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2013 Chemistry NCEA L2 2.4 Bonding, Structure and Energy GZ Science Resources 2013 1 SJ Gaze Achievement Criteria Bonding, structure and energy changes are limited to: Lewis structures, shape and polarity of simple molecules. Simple molecules have no more than four electron pairs about any atom (including multiple-bonded species) Intermolecular forces (the distinction between the different types of intermolecular forces is not required) Ionic, covalent and metallic bonding Molecular, ionic, metallic and covalent network substances Properties are limited to hardness (including malleability and ductility), electrical conductivity, melting and boiling points and solubility. Exothermic and endothermic reactions including energy changes associated with the making and breaking of chemical bonds, differing amounts of substances and changes of state. These may involve calculations. GZ Science Resources 2013 2 Introduction Chemistry is the study of matter and energy and the interaction between them. The elements are the building blocks of all types of matter in the universe. Each element is made up of only one type of atom, each with its specific number of protons known as its atomic number. GZ Science Resources 2013 3 Introduction A large amount of energy is required to break an atom down into smaller particles. The elements occur in widely varying quantities on earth. The ten most abundant elements make up 98% of the mass of earth. Many elements occur only in traces, and a few elements are synthetic and highly unstable. 4 Atomic Theory Atoms are the building blocks of elements. Scientists and philosophers have guessed that all matter is made up of building blocks for a very long time. Discovery of the actual structure of the atom has only been in relatively recent times however. GZ Science Resources 2013 5 Atomic Theory Democritus – Greek philosopher 400 B.C. The word atom comes from the Greek word atomos meaning indivisible. Democritus reasoned that you could continue to half a piece of matter only to a particular point – the smallest particle that could no longer be divided was known as an atom. The structure of the atom was unknown at this time. GZ Science Resources 2013 6 Atomic Theory Boyle – English physicist 1661 Robert Boyle investigated the elements, gold and silver, and found they could not be changed into earth, air, fire or water, that previously Aristotle (Greece 350BC) claimed all matter was made of. He concluded that gold and silver were true elements and created a definition for an element: An element is any substance that cannot be broken down into a simpler substance. GZ Science Resources 2013 7 SJ Gaze Atomic Theory Lavoisier – French Chemist 1743 - 1794 Antoine Lavoisier used a weighing balance to investigate mass relationships in chemical reactions. The law of Conservation of Mass is based on his findings. The total quantity of matter before and after a chemical reaction is the same. 8 Atomic Theory Proust – French Chemist 1799 Joseph Proust investigated individual elements that made up compounds. The law of Constant Composition is based on his findings. All pure samples of a given compound contain the same elements combined in the same proportion by mass. GZ Science Resources 2013 9 Atomic Theory Dalton – English Chemist 1808 John Dalton lived most of his life as a teacher and public lecturer, but his curiosity of the world around him led him into research and experimentation in many areas of Science. One of his most valuable areas of study was in Chemistry concerning the atom and elements. Dalton devised his own notation for elements known at the time. GZ Science Resources 2013 10 Atomic Theory Dalton – English Chemist 1808 John Dalton combined previous ideas about atoms in a published a book, called A New System of Chemical Philosophy, adding his own ideas. A summary of the main ideas from his Atomic Theory are: All matter is made up of extremely small particles called atoms. All atoms of one element are identical. Atoms of one element differ in size and mass from atoms of another element. Atoms are indestructible and merely rearrange themselves during chemical reactions. Atoms of different elements combine in simple whole number ratios to form chemical compounds. GZ Science Resources 2013 11 Dalton’s Atomic Theory 1. All Matter is made up of atoms 2. Matter can neither be created nor destroyed 3. Atoms of a particular element are alike GZ Science Resources 2013 4. Atoms of different elements are different 5. A chemical change (reaction) involves the union or separation of individual atoms Atomic Theory Dalton – English Chemist 1808 Dalton also investigated compounds and came up with the following ideas: Compounds are composed of molecules Molecules are composed of atoms in definite proportions GZ Science Resources 2013 13 Atomic Theory Avogadro – Chemist 1811 Amedeo Avogadro also demonstrated that some elements, such as hydrogen and oxygen, existed in their natural state as more than one atom bonded together. He called those particles molecules. A molecule is the smallest particle of a particular substance which can exist in a free state. 14 GZ Science Resources 2013 Atomic Theory Berzelius – Swedish professor 1813 JÖns Berzelius developed a system of chemical symbols to represent elements. Dalton had devised little pictures but these were difficult to draw. He used letters of the alphabet for the latin name of each element, and a further letter if there was more than one element that started with the same name. Berzelius’s system is now used universally by scientists. The first letter is always a capital letter The second (if there is a second) is always a lower case letter GZ Science Resources 2013 15 Atomic Theory Elements consist of only one type of atom. Each element can be represented by a chemical symbol. Most symbols are one or two letters, formed from the name of the element, e.g. Hydrogen H, or Helium He. The first letter of the symbol is always a capital letter. Any other letters are lower case. e.g. Helium is He not HE If the symbols are not based on a elements English name then it is most likely to be based on it’s Latin name, the original language of Science. 16 Atomic Theory JJ Thompson – English Physicist 1897 Thompson used cathode ray tubes to discover the presence of negatively charged particles 1/2000 the mass of atoms. These particles, called electrons, were found in all atoms. He developed the ‘plum pudding’ model to explain that the negative electrons must be balanced by positive particles to produce a neutral atom. 17 Atomic Theory Rutherford – New Zealand Physicist 1911 Ernest Rutherford discovered the true structure of atoms by using alpha particles (helium nuclei) fired at gold foil. A large number of these particles travelled straight through and he surmised: Almost all of the space occupied by an atom must be empty From the small number of particles that bounced directly back he surmised: The centre of an atom must be very dense and small From the way the positive alpha particles were deflected is surmised: The centre of an atom must contain a region with a very great positive charge GZ Science Resources 2013 18 Atomic Theory Rutherford – New Zealand Physicist 1911 Results from Rutherford’s gold foil experiment could not be explained by the ‘plum pudding’ model of Thompson so Instead, in 1911, Rutherford