ࡱ>  '` abjbj lA>>>>?,\jA$8B8B8B8BCJ=DYD[[[[[[[^h\aR[uiDC"CiDiD[8B8BD\KKKiD8B8B[KiD[KKrUTU8BA pco>GUW$Z\0\UaIaUUnaaVHiDiDKiDiDiDiDiD[[JiDiDiD\iDiDiDiDD*,/,/ 1.6 Bonding 1 Ionic bonding 1.6.1a Evidence for ions recall and interpret evidence for the existence of ions, limited to physical properties of ionic compounds, electron density maps and the migration of ions, eg electrolysis of aqueous copper chromate(VI) Calcite crystals, formed from calcium carbonate, CaCO3, break only along definite lines suggesting a very regular arrangement of calcium and carbonate ions. Sodium chloride, NaCl, shows similar properties.  INCLUDEPICTURE "http://www.nordskip.com/viking/cleave.jpg" \* MERGEFORMATINET ( HYPERLINK "http://www.nordskip.com/calciteoptics.html" http://www.nordskip.com/calciteoptics.html) X-ray diffraction can be used to make electron density maps. These show electrons around spherical ions with no electron sharing. 1A =10-8cm The existence of charged ions is supported by their movement in electric fields.  INCLUDEPICTURE "http://www.practicalchemistry.org/data/images/width350/migration-ions-1-129.jpg" \* MERGEFORMATINET  Purple negative manganateVII ions move to the positive anode.  INCLUDEPICTURE "http://www.practicalchemistry.org/data/images/width350/migration-ions-2-130.jpg" \* MERGEFORMATINET  Yellow chromate ions move to the anode where silver ions form red silver chromate. 1.6.1b ion formation b describe the formation of ions in terms of electron loss or gain Ionic (or electrovalent) Bonding is formed by the transfer of electrons. For example the sodium atom has one electron on its outer shell, the chlorine atom has seven electrons on its outer shell. During ionic bonding the sodium ion transfers its outer electron to the chlorine atom, and becomes a Na+ ion with the stable configuration of an inert gas. At this time the chlorine atom gains the transferred electron and so forms a Cl- ion also with an inert gas configuration. This results in electrostatic attraction between the new ions of the compound, and so ionic bonds are formed. 1.6.1c dot and cross diagrams draw electron configuration diagrams of cations and anions using dots or crosses to represent electrons  INCLUDEPICTURE "C:\\Documents and Settings\\David Bateman\\My Documents\\Dave\\My Webs\\school science uk web\\asa2sums\\sum1.3\\doc1.gif" \* MERGEFORMATINET  MgO, CaF2 and Li2O are other examples of compounds that use ionic bonding. Task 1.6.1b Draw dot and cross diagrams for these examples. LiF, KF, LiCl, NaF, MgCl2, AlF3, MgO, MgS, Na2O, CaF2 and Li2O, Al2O3. 1.6.1d ionic crystal lattices describe ionic crystals as giant lattices of ions Ionic structures.  INCLUDEPICTURE "C:\\Documents and Settings\\David Bateman\\My Documents\\Dave\\My Webs\\school science uk web\\asa2sums\\sum1.3\\image18.gif" \* MERGEFORMATINET  sodium chloride INCLUDEPICTURE "C:\\Documents and Settings\\David Bateman\\My Documents\\Dave\\My Webs\\school science uk web\\asa2sums\\sum1.3\\image17.gif" \* MERGEFORMATINET  Caesium chloride Sodium Chloride 6:6 co-ordination: each chloride ion has 6 sodium ions as its nearest neighbours. Each sodium ion is also surrounded by six chloride ions as its nearest neighbours. Task 1.6.1d Draw a 2 dimensional structure for NaCl showing the ions. Extend this to 3 dimensions. 1.6.1e ionic bond strength describe ionic bonding as the result of strong net electrostatic attraction between ions The strength of ionic bonds are not just due to two oppositely charged ions. Each positively charged ion is attracted to all of its negatively charged nearest neighbours (e.g. 6 Cl- around each Na+). This ion is also attracted to another ring of oppositely charged ions further out and so on all the way the edge of the crystal. The same is true of each negatively charged ion. The sum of all of these ionic attractions gives the high strength of an ionic bond. Task 1.6.1e Draw a diagram to illustrate this meaning. 