle can posses.

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The area underneath the curve represents the number of particles. Since the average kinetic energy would have increased (because temperature increased) the point of average kinetic energy must be shifted to the right. In order to keep the area underneath the curve constant (because the number of particles are the same) the peak must be shifted down. At this higher temperature a larger proportion of the particles have an energy greater than the activation energy, which is why effective collisions take place more frequently at a higher temperature.

6.2.6 Describe the effect of a catalyst on a chemical reaction.

- A catalyst is a chemical compound that alters the rate of reaction without itself undergoing any chemical change -Usually be providing the reactants with another method of becoming the products, in other words providing an alternative reaction pathway . This pathway requires the reactants to have LESS energy to become the products. - Catalyst can be homogenous or heterogenous - Homogenous catalysts are those that are in the same state as the reactants 2I- + Fe3+--> I2 + Fe2+ S2O8 + Fe2+ Fe3+ + 2SO42- Heterogenous catalysts aree those that are in a different state to the reactants eg. C2H4(g) + H2(g) ----> C2H6 (Ni)s 6.2.7 Sketch and explain MaxwellBoltzmann curves for reactions with and without catalysts

The catalyzed reaction has a lower activation energy than the uncatalyzed one. To the right of the catalyzed Ea are the particles that have sufficient energy to undergo successful

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collisions. This area is greater than the area of the particles with sufficient energy in the uncatalyzed reaction. This is why a catalyst increases the rate of reaction. The number of particles with sufficient activation energy increases, meaning there are more frequent effective collisions.

Topic 7: Equilibrium
7.1 Dynamic Equilibrium 7.2 The Position of Equilibrium

Topic 8: Acids and Bases

8.1 Theories of Acids and Bases 8.2 Properties of Acids and Bases 8.3 Strong and Weak Acids and Bases 8.4 The pH Scale

Topic 9: Oxidation and Reduction

9.1 Introduction to Oxidation and Reduction 9.2 Redox Equations 9.3 Reactivity 9.4 Voltaic Cells 9.5 Electrolytic Cells

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Topic 10: Organic Chemistry

10.1 Introduction 10.2 Alkanes 10.3 Alkenes 10.4 Alcohols 10.5 Halogenoalkanes 10.6 Reaction Pathways

Topic 11: Measurement and Data Processing

11.1 Uncertainty and Error in Measurement 11.2 Uncertainties in Calculated Results 11.3 Graphical Techniques

Higher Level

Topic 15: Energetics

15.1 Standard Enthalpy Changes of Reaction 15.2 Born-Haber Cycle 15.3 Entropy 15.4 Spontaneity

Topic 16: Kinetics

16.1 Rate Expression
16.1.1 Distinguish between the terms rate constant, overall order of reaction and order of reaction

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with respect to a particular reactant. Rate = [A]n [B]m k is the rate constant for a particular reaction at a specified temperature. The order of reaction is the exponent to which the concentration term of a substance in the rate equation is raised to (n.m) A and B are the concentration values of substance A and B. Overall order of reaction is the sum of the exponents to which the reactants are raised to. m+n Order of Reaction the exponent term in the equation indicates the relationship between the concentration of the reactant and the rate of reaction. Usually there are 3 different orders; zero, first or second order reactions. R0 (zero order) Rate is constant even with concentration changing. R1 (1st order) Rate is directly proportional with concentration changing it by the same factor. R2 (2nd order) Rate is directly proportional to concentration changing it by the square factor. 16.1.2 Deduce the rate expression for a reaction from experimental data.

Concentration of Br2 doubles rate quadruples. Br2 order of reaction must be 2. Concentration of NO quadruples, rate remains the same. NO order of reaction must be 0. Therefore the answer is C. 16.1.3 Solve problems involving the rate expression.

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i) NO doubles, rate quadruples; second order with respect to NO H2 doubles, rate doubles; first order with respect to H2 ii) rate = k[NO]2[H2] iii) k = (10.00x10-5) / (10.00x10-3)2 (4.00x10-3) = 2.50 x 102 mol-2 dm6 s-1 16.1.4 Sketch, identify and analyse graphical representations for zero-, first- and second-order reactions.

Zero order reactions have a linear relationship between time and concentration. The half life decreases. First and second order reactions both look like exponential decay graphs, but 1st order graphs have a constant half life. 2nd order reactions have an increasing half life.

16.2 Reaction Mechanism

16.2.1 Explain that reactions can occur by more than one step and that the slowest step determines the rate of reaction (rate-determining step). It is extremely unlikely for more than 2 molecules to collide simultaneously. Therefore, the reaction will occur in multiple stages. This process is called the reaction mechanism. Eg. CO + NO2 CO2 + NO This reaction occurs in 2 steps. 2 NO2 NO3 + NO (slow) NO3 + CO NO2 + CO2 (fast) The slowest step determines the rate of the reaction and is called the rate-determining step.

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Keep in mind that when proposing a reaction mechanism to not involve more than 2 molecules in one step as it is extremely unlikely that those collision will occur. 16.2.2 Describe the relationship between reaction mechanism, order of reaction and rate-determining step. The order of reaction always matches the number of molecules involved in the rate-determining step and the steps before. If you are given the rate expression you can check your proposal if it is correct. Eg. 2NO(g) + 2H2(g) N2(g) + 2H2O(g) The rate equation is: rate=k[NO]2[H2] Deduce the 3 step mechanism and state the rate determining step. There has to be 2 NO molecules reacting in the rate determining step and before. 1 H2 molecule has to aswell. NO(g) + NO(g) N2O2(g) N2O2(g) + H2(g) H2O(g) + N2O(g) N2O(g) + H2(g) N2(g) + H2O(g) Step 2 is the rate determining step. This is constant with the rate equation as N 2O2 is a intermediate and cancels. This leaves NO appearing twice and H2 appearing once.

16.3 Activation Energy

16.3.1 Describe qualitatively the relationship[ between the rate constant (k) and temperature (T). As temperature increases, the average kinetic energy of the reactants increase, and more molecules will have the required activation energy to successfully react. The activation energy is the minimum amount of energy required in a collision between molecules in order for a chemical reaction to occur. For every 10O C rise in temperature, the rate of reaction will almost double. Rate = k [A]m [B]n - Therefore, as the temperature of the reaction increases, the time taken for the reaction to occur reduces. - Since we are aware of the inverse relationship between time and rate, as time reduces, the rate increases - This means that since the concentration of the reactants stay the same, the rate constant must increase - Therefore, as temperature increases, time of reaction decreases, so rate increases, so rate cosntant increases 16.3.2 Determine activation energy (Ea) values from the Arrhenius equation by a graphical method.

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Therefore, to find the activation energy we need to - Get the ln k and i/T values - plot them in a graph - Find the gradient - Multiply the gradient by the Gas constant R = 8.31 - Final result is the activation energy of the reaction

Topic 17: Equilibrium

17.1 Liquid-Vapour Equilibrium 17.2 The Equilibrium Law

Topic 18: Acids and Bases

18.1 Calculations Involving Acids and Bases 18.2 Buffer Solutions 18.3 Salt Hydrolysis 18.4 Acid - Base Titrations 18.5 Indicators

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Topic 19: Oxidation and Reduction

19.1 Standard Electrode Potentials 19.2 Electrolysis

Topic 20: Organic Chemistry

20.1 Introduction 20.2 Nucleophilic Substitution Reactions 20.3 Elimination Reactions 20.4 Condensation Reactions 20.5 Reaction Pathways 20.6 Stereoisomerism

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