proposed a new model of the atom in which all of the positive charge is condensed into a tiny, massive nucleus about ten thousand times smaller than the entire atom. Rutherford explained the much lighter electrons circulated outside the nucleus. This was a revolution in the ideas of atoms as Rutherford’s model implied that matter consisted almost entirely of empty space. GZ Science Resources 2013 19 Atomic Theory Ernest Rutherford named the positive particles protons found in the dense centre nucleus. Because this accounted for only around half the mass in most atoms he deduced there must be a similar amount of neutral particles - he named these neutrons. Electron -ve Nucleus Neutron N NP P N N P P P NP N Proton +ve Shell 1 Shell 2 GZ Science Resources 2013 Atom Charges Protons are positively charged; electrons are negatively charged; neutrons have o electrical charge. Atoms have no overall charge because the number of protons = number of electrons. All matter is made up of atoms. Atoms consist of protons, neutrons and electrons. The charges of protons and electrons are equal and opposite. GZ Science Resources 2013 21 Atom Summary Subatomic particle symbol Mass compared to a proton charge location Proton p 1 +1 In the nucleus Neutron n 1 0 In the nucleus Electron e 1/1840 -1 GZ Science Resources 2013 22 Moving outside the nucleus Atomic Theory Moseley – English physicist 1914 Henry Moseley worked alongside Rutherford in investigating atom structure. He discovered some elements had different atomic masses even though they had the same number of protons. He realised elements could be found with different numbers of neutrons and called these varieties isotopes. Atoms with the same number of protons but different numbers of neutrons are called isotopes. Isotopes Isotopes of elements occur when atoms have the same atomic number (Z) but different numbers of neutrons in the nucleus. The numbers of neutrons in an atom does not affect the way an element behaves chemically, but it does affect the way it behaves physically. Isotopes found in nature are generally stable, however radioactive isotopes do exist such as 238Uranium GZ Science Resources 2013 24 Atomic Number Atomic number = number of protons. Symbol = Z The atomic number is unique for each element. An atom has the same number of electrons as protons. The periodic table is arranged in order of an elements atomic number. GZ Science Resources 2013 25 Mass number Mass number = number of protons and neutrons. Symbol = A The Mass number is the number of protons + number of neutrons. The Mass number is close to double of the Atomic number. An isotope is an element with a different Mass number because it has more or less neutrons than normal. Mass number SJ Gaze GZ Science Resources 2013 26 Atomic Theory Bohr – Danish Physicist 1885 - 1962 Niels Bohr was a physicist who also worked alongside Rutherford. He devised a new theory to explain how electrons continuously orbit the nucleus and not gradually lose energy and spiral into it. The main points of his theory were: Electrons only occupy certain orbits of fixed energy Electrons that remain in an orbit don’t emit or absorb energy Electrons can move between orbits. By absorbing energy an electron can move to an orbit further away at a higher energy level. By emitting energy (in the form of light) an electron can move into a lower energy level that is closer to the nucleus. The electron orbits are called energy levels or shells. GZ Science Resources 2013 27 SJ Gaze Energy Levels in Atoms Electrons move further away from the nucleus as they gain in energy. Energy can be provided in the form of heat or light. GZ Science Resources 2013 28 Quantum physics and energy levels Why are electrons in shells or energy levels? It all has to do with quantum physics, where particles, in this case electrons can only contain particular packages of energy. The more packages of energy an electron has, the further out shell it sits in from the nucleus. There can be no half packages or quarter packages; only whole packages, thus the word quantum meaning quantity. Classical physics A turtle sitting on a ramp can have any height above the ground- and so, any energy level. Quantum physics A turtle sitting on a staircase can only sit at certain heights, therefore has only certain energy levels. GZ Science Resources 2013 29 The electrons in an atom are arranged in a series of shells. Electrons move or ‘orbit’ around the nucleus in energy levels or shells. The shells further away from the nucleus are able to fit more electrons. The first shell is filled first, followed by the second and so on until all the electrons (the same number of protons in an atom) have been used. Maximum numbers of electrons in each shell are: >2 in the first shell (nearest the nucleus) >8 in the second shell >8 in the third shell (before the fourth shell starts to fill) >18 in the fourth shell Moving electrons occupy space. Only a certain number can occupy each shell, additional electrons after that must move into a higher level shell. 30 Valence electrons The electrons in the outermost shell of an atom are known as valence electrons. These valence electrons are the particles that react with other atoms in a chemical reaction. The number of valence electrons can determine how an atom will react with others. 31 There is a relationship between the period number and the number of electron shells an atom has. At this time, the maximum number of electron shells (or electron orbitals) for any element is seven. GZ Science Resources 2013 32 In the periodic table, elements have something in common if they are in the same row. All of the elements in a period have the same number of electron shells. Every element in the top row (the first period) has one shell for its electrons) All of the elements in the second row (the second period) have two shells for their electrons. It goes down the periodic table like that.. Electron configuration A shorthand way of describing the way electrons are arranged in an atom is called the electron configuration. The information for the number of electrons is found by an elements Atomic Number (number of electrons = number of protons in a neutral atom). Each shell is filled to its maximum capacity, starting with the lowest shell first (shell number 1 or M shell). The shells are separated by a comma. The shells are filled until all the electrons are placed. 12 Atomic number The total of the electronic configuration must equal the atomic number in an atom 2, 8, 2 Mg First shell, second shell, third shell 24 GZ Science Resources 2013 33 Atomic Theory Latest theories in atomic structure. Atoms consist of a nucleus and surrounding electron cloud. The electrons are obeying quantum mechanics; their The mechanics of exact position and speed can’t be measured but we can only give areas of probability in which the electrons can be found. Area where the electrons are most likely to be found orbiting around the nucleus nucleus ions Ions are charged particles. Ions form when atoms gain or lose electrons. An ion is an atom or group of atoms which has gained or lost electrons. Elements are most stable when the outer shell (valence shell) is full. Elements can lose or gain electrons when they react with other chemicals to form ions and achieve stability. 