1.6.1f Trends in ionic radii recall trends in ionic radii down a group and for a set of isoelectronic ions, eg N3- to Al3+ ionRadius/nmionRadius/nmLi+0.074O2-0.140Na+0.102S2-0.185K+0.138Se2-0.195Mg2+0.072 F-0.133Ca2+0.100Cl-0.180Sr2+0.113Br-0.195N3-0.171I-0.215 HYPERLINK "http://chemit.hostinguk.com/uploads/java/rsc_periodicity/applet.htm" http://chemit.hostinguk.com/uploads/java/rsc_periodicity/applet.htm The trend in group 1 ions is that the size of the ion increases down the group. This is because the outer electrons are in quantum shells progressively further from the nucleus leading to increasingly large ions. Isoelectronic ions contain the same number of electrons. Examples are: N3- O2- F- Na+ Mg2+ . These ions decrease in size in the order that they are written as outer electrons are all in the same quantum shell but there is an increasing nuclear charge. Task 1.6.1f.1 Draw ions and state and explain the trend in ionic size in group 7. Task 1.6.1f.2 Draw ions and state and explain the trend in the set of isoelectronic ions S2- Cl- K+ Ca2+ 1.6g Forming ionic crystals 1.6g recall the stages involved in the formation of a solid ionic crystal from its elements and that this leads to a measure value for the lattice energy (students will not be expected to draw the full Born-Haber cycles) Lattice enthalpies cannot be determined directly and are found instead by cycles, called the Born-Haber cycles, which is similar to the cycles used for determining enthalpy changes using Hess's law. e.g. The reaction between sodium and chlorine may be considered to take place in a series of steps and the enthalpy changes involved in these steps may be determined. These steps may now be put into the Born-Haber cycle, with endothermic steps shown by upward arrows and exothermic reactions shown as downward arrows.  HYPERLINK "http://www.drbateman.net/asa2sums/sum4.1/BornHcyc.ppt" Building up the Born Haber Cycle. (Needs Powerpoint.) The steps needed are: Enthalpy of formation of sodium chloride Hf[NaCl(s)] = -411kJmol-1 enthalpy of atomisation of sodium Hat[Na(s)] = 107kJmol-1 1st ionisation energy of sodium Hi1[Na(g)] = 496kJmol-1 enthalpy of atomisation of chlorine Hat[Cl2(g)] = 122kJmol-1 1st electron affinity of chlorine He[Cl(g)] = -349kJmol-1 Lattice enthalpy of sodium chloride Hlat[NaCl(s) ___________________ Na+(g) + Cl(g) _______________ /\ | 1st electron affinity | enthalpy of atomisation of chlorine| of chlorine | | |____Na+(g) + 1/2Cl2(g)____ \/ ____Na+(g) + Cl-(g)____ /\ | | 1st ionisation enthalpy of sodium | lattice enthalpy of sodium chloride | | |____Na(g) + 1/2Cl2(g)____ | /\ | | enthalpy of atomisation of sodium | | | |____Na(s) + 1/2Cl2(g)____ | | | | enthalpy of formation of sodium chloride | | | \/_____________________ NaCl(s) _____ \/________________ Task 1.6g Describe the steps in forming MgCl2 1.6h Testing ionic models 1.6h test the ionic model for ionic bonding of a particular compound by comparison of lattice energies obtained from the experimental values used in Born-Haber cycles, with provided values calculated from electrostatic theory Experimental values for lattice energy are based on the Born Haber cycle. Theoretical values for lattice energy are based on the equation: Force of attraction between ions =a constant * charge on ion1 * charge on ion2/separation2 compoundLattice enthalpy value based on theoretical ionic modelLattice enthalpy value based on experimentsodium chloride-766.1 kJmol-1-776.4 kJmol-1silver chloride-768.6 kJmol-1-916.3 kJmol-1Good fit e.g. sodium chloride, indicates strongly ionic compound. Poor fit e.g. silver chloride, indicates some covalent nature in compound. Task 1.6i Comment on the ionic character of NaF and NaI. (State which is most ionic and why). compoundLattice enthalpy value based on theoretical ionic modelLattice enthalpy value based on experimentNaF-912 kJmol-1-918 kJmol-1NaI-687 kJmol-1-705 kJmol-1 1.6i Ion polarisation 1.6i explain the meaning of the term polarization as applied to ions Not all ionic bonds are completely ionic. The cation (+ve) may pull electrons from the anion (-ve). Covalent character appears when negative ions are polarized. Negative ions are polarized by positive ones. Below Na+ leaves O2- as a normally formed ion. Bigger charges on ions e.g. Al3+ pull electron density away from O2- and lead to some electron sharing (covalent bonding).  INCLUDEPICTURE "http://scienceaid.co.uk/chemistry/fundamental/images/polarisation.jpg" \* MERGEFORMATINET  Task 1.6i Draw diagrams of ions to illustrate the following: A potassium ion does not polarize a chloride ion. A lithium ion strongly polarizes an iodide ion. 1.6j Factors affecting polarization of ions 1.6j demonstrate an understanding that the polarizing power of a cation depends on its radius and charge, and the polarizability of an anion depends on its size Factors for high polarizing power Small radius cation : high charge density Highly charged cation : high charge density. Factor for high polarizability Large anion : distant electrons less firmly held. Examples easily polarized anions : Chloride-, Bromide-, Iodide-. highly polarizing cations : Lithium+, Berylium2+, Aluminium 3+. Task 1.6j.1 Select the most easily polarized anion and give a reason for the following pairs: bromide and chloride, chloride and iodide, bromide and iodide. Task 1.6j.2 Select the cation with the best polarizing power and give a reason for: sodium and magnesium, lithium and sodium, aluminium and lithium, potassium and sodium. Task 1.6j.3 The data below shows the decomposition temperatures of the carbonates of two Group 2 elements. Compound Decomposition temperature/ oC MgCO3 400 BaCO3 1360 Use the idea of polarisation of ions to explain why MgCO3 decomposes more readily than BaCO3. 