35 ions Atoms that lose electrons form positively charged ions, or cations. Atoms that gain electrons form negatively charged ions, or anions. Cation (Cat) Anion (an Iron) + Non-Metals gain electrons to form Anions. They have 7-8 electrons in their outside shell. Metals lose electrons to form Cations. They have 1-3 electrons in their outside shell GZ Science Resources 2013 36 ions Atoms with filled outer shells are the most stable. An atom will gain or lose electrons in order to have a filled valence shell. Ions have different chemical properties and a physical appearance to the elements they originated from Cation Sodium (Na) 11+ Sodium now becomes the sodium ion Na+ Anion Chlorine (Cl) 17+ Chlorine now becomes the chlorine ion Cl- Ion Chart - Cations ions 1+ 2+ sodium Na+ magnesium potassium K+ iron (II) ferrous silver ammonium Ag+ NH4+ copper (II) cupric Mg2+ Fe2+ Cu2+ zinc Zn2+ barium Ba2+ Copper (I) cuprous Cu+ Hydrogen H+ lead Pb2+ Lithium Li+ tin Sn2+ 3+ aluminium iron (III) ferric Chromium Al3+ Fe3+ Cr3+ Ion Chart - Anions 1- 2- chloride Cl- carbonate CO32- permanganate MnO4- oxide O2- thiocyanate SCN- sulfide S2- iodide I- sulfate SO42- hydroxide OH- sulfite SO32- hydrogen carbonate HCO3- thiosulfate S2O32- hydrogen sulfide HSO3- chromate CrO42- fluoride F- dichromate Cr2O72- bromide Br- nitrate NO3- hypochlorite OCl- GZ Science Resources 2013 3phosphate 39 PO4-3 Periodic table Mendeleev – Russian professor of Chemistry 1834 - 1907 Dimitry Mendeleev was a Chemist who created a periodic table based on elements relative atomic mass and placed the elements in groups based on the elements similar properties. Not all of the elements had been discovered at the time he created the table so he left gaps that has subsequently been filled. Groups 3 to 12 were added after Mendeleev’s table – these are called the transition metals Group 18 – the noble gases, were not discovered at that time and were also added after. GZ Science Resources 2013 40 Periodic Table The columns (downwards) of a periodic table are called groups. The rows (across) of a periodic table are called periods. Elements in the same group all have the same number of electrons in their outer (or valence) shells. GZ Science Resources 2013 Elements in the same period all have the same number of shells of electrons in their atoms 41 Group 1 elements These elements are called the Alkali Metals. They are all very reactive with air and, especially so, water. The further down the group the more reactive they are. Hydrogen is not included in this as it does not share similar properties with the rest of the elements. GZ Science Resources 2013 43 Group 2 elements These elements are called the Alkali Earth Metals. They all react with air, but are less reactive than group 1. GZ Science Resources 2013 44 Group 17 elements These elements are called the Halogens. They are highly reactive, with reactivity decreasing down the table. They all contain 7 valence electrons and readily accept an electron from other atoms. GZ Science Resources 2013 45 Group 18 elements These elements are called the Inert Gases (sometimes called Noble gases). They all have full valence shells and are very unreactive. This property makes them useful in many practical applications. GZ Science Resources 2013 46 Compounds Compounds form from two or more different elements bonded together. Compounds The compounds are often more stable than the elements they originated from and may release this extra energy in the form of heat and/or light when bonding together. There are two main types of bonding holding atoms together in a compound; Ionic and Covalent. GZ Science Resources 2013 48 Ionic Bonding Ionic Bonding is where one atom completely takes valence electrons from another to form ions and the resulting negative and positive ions hold together with electrostatic attraction. GZ Science Resources 2013 49 Covalent Bonding Covalent Bonding is where valence electrons are shared between neighbouring atoms. These occur between Non-Metal and NonMetal or between Metal and Metal 50 Covalent Bonding The valance electrons are involved in bonding. These electrons orbit in pairs. The negative charge of the electron pair will attract the positively charged nuclei of other atoms, and this holds the atoms together in a molecule. GZ Science Resources 2013 51 Covalent Bonding All covalent bonds are strong. That is it requires a large amount of energy to ‘break’ the bond. However, some covalent bonds are stronger than others. The greater the overlap of valence orbitals (the area the valence electrons orbit the nucleus) the stronger the bond. GZ Science Resources 2013 52 Covalent Bonding The electron-pair must lie between the nuclei for the attraction to outweigh the repulsion of the two nuclei. This ‘sharing’ of electrons between atoms creates a covalent bond – giving both atoms the stability of a full outer shell. Covalent bonds are normally formed between pairs of non-metallic atoms. Some covalent bonds involve only one pair of electrons and are known as single bonds. Other covalent bonds can involve two pairs of electrons; double bonds and three pairs of electrons; triple bonds. GZ Science Resources 2013 53 Chemical Reactions A chemical reaction is a process that produces a chemical change to one or more substances. A chemical reaction will produce a new substance. Other observations may include a temperature change, a colour change or production of gas. Chemicals that are used in a chemical reaction are known as reactants. Those that are formed are known as products. GZ Science Resources 2013 Reactants 54 → Products Naming compounds Lavoisier – French Chemist 1789 Lavoisier devised a system of naming compounds based on their chemical composition. If the compound is formed between a Metal cation (+ve) and a Non-Metal anion (-ve), then the compound name joins the two names together with the metal name first. Names of the ions need to be remembered. Sodium + hydroxide GZ Science Resources 2013 55 Chemical compound formula 1. Write down the ions (with charges) that react to form the compound. Cation comes before Anion. Al3+ O2- 2. Cross and drop the charge numbers. 3. Place brackets around a compound ion. Al2O3 4. If the numbers are both the same remove. 5. If any of the numbers are a 1 they are removed 6. Remove any brackets if not followed by a number H+ SO4-2 H2(SO4)1 GZ Science Resources 2013 H2SO4 56 Balancing chemical equations Balanced equations must have the same number of atoms on each side of the equation i.e. reactants and products. 2Na Na + Na GZ Science Resources 2013 2H2O H H H O = H O 57 2NaOH O H O Na Na + H2 H HH Drawing chemical compounds G Lewis – American Chemist 1916 G Lewis devised a system of drawing covalent molecules showing arrangement of atoms and valence electrons – both those involved in bonding and those that are not (called lone pairs). Electrons in inner shells are not involved in bonding. These diagrams are called Lewis diagrams. The Lewis diagram is drawn so that each atom has eight electrons associated with it (except for hydrogen which has two). This is the octet rule. Lewis diagram of H2O (water) Hydrogen electron Bonded pair x H O Oxygen electron x H Lone pair Lewis Diagrams 1. Calculate valence electrons of all atoms. If the molecule is an ion then subtract the charge from the total electrons and place the charge outside of square brackets of the Lewis diagram at the end. Example carbon dioxide. C=4 CO2 O=6 O=6 16 2. Write down number of pairs of electrons. 16 / 2 = 8 pairs 3. Place atom with least filled valence shell in the centre with the other atoms arranged around the out side (periphery) O C O GZ Science Resources 2013 59 Lewis Diagrams 4. Bond all atoms together (either x or O C = one pair of electrons) 8 pairs – 2 pairs = 6 pairs remaining O 5. Place remaining e- pairs around the periphery atoms so each has 4 pairs (including bond pair) around it. xx x xO xx 6 pairs – 6 pairs = 0 pairs remaining xx C O xx xx 6. If there any remaining pairs place them around the outside of the central atom. 7. Rearrange lone pairs (pairs not bonded) into bonded pairs if the central atom does not have 4 pairs around it. GZ Science Resources 2013 60 Rule of orbitals If there are extra Lone Pairs of electrons left after all of the periphery atoms are filled in accordance with the octet rule then they are placed around the central atom(s) according to the Rule of Orbitals. The Rule of Orbitals: the total number of lone pairs and bond pairs (LP+BP) associated with an atom cannot exceed the number of Valence Shell Orbitals (VSO = n2, where n is the row of the Periodic Table in which that atom resides). n = 1 (H): maximum VSE pairs (LP+BP) = VSO = 1; n = 2 (B, C, N, O, F): maximum VSE pairs (LP+BP) = VSO = 4 ("octet rule") n = 3 ((Al, Si, P, S, Cl): maximum VSE pairs (LP+BP) = VSO = 9; etc. F B F GZ Science Resources 2013 61 F Lewis Diagrams The number of covalent bonds an atom forms is called its valence. Some atoms have fixed valence. E.g: H = 1, C = 4, F = 1. Some atoms have variable valence. For example: O = 2 (sometimes 3), B, N = 3 (sometimes 4). an atom bonded to only one other atom is peripheral (monovalent atoms such as H and F are always peripheral). an atom bonded to two or more other atoms is central. Often, the formula is written to indicate connectivity. For example: HCN = H bonded to C, C bonded to N, H and N are not bonded. GZ Science Resources 2013 62 Predicting molecular shapes Sidgwick and Powell – 1940 Sidgewick and Powell devised a theory to predict the shapes molecule formed. It is based on the following ideas: Each electron pair is a region of negative charge Negative charges repel each other Electron pairs will be spaced as far apart as possible around a central atom. This theory is called the Valance Electron Pair repulsion theory. Three pairs GZ Science Resources 2013 Four pairs 63 Predicting molecular shapes The shapes of molecules are determined by the way clouds of electrons are arranged around the central atom in the molecule. A cloud may consist of one lone pair or one bonded pair or two bonded pairs or three bonded pairs. All of these electron arrangements occupy the same area of space or cloud. GZ Science Resources 2013 64 Shapes – two clouds Since clouds of electrons are negatively-charged, they repel each other. Two clouds arrange themselves on opposite sides of the central atom. The bond angle will be 180°. The shape name is linear. Bonded pair of electrons (one cloud) atom 180° GZ Science Resources 2013 65 Bond angle Shapes – three clouds (0 lone pairs) Three clouds of electrons will cause a bond angle from of 120°. All the atoms still lie on a flat plane (like a sheet of paper). The shape is trigonal planar. (or triangular planar) Periphery atom 120° Central atom Shapes – two clouds (1 lone pair) When one of the clouds of electrons is a lone pair it will have a slightly greater push to the bonded pairs. This is because the lone pair are only orbiting around one positive nucleus and their negative charge is less ‘neutralised’ than if they had another nucleus to orbit around. The bond angle between the remaining pairs therefore is slightly smaller at approximately 120° (actually 119°). The shape formed is called bent. Lone pair Bonded pair ~120° GZ Science Resources 2013 67 Shapes – four clouds (0 lone pairs) When four clouds of electrons are around a central atom they repel each other into a 3-dimensional shape. The bond angle is now 109°. This is because it is a sphere divided into 4 rather than a circle. This shape is tetrahedral. 109° Shapes – four clouds (1 lone pair) The four clouds of electrons still occupy a 3-dimensional shape. The lone pair, however, exerts a stronger repulsion to the remaining bonded pairs. The bond angle becomes 107°. The shape is a trigonal pyramid (or a triangonal pyramid) Lone pair 107° Shapes – four clouds (2 lone pairs) The two lone pairs create a much stronger repulsion than one lone pair and the bond angle between the remaining bonded pairs is smaller again at approximately 109°(actually 105°) The shape is called Bent. Lone pair ~109° Shape Summary Electron clouds (lone pairs or bond groups) 2 Linear 3 4 no lone pairs 1 lone pair no lone pair 1 lone pair 2 lone pair triangular planar Bent Tetrahedral triangular pyramid CH4 109° NH3 107° CO2 180° GZ Science Resources 2013 BF3 120° SO2 119° bent H2O 105° Drawing Shapes 1. Draw molecule – Lewis diagram 2. Calculate number of clouds of electrons around central atom • • receding Single, double or triple electron bonds occupy 1 cloud Same plane A lone pair of electrons occupy 1 cloud 3. Calculate how many atoms are joined to the central atom 4. Name / draw shape approaching GZ Science Resources 2013 72 Discussing shapes questions Explain why the shape of the CO2 molecule is linear but the shape of H2O is bent? 1. The C (central atom) of CO2 has two electron clouds around it in the form of double bonds connected to a O atom. (draw lewis diagram) 2. Each of the electron clouds repel each other the furthest away from each other in 3 dimensional space. 3. the CO molecule therefore forms a linear shape 1. The O molecule (central atom) of H2O has 4 electron clouds around it in the form of two single bonds connected to a H atom and two lone pairs. (draw lewis diagram) 2. Each of the electron clouds repel each other the furthest away from each other in 3 dimensional space. 3. The H2O molecule therefore forms a bent shape GZ Science Resources 2013 73 Electronegativity Electronegativity is the attraction that an atom has towards electrons from another atom. The greater the electronegativity the stronger the pull it has towards other electrons. Trends in the periodic table The larger the nucleus (with the positive protons) the stronger the electronegativity, this means it increases from left to right. The further the valence electrons are from the nucleus the lesser the electronegativity, therefore the electronegativity decreases down a group. Electronegativity We use a pauling scale to determine electronegativity. The scale starts close to 0 – with minimal electronegativity and goes up to 4 with the highest electronegativity. Most of the Inert gases do not have a value because of there non reactivity with other atoms. Ionic – covalent bond continuum Bond types between atoms can depend on the electronegativity of the atoms. Rather than discrete categories, molecules fall along a continuum Covalent 0—0.4 GZ Science Resources 2013 Polar Covalent 0.4—1.6 76 Ionic >1.6 Polarity If two identical atoms are bonded together then they have exactly the same amount of attraction to the shared electrons in the bonded pair. This is because their electronegativity is the same. This becomes a non-polar molecule with non-polar bonds. Example - Iodine molecule I2 Path of electrons Evenly shared If two different types of atoms are bonded together then they will exert different