1.6k Covalency and polarization 1.6k demonstrate an understanding that polarization of anions by cations leads to some covalency in an ionic bond, based on evidence from the Born-Haber cycle See 1.6h and 1.6i 1.6l Relative stability of ionic compoundsl use values calculated for standard heats of formation based on Born-Haber cycles to explain why particular ionic compounds exist, eg the relative stability of MgCl2 over MgCl or MgCl3 and NaCl over NaCl2.  Assuming Lat E [NaCl2] = Lat E [MgCl2] = -2526kJmol-1 Calculated value of Hf [NaCl2] = +2186kJmol-1 Calculated value of Hf [NaCl] = -411kJmol-1 Hence NaCl has a more negative Hf and so is more stable than NaCl2 Task 1.6l Calculate Hf for MgCl and compare it the value for MgCl2 of -653kJmol-1. Data: Enthalpy of atomisation of Mg = 148kJmol-1 1st ionisation energy of Mg =738kJmol-1 Lattice enthalpy of NaCl (hence MgCl) = -780jKmol-1 enthalpy of atomisation of chlorine Hat[Cl2(g)] = 122kJmol-1 1st electron affinity of chlorine He[Cl(g)] = -349kJmol-1 2 Covalent bonding 1.6.2a The strength of covalent bonds 1.6.2a demonstrate an understanding that covalent bonding is strong and arises from the electrostatic attraction between the nucleus and the electrons which are between the nuclei, based on the evidence: i the physical properties of giant atomic structures ii electron density maps for simple molecules Bond structuree.g.Mp/oCBp/oCHfusion /kJmol-1metallicgiantMg64910909.07covalentSimple molecularS81194451.24covalentSimple molecularH2O01006.03covalentGiant atomicC diamond35504827-covalentGiant atomicSiO2 quartz1610223014.28Covalent substances with giant atomic structures generally have high melting points, high boiling points and high enthalpies of fusion due to the strength of the covalent bond. E.g. bond strengths/kJmol-1: C-C 347, Si-O 466, C-Si 307. Covalent bonds are electrostatic attractions between electrons and nuclei of atoms. See:  HYPERLINK "http://khs-net.kingsbury.brent.sch.uk/online_resources/21st_century_science/additional-science/c5/resources/pp/IC5_4.ppt" http://khs-net.kingsbury.brent.sch.uk/online_resources/21st_century_science/additional-science/c5/resources/pp/IC5_4.ppt Electron density maps show the space between atoms as occupied by the electrons which pull atoms together.  Task 1.6.2a Compare and contrast the physical properties of the following pairs:sulphur and quartz, water and diamond, magnesium and diamond. 1.6.2b Representing covalent bonds 1.6.2b draw electron configuration diagrams for simple covalently bonded molecules, including those with multiple bonds and dative covalent bonds, using dots or crosses to represent electrons. Covalent bonding involves atoms of non-metals completing their outer shells by sharing pairs of electrons. E.g. the hydrogen atom has one electron in its outer shell. Within the hydrogen molecule, (H2) each atom contributes one electron to the bond. Consequently each hydrogen atom now has control of 2 electrons, one of its own and a second from the other atom, giving it the configuration of an inert gas (He).  INCLUDEPICTURE "http://www.drbateman.net/asa2sums/sum1.3/image3.gif" \* MERGEFORMATINET  Task 1.6.2b.1 Draw diagrams for single atoms of H (1), C (6), N(7) O(8), F(9), Cl(17) Task 1.6.2b.2 Draw dot and cross diagrams to show the bonding in HF, F2, H2O, F2O, NH3, CH4, CHCl3, O2,CO2, C2H4, C2H2. Dative covalent bonds. Dative covalent bonding. Normally each atom contributes 1 electron to a covalent bond. In a dative covalent bond, 1 atom contributes both electrons to the covalent bond. For a dative covalent bond, an arrow replaces the straight line.  INCLUDEPICTURE "http://www.drbateman.net/asa2sums/sum1.3/nh4.gif" \* MERGEFORMATINET  INCLUDEPICTURE "http://www.drbateman.net/asa2sums/sum1.3/sum1.31.gif" \* MERGEFORMATINET  This hydrated magnesium ion has 6 coordinate (dative covalent) bonds formed by the lone pairs on each of the 6 surrounding water molecules. 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