levels of attraction for the orbiting electrons. That is because they may have different numbers of electron shells and different numbers of protons in their nucleus. This will cause an electronegativity difference. These bonds become polar bonds. Example – hydrochloric acid HCl Slightly positive Electrons orbit less GZ Science Resources 2013 δ+ δ- Slightly negative Electrons orbit more 77 Polarity δ- δ+ Cl H Polarity may also be shown as an arrow, with a cross, +ve, at the tail. The arrow head is the –ve end. GZ Science Resources 2013 78 Polarity If two bonded atoms are the same, the bond is said to be non-polar. i.e. I2 The whole molecule is also non-polar because there is no electronegativity difference and the valence electrons orbit each atom evenly. If two different atoms are bonded they form a polar bond, as there is an electronegativity difference and the valence electrons spend more time around the atom with the higher electronegativity value (that atom becomes slightly negative ) The atom that the valence electrons spend less time around becomes slightly positive. GZ Science Resources 2013 79 Symmetry and Polarity The polarity of a molecule with polar bonds depends upon whether the molecule is symmetrical or not. A symmetrical molecule (one where the centres of peripheral atoms coincide) becomes a non-polar molecule – as the charges balance out An unsymmetrical molecule (one where the centre of peripheral atoms do not coincide) is a polar molecule. GZ Science Resources 2013 80 Answering Polarity Questions Explain why molecules x (CCl4) and y (NCl3) are polar and non-polar? Polar molecule 1. molecule (NCl3) is polar (state which one) 2. (NCl3) contains polar bonds due to electronegativity difference of N and Cl. 3. over the whole molecule the atoms are not distributed symmetrically in 3 dimensions because its shape is (state which one) 4. polar bonds do not cancel each other out and the whole molecule is polar. GZ Science Resources 2013 Non-polar molecule 1. molecule (CCl4) is non-polar (state which one) 2. (CCl4) contains polar bonds due to electronegativity difference of C and Cl. Cl attracts more electrons than C because it has a bigger atomic number than C but with the same number of shells 3. over the whole molecule the atoms are distributed symmetrically in 3 dimensions because its shape is (state which one) 4. polar bonds cancel each other out and the whole molecule is non-polar. 81 Polar Solvents The water molecule has two polar bonds. Due to the asymmetry of the molecule, their polarities reinforce making the oxygen side of the molecule partially negative (δ-) and the hydrogen side partially positive (δ+). Such molecules are called ‘polar’. The separation of charge in the molecule (δ+ - δ) is called a ‘dipole’. Polarity causes a stream of water molecules to attract to a charged plastic pen. GZ Science Resources 2013 82 Common Polar and Non-polar molecular substances Polar Non-Polar water methanol ethanol acetic acid hydrogen chloride cyclohexane benzene hydrocarbons (e.g. petrol) oxygen hydrogen nitrogen iodine 2006 Question 5(b) Potassium chloride will not dissolve in non-polar solvents, but will dissolve in water. Explain by relating the property to the structure and bonding within the solid. 2003 Question 1(e) Use the structure and bonding in H2O and SO2 to explain why SO2 is soluble 83 in H2O. Weak intermolecular forces Weak intermolecular forces of attraction 3 kinds instantaneous dipole – induced dipole permanent dipole – permanent dipole hydrogen bonding Note the distinction: Intra-molecular Forces: the strong bonding forces within a molecule. i.e. the covalent bonds holding the molecule together. Inter-molecular Forces: the weak bonding forces between molecules due to the attractions between partial charges. i.e. permanent dipole GZ Science Resources 2013 84 Solubility The solubility of a substance is the amount of that substance that will dissolve in a given amount of solvent. Solubility is a quantitative term. Solubility's vary depending on the solvent and the solute. The terms soluble and insoluble are relative. Some substances can be sparingly soluble where only the most minute percentage dissolves. For a solute to dissolve the attraction to the solvent molecules must be stronger than the bonds holding the atoms/molecules of the solute together. GZ Science Resources 2013 85 Solutions form when a solute is dissolved in a solvent When a solid mixes into a liquid and can longer be seen it has dissolved. The liquid is called the solvent and it pulls apart the bonds between the solid particles, called the solute, and they diffuse. A solution is then created when the solvent particles (often water) are mixed up with the broken apart solute particles. 86 GZ Science Resources 2013 Water as a solvent Solute (salt) Solvent (water) Solution (saltwater) GZ Science Resources 2013 87 A solution is made up of a solvent and a solute. A solvent is a substance such as water that is able to dissolve a solute. The solvent ‘pulls apart’ the bonds that hold the solute together and the solute particles diffuse (spread randomly by hitting into each other) throughout the solvent to create a solution. The solution is a mixture with evenly spread solvent and solute particles. These particles can be physically separated by evaporation. Solubility For a solute to dissolve, the solvent particles must form bonds with the solute particles that are of similar strength, to the bonds between the solute particles. Water, being polar attracts ions because they are charged and so dissolves many ionic substances. GZ Science Resources 2013 88 Dissolving and Polarity Polar substances dissolve polar substances. e.g. Water, being polar attracts the molecules of other polar substances (e.g. HCl) and will dissolve them. Polar substances will not dissolve non-polar substances. e.g. Water, (polar) has a stronger attraction to itself than to non-polar molecules (e.g. cyclohexane) and will not dissolve them. Non-polar substances dissolve non-polar substances. e.g. Non polar solvents (like cyclohexane) attract non-polar solutes (like napthalene) by the same weak Van der Waals forces they attract themselves by and so will dissolve non-polar solutes. Ionic solid dissolving in water GZ Science Resources 2013 89 Molecular solids non-metal + non-metal Molecules are held together by weak intermolecular forces caused by temporary dipoles induced by electrons randomly spending more time around one nucleus than the other. Within the Molecules, the atoms are held together by strong covalent bonds. Weak intermolecular bond Strong covalent bond GZ Science Resources 2013 90 Molecular solids non-metal + non-metal 91 Molecular solids Polar molecules held together by weak inter molecular forces caused by permanent dipoles induced by electrons spending more time around one nucleus in the molecule that has greater electronegativity than the other. The δ –ve end of one molecule is attracted to the δ +ve end of another. δ +ve δ -ve δ +ve δ +ve δ +ve δ -ve δ +ve GZ Science Resources 2013 92 δ -ve δ +ve Molecular solids - solubility 1. X is a molecular solid 2. X is made up of covalently bonded atoms to form molecules 3. these molecules are held together by weak intermolecular forces 4. these molecules are polar therefore the electrostatic attractions of water molecules (which is stronger than the weak intermolecular forces) have sufficient strength to pull the molecules apart hence x is soluble GZ Science Resources 2013 Polar molecules Cl H H Cl Cl H δ -ve H δ +ve 93 O H δ +ve Molecular solids - solubility 1. X is a molecular solid 2. X is made up of covalently bonded atoms to form molecules 3. these molecules are held together by weak intermolecular forces 4. non-polar therefore the electrostatic charges of the water do not have sufficient strength to overcome the weak intermolecular forces holding the molecules together hence x is insoluble + + δ -ve O H H δ +ve + + δ -ve O δ +ve H δ +ve Non- Polar molecules GZ Science Resources 2013 94 H δ +ve Molecular solids – Melting point 1. X is a molecular solid 2. X is made up of covalently bonded atoms to form molecules 3.these molecules are held together by weak intermolecular forces 4. these forces require small amounts of energy to break apart the solid (but not the individual molecules which are held together by strong covalent bonds) therefore x has low melting point O Heat O C GZ Science Resources 2013 O C O 95 Molecular solids - hardness 1. X is a molecular solid 2.X is made up of covalently bonded atoms to form molecules 3.these molecules are held together by weak inter molecular forces 4. these forces require small amounts of energy to break apart the solid (but not the individual molecules which are held together by strong covalent bonds) therefore x is easily broken up S S S S S S Force applied S GZ Science Resources 2013 S Weak intermolecular force Molecular solids - conductivity 1. X is a molecular solid 2. X is made up of covalently bonded atoms to form molecules these molecules are held together by weak intermolecular forces 3. there are no free moving charges therefore x cannot conduct electricity nucleus + + Valence electrons + Covalently shared electrons Weak intermolecular bonding + Fully occupied valence electrons remain in ‘fixed orbit’ around nucleus and are not available to carry charge. The molecule is neutral Metallic Solids Metals atoms are arranged as positive ions held in place in ordered layers by strong attractive forces, forming a lattice. - this gives metals strength. The atoms are packed tightly together - this makes metals dense GZ Science Resources 2013 98 Metallic Solids - Conductivity Electrons from the outer shells of the metal atoms move freely throughout the lattice. - this makes metals excellent conductors of heat and electricity GZ Science Resources 2013 99 Metallic Solids - Conductivity 1. X is a metallic solid 2. X is arranged as positive ions held in place in ordered layers by strong attractive forces, in a sea of de-localised electrons 3. electrons are free moving hence can carry a charge 4. therefore x can conduct electricity GZ Science Resources 2013 100 Metallic Solids - Solubility 1. X is a metallic solid 2. X is arranged as positive ions held in place in ordered layers by strong attractive forces, in a sea of delocalised electrons 3. these forces require a large amount of energy to break therefore the electrostatic attractions of water molecules do not have sufficient strength to pull the atoms apart 4. hence x is insoluble GZ Science Resources 2013 101 Metallic Solids - Solubility 1. X is a metallic solid 2. X is arranged as positive ions held in place in ordered layers by strong attractive forces, in a sea of delocalised electrons 3. these forces require a large amount of energy to break therefore the electrostatic attractions of water molecules do not have sufficient strength to pull the atoms apart 4. hence x is insoluble GZ Science Resources 2013 102 Metallic Solids - Hardness Layers of ions can slide over each other without breaking- this makes metals hard and also malleable and ductile GZ Science Resources 2013 103 Metallic Solids - Hardness 1. X is a metallic solid 2. X is arranged as positive ions held in place in ordered layers - a lattice, by strong attractive forces, in a sea of delocalised electrons 3. these forces require large amounts of energy to break apart the solid therefore x is not easily broken up 4. However Layers can slide over each other, and as the attractive forces are multi-direction the metallic particles remain strongly bonded. – this gives the metallic solids the properties of being malleable (moulded into flat sheets) and ductile (drawn out to thin wires) GZ Science Resources 2013 104 Metallic Solids – melting point 1. X is a metallic solid 2. X is arranged as positive ions held in place in ordered layers by strong attractive forces, in a sea of de-localised electrons 3. These forces require a large amount of energy (high temperature) to break apart the metallic solid therefore the melting point is very high. (most metals are solids at room temperature) GZ Science Resources 2013 105 Metallic properties Free moving electrons in the metallic lattice strongly absorb light, then quickly reflect nearly all of it. - This makes metals shiny, called lustre. GZ Science Resources 2013 106 Ionic Solids Metal + Non-Metal An ionic solid is made up of ions held together by strong electrostatic forces between +ve (cations) and –ve (anions) ions in a lattice. GZ Science Resources 2013 107 Ionic Solids - Solubility 1. X is an ionic solid 2. X is made up of ions held together by strong electrostatic attractions between +ve and –ve ions in a lattice 3. the electrostatic attractions of water molecules have sufficient strength to pull the ions apart however 4. hence the solid will dissolve GZ Science Resources 2013 Ionic Solids - Conductivity 1. X is an ionic solid 2. X is made up of ions held together by strong electrostatic forces between +ve and –ve ions in a lattice 3. when solid the ions are not free to move therefore it doesn’t conduct electricity 4. when melted the bonds are broken and the ions are free to move therefore conduct electricity GZ Science Resources 2013 Na+ Cl- Na+ Cl- Cl- Na+ Cl- Na+ 109 Distilled water does not conduct a current Positive and negative ions fixed in a solid do not conduct a current In solution, positive and negative ions move and conduct a current Ionic Solids - Hardness 1. X is an ionic solid 2. X is made up of ions held together by strong electrostatic attractions between +ve and –ve ions in a latice 3. if force is applied ions of the same charge come in contact with each other and repel hence the ionic solid is brittle Na+ Cl- Na+ Cl- Na+ Cl- Na+ Clforce ClGZ Science Resources 2013 Na+ Cl- Na+ Cl111 Na+ Cl- Na+ Ionic Solids – Melting Point 1. X is an ionic solid 2. X is made up of ions held together by strong electrostatic attractions between +ve and –ve ions in a lattice 3. these strong bonds require a large amount of energy to break therefore the ionic solids have a high melting point. GZ Science Resources 2013 Na+ Cl- Na+ Cl- Cl- Na+ Cl- Na+ 112 Covalent Network Solids non-metal + non-metal All atoms are held together by strong covalent bonds Diamond is a 3-dimensional covalent network structure where atoms are held together by strong covalent bonds in all planes Graphite is a covalent network structure that is in 2 dimensional sheets (graphite). Between the layers are free moving electrons from the valance electrons of the carbon atoms. GZ Science Resources 2013 113 Covalent Network (3D) - Conductivity 1. X is a 3dimensional covalent network structure (diamond) 2. all atoms are held together by strong covalent bonds 3. there is no free moving charged particles 4. therefore x cannot conduct electricity GZ Science Resources 2013 114 Covalent Network (2D) - Conductivity 1. X is a covalent network that is in 2 dimensional sheets (graphite) 2. between the layers are free moving electrons from the valance electrons of the carbon atoms. 3. the free moving electrons can carry a current 4. therefore x can conduct electricity 115 GZ Science Resources 2013 Covalent Network Solids - Solubility 1. X is a 3-dimensional (or 2-dimensional) covalent network structure 2. all atoms are held together by strong covalent bonds 3. these forces require a large amount of energy to break therefore the electrostatic attractions of water molecules do not have sufficient strength to pull the ions apart 4. hence x is in-soluble GZ Science Resources 2013 116 Covalent Network Solids - Melting Point 1 X is a 3-dimensional (or 2-dimensional) covalent network structure 2. all atoms are held together by strong covalent bonds 3. these forces require a large amount of energy to break 4. therefore x has a very high melting point. GZ Science Resources 2013 117 Covalent Network Solids - Hardness 1. X is a 3-dimensional (or 2-dimensional) covalent network structure 2. all atoms are held together by strong covalent bonds 3. these forces require a large amount of energy to break 4. therefore x is very hard. GZ Science Resources 2013 118 Solids Summary Name of solid substance Type of particle in solid Attractive force broken when solid melts Attractive force between particle – weak or strong (hardness) Relative melting point solubility Electrical conductivity molecular molecules Weak intermolecular weak low Yes if polar No if nonpolar no metal atoms Metallic bonding strong high no yes ionic ions Electrostatic strong high yes Only if molten or in solution strong high no no Ionic bonding covalent atoms Covalent bonding Property Type of Solid Molecular Solubility in Water Electrical Conductivity Melting Point Hardness Covalent network Ionic Metallic Halogen Trends The elements of Group 17 of the Periodic Table all exist as diatomic molecules with (non-polar) covalent bonding strongly holding the pairs of atoms together as a molecule, but only weak van der Waals forces between the molecules. The molar mass increases down the group and so therefore does the melting and boiling points as the strength of the inter-molecular forces increases. Halogen F2 Cl2 Brr I2 Physical state at 25 oC Pale yellow gas Greenishyellow gas Red liquid Black shiny solid GZ Science Resources 2013 121 Oxides of the Third Row Metals Non - Metals Most metal oxides are basic oxides. Non-metal oxides are acidic oxides. The oxides of Group 1 metals, are soluble in water and form solutions of the metal hydroxides e.g. Na2O dissolves to form a solution of NaOH. When dissolved in water, they react to form acids that dissociate in water producing H3O+ ions. All the metal oxides are ionic salts; they are solids with high melting points and only conduct electricity when molten or in an aqueous solution. GZ Science Resources 2013 The non-metal oxides (oxides of elements in Groups 14 - 17) are all molecular substances. They are substances with low melting points and are often liquids or gases at room temperature. 122 Chlorides of the Third Row The melting point of these chlorides reduces from left to right as the structure changes from ionic through polar covalent to non-polar molecules as shown in the table below. Formula NaCl MgCl2 AlCl3 SiCl4 PCl3 SCl2 Cl2 M.P. (oC) 801 710 sub 150 - 70 - 112 - 78 -101 State Solid Solid Solid Liquid Liquid liquid (Yellowgreen) Gas Type of solid Ionic Ionic Ionic Molecular Molecular Molecular Molecular Nature of bonding GZ Science Resources 2013 Ionic Covalent bonding between atoms in the molecules but weak van der Waals forces between the molecules 123 Energy Changes Enthalpy and Enthalpy Change ∆H Enthalpy (or Heat Content) is the energy in a substance due to kinetic energy of particles and potential energy in chemical bonds Enthalpy change ∆H is the difference in enthalpy of products HP and reactants HR ∆H = HP - HR GZ Science Resources 2013 124 Enthalpy Change HP (products) and HR (reactants) cannot be measured. We can measure Enthalpy change ( ∆H ) by measuring energy; Released to surroundings (Exothermic Reactions) GZ Science Resources 2013 Absorbed from surroundings (Endothermic Reactions) 125 Exothermic Reactions These are reactions where heat energy is released into the surroundings. Surroundings gain heat energy. (increase in temperature ) Products will have less energy than reactants. ∆H is NEGATIVE (-) Endothermic Reactions These are reactions where heat energy is absorbed from the surroundings. Surroundings lose heat energy. (Decrease in temperature) Products will have more energy than reactants. ∆H is POSITIVE (+) Exothermic reactions Any combustion reaction is exothermic. The bonds holding the atoms of fuel molecules together (usually consisting of carbon and hydrogen atoms) release a lot of energy in the form of light and heat when they are broken. The total energy holding the bonds together in the products are less than the total energy in the reactions and the difference is released. GZ Science Resources 2013 127 Endothermic reactions Melting ice is an example of an endothermic reaction. The solid ice (water) atoms that are in a fixed pattern are barely moving and need to absorb energy in order to move faster and break the bonds to form water in a liquid state. GZ Science Resources 2013 128 Enthalpy Diagrams Exothermic Reactions Endothermic Reactions e.g. Reacting methane with steam at high pressure and temp. Energy is absorbed e.g. Burning of methane in air. Energy is released 12 12 10 H R 10 H P 8 8 6 4 Energy 6 H H 4 2 H0P H0R GZ Science Resources 2013 Reaction Progress Reaction Progress 2 129 Energy Enthalpy Change An exothermic reaction will release energy and the products will be at a lower enthalpy level than the reactants. The reaction system will feel will feel hot to the touch as the energy is released as heat energy. An endothermic reaction will absorb energy and the products will be at a higher enthalpy than the reactants. The reaction system will feel cool to the touch as heat energy is taken from the surroundings, including your skin, and used to break bonds in the molecules. GZ Science Resources 2013 Energy Diagrams Endothermic Reaction e.g. Reacting methane with steam at high pressure and temp. Energy is absorbed GZ Science Resources 2013 131 Energy Diagrams Exothermic Reaction e.g. concentrated Hydrochloric acid reacting with zinc metal HR HP GZ Science Resources 2013 132 Standard conditions Measurements depend on conditions When measuring a enthalpy change you will get different values under different conditions. For example, the enthalpy change of a particular reaction will be different at different temperatures, different pressures or different concentrations of reactants. The values for enthalpy are given for standard conditions, indicated by the superscript θ Standard conditions include: Temperature of 25°C Atmospheric pressure conditions of 1ATM Concentration of 1mol per Litre GZ Science Resources 2013 Thermochemical Equations Exothermic CH4 + 2O2 Endothermic CO2 + 2H2O CH4 + H2O ∆H = -888kJmol-1 CO + 3H2 ∆H = 206 kJmol-1 This thermochemical equation reads; 888kj of heat is released when 1 mole of CH4 reacts with 2 moles of O2 to produce 1 mole of CO2 and 2 moles of H2O Use thermochemical equations to find This thermochemical reaction reads; 206kJ of heat is absorbed when 1 mole of CH4 reacts with 1 mole of H2O to produce 1 mole of CO and 3 moles of H2. ∆H, n and m. n = m/M n = moles (6.02 x 1023 particles) m = mass (grams) M = Molar Mass (gmol-1 ) GZ Science Resources 2013 134 Thermochemical Equations CH4 + 2O2 1. CO2 + 2H2O ∆H = -888kJmol-1 Use the equation above to find heat released if 2.5 moles of CH4 burns. GZ Science Resources 2013 135 Thermochemical Equations CH4 + 2O2 1. CO2 + 2H2O ∆H = -888kJmol-1 Use the equation above to find heat released if 2.5 moles of CH4 burns. 1 mole of CH4 releases 888kJ 2.5 moles CH4 releases x kJ x = 2.5 x 888 = 2220kJ GZ Science Resources 2013 136 Thermochemical Equations CH4 + 2O2 CO2 + 2H2O ∆H = -888kJmol-1 2. Calculate the amount (in moles) of H2O produced when the reaction above releases 10000kJ. GZ Science Resources 2013 137 Thermochemical Equations CH4 + 2O2 CO2 + 2H2O ∆H = -888kJmol-1 2. Calculate the amount (in moles) of H2O produced when the reaction above releases 10000kJ. 2 moles H2O when 888kJ released x moles H2O when 10000kJ released x = 2 x 10000 = 22.5 moles 888 GZ Science Resources 2013 138 Thermochemical Equations CH4 + H2O ∆H = 206kJmol-1 CO + 3H2 M(C) = 12gmol-1 M(O) = 16gmol-1 3. Calculate the energy required to produce 1kg of CO gas from the reaction above GZ Science Resources 2013 139 Thermochemical Equations CH4 + H2O ∆H = 206kJmol-1 CO + 3H2 M(C) = 12gmol-1 M(O) = 16gmol-1 3. Calculate the energy required to produce 1kg of CO gas from the reaction above 3. M = 1000g M(CO) = 28gmol-1 moles of CO produced n = m/M = 1000/28 = 35.7 moles 1 mole CO produced requires 206kJ 35.7 mols CO produced requires x x = 35.7 x 206 = 7354kJ GZ Science Resources 2013 140 Calculating enthalpy using temperature change ΔH can be calculated if you can measure the temperature change (°C) of a particular mass (g) ΔH = m x c x ΔT ΔH = mass (g) x ΔT (°C) x specific heat capacity (c) (c = 4.18 J g-1 °C) 1. Calculate the mass of reactants – record in grams (one ml liquid = one gram) 2. Measure the temperature of the reactants and the temperature of the products and calculate ΔT (°C) 3. Calculate ΔH using formula above GZ Science Resources 2013 141 Enthalpy of Reaction using calorimetry To measure enthalpy changes, the reaction it is carried out in an insulated container (such as a polystyrene cup) and the temperature change (in °C) is measured. Using this temperature change, ΔT, and the value of the specific heat capacity, c, the amount of energy transferred to the mass m of substance (usually water) can be calculated using the expression ∆H = m c ΔT The specific heat capacity of the water is 4.18 J °C-1 g-1. Every 1mL of water can be taken as 1g due to its density 1. Calculate the mass of reactants – record in grams (one ml liquid = one gram) 2. Measure the temperature of the reactants and the temperature of the products and calculate ΔT (°C) 3. Calculate ΔH using formula above GZ Science Resources 2013 Specific Heat Capacity (c) The heat required to produce a 1oC rise in 1 kg of a substance. e.g. c(H2O) = 4.18 kJ oC-1kg-1 The energy change when a body of mass m experiences a temperature rise of ΔT is given by: Q = m c ΔT energy change = mass x specific heat capacity x change in temperature Example: Calculate the energy change when a 9 kg mass of water increases its temperature by 20 oC. Q = m c ΔT = 9 kg x 4.18 kJ oC-1kg-1 x 20 oC = 752 kJ Note: Watch units g or kg, J or kJ and be ready to convert if required. GZ Science Resources 2013 143 Calculations using ∆rH° ∆rH°= ∑ ∆fH°= (products) - ∆fH°= ∑(reactants) Step 1. Construct a balanced equation for the reaction Step 2. Calculate ∑ ∆fH° of the products Step 3. Calculate ∑ ∆fH° of the reactants Step 4. Use Hess’s Law to calculate ∆rH° 8Al(s) + 3Fe2O4(s) → 4Al2O3(s) + 6Fe(s) ∆fH° Fe2O4 = -1120.9 Kjmol-1 ∆fH° Al2O3 = -1669.8 Kjmol-1 GZ Science Resources 2013 Enthalpy Changes Exothermic - energy released ∆ H negative Endothermic - energy absorbed ∆ H positive Enthalpy of reaction (∆rH) for any given reaction Standard conditions (∆rH°) 1 atmosphere of pressure, 25°C Enthalpy of fusion (∆fusH°) 1 mol solid to liquid state Enthalpy of vapourisation (∆vapH°) 1 mol liquid to gas state Enthalpy of sublimination (∆subH°) 1 mol solid to gas state solid ∆subH° ∆fusH° gas GZ Science Resources 2013 liquid ∆vapH° Breaking Bonds - endothermic Bonds holding atoms and molecules together require the input of energy in order to break them apart therefore breaking of bonds is an endothermic reaction. The input of energy (usually light or heat energy) cause the atoms and molecules to move faster and ‘pull away’ from each other. Each type of bond has its own specific amount of energy, called bond energy measured in kJ, required to break its bond. GZ Science Resources 2013 146 Forming Bonds - exothermic Bonds forming between atoms and molecules release energy therefore bond forming is an exothermic reaction. Bonds are formed to form a stable molecule. If more energy is required to break the bonds of the reactants than released when the bonds of the products are form then the overall reaction is endothermic. If less energy is required to break the bonds than is released when the bonds of the products are formed then the overall reaction is exothermic. GZ Science Resources 2013 147 Enthalpy in Dissolving If more energy is released when water bonds to the solute than it takes to separate the solute, the dissolving is exothermic and the temperature increases. An example is adding a strong acid (such as sulfuric acid) or base (such as sodium hydroxide) GZ Science Resources 2013 148 Bond Energies Bonds Broken – Endothermic Bonds formed – Exothermic ∆rH°= ∑ (energy of bonds broken) - ∑(energy of bonds formed) Note: Bond energies calculated for gases. Convert using ∆vapH° or ∆subH° if in solid or liquid state. CO(g) + H2O(g) → H2(g) + CO2(g) Bonds Broken CΞO H-O x 2 995Kj 2(463)Kj 1921Kj ∆rH°= -1.0 Kjmol-1 Bonds formed C=O x 2 H-H 2(743)Kj 436Kj 1922Kj ∆rH°= 1921Kjmol-1 – 1922Kjmol-1 The equation can also be arranged ∆rH°= -1.0 Kjmol-1 to calculate unknown bond energy Using Bond Enthalpies to calculate ∆rH° Bond enthalpy is the change in enthalpy when the covalent bond, in a gaseous molecule, is broken. It is always a positive value because bond breaking always requires an input of energy. Making bonds releases energy so generally speaking the more bonds a substance can form the more stable it will be. The stronger a covalent bond, the higher the value of the bond enthalpy. The units are kJ mol-1. GZ Science Resources 2013 Bond Enthalpy The high values for bond enthalpy explains why some substances are very resistant to chemical attack and form very stable molecules In a polyatomic (more than one atom) molecule, the bond strength between a given pair of atoms can vary slightly from one compound to another. The value given for bond enthalpy is the average of all these variations. A multiple bond (double/triple) is always stronger than a single bond because more electrons bind the multiple bonded atoms together. The table below shows some common average bond enthalpies. Bond enthalpy /kJ mol-1 H-H GZ Science Resources 2013 436 Bond enthalpy /kJ mol-1 C-H Bond enthalpy /kJ mol-1 412 C=C 612 837 H-O 463 C - Cl 338 C=oCC C H-N 388 C-F 484 C=O 743 H - Cl 431 C-O 360 O=O 496 H-F 565 C-C 348 NN 944 F-F 158 O–O 146 Cl - Cl 242