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Iconic Bonding: The Evidence That Ions Exist
Iconic Bonding: The Evidence That Ions Exist
Iconic bonding
The evidence that ions exist
Physical properties of ionic compounds: high melting temperatures, showing strong forces of attraction between ions, soluble in polar solvents, conduct electricity when molten or in aqueous solution. Electron density maps of compounds produced from X-ray diffraction patterns show zero electron density between ions meaning complete electron transfer. Migration of ions in electrolysis. For example, electrolysis of green aqueous copper(II) chromate(VI) attracts a yellow colour (chromate(VI) ions) to the anode and a blue colour (copper(II) ions) to the cathode.
B A
0.1 nm Electron density map for sodium chloride clearly showing separate ions
Formation of ions
An ion is formed when an atom gains or loses one or more electrons. For example, a copper atom loses two electrons: Cu(g) Cu21(g) 1 2e2 to form a copper cation. A chlorine atom gains one electron: Cl(g) 1 e2 Cl2(g) to form a chloride anion. A positive ion is called a cation, it is attracted towards the cathode in electrolysis. A negative ion is called an anion, it is attracted towards the anode in electrolysis. When ions are formed they tend to have a full outer shell, i.e. eight electrons. This is called the octet rule. Ions with full outer shells have the same electronic configurations as noble gases (Group 0) for example, a Ca21 ion has the same electronic configuration as argon; they are isoelectronic.
Watch out!
The formation of an ion is not the same as the formation of an ionic bond. Ions are formed as ionic bonds are made, but they can also be formed by other means, e.g. electron bombardment in a mass spectrometer.
Cl
F Ca + F Ca
(a)
Na +
Cl
Na
Cl
2+
F F
Electrons are transferred from one atom to another to form ions, each with an outer shell of eight electrons. You must show the charge on F F each ion in the compound. The new 1 21 2+was an inner shell in the atoms it is not usually outer shell of the Na and Ca cations Ca (b) Ca + shown in dot-and-cross diagrams (although you may be asked to show all electrons).
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An ionic bond is an omnidirectional electrostatic force of attraction between oppositely charged ions. The forces of attraction are equal in all directions. In ionic compounds each ion is surrounded by ions of the opposite charge. Ionic compounds form giant ionic lattices in the solid state (also called an ionic crystal).
Cl ion
Examiner tip
It really is best not to draw ionic lattices with lines joining the ions. These lines imply there are individual bonds between pairs of ions this is not the case. An ionic bond is formed between an ion and all those of opposite charge that surround it hence it is omnidirectional.
0.157 nm
Na 0.191 nm
Na 0.102 nm
Cl 0.099 nm
Cl 0.180 nm
Br
Br
0.235 nm
0.196 nm
0.144 nm
0.195 nm
Ionic radius increases down a group cations are smaller than their atoms
Ionic radius increases down a group anions are larger than their atoms
Quick Questions 1 2 3 4 In how many directions does an ionic bond act? How is an ion formed? Draw a dot-and-cross diagram to represent magnesium chloride. a Using your data book, draw scale diagrams, in decreasing order of size, of the following ions: N32, O22, F2, Na1, Mg21 and Al31. b What are their electronic configurations? c Why do the ions have different sizes?
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Topic 4: Bonding
Worked Example
Calculate the lattice energy for calcium chloride: Ca21(g) 1 2Cl2(g) CaCl2(s). The enthalpy changes involved in the formation of calcium chloride from calcium and chlorine are: 1 Ca(s) Ca(g) DHat [Ca(s)] standard enthalpy change of atomization of calcium 2 Ca(g) Ca1(g) 1 e2 DHi1 [Ca(g)] 1st ionization energy of calcium 3 Ca1(g) Ca21(g) 1 e2 DHi2 [Ca(g)] 2nd ionization energy of calcium 1 4 Cl2(g) 2Cl(g) 2 DHat [_ 2 Cl2(g) ] standard enthalpy change of atomization of chlorine 5 2Cl(g) 1 2e2 2Cl2(g) 2 DHe [Cl(g)] 1st electron affinity of chlorine 6 Ca(s) 1 Cl2(g) CaCl2(s) DHf enthalpy change of formation of CaCl2
Ca2(g) 2e 2Cl(g) -[ 1 2 Hat 2 Cl2(g) ] 2 122 244 kJ moI1 Ca2(g) 2e Cl2(g)
Watch out!
Make sure you include all the ionization energies for the metal. This means only the 1st I.E. for Group 1 metals, but the sum of the 1st and 2nd I.E. for Group 2 metals (not just the 2nd I.E.). Also, the standard enthalpy of atomization is associated with the production of 1 mole of gaseous atoms when you have to produce 2 moles of atoms, you must multiply by 2.
Examiner tip
Ca2(g) 2Cl(g)
Ca (g) e Cl2(g)
Ca(g) Cl2(g) - [ CaCl2(s) ] ? Hlat -[ Ca(s) ] 178 kJ moI1 Hat Ca(s) Cl2(g)
You will not have to draw a full BornHaber cycle but you can expect to have to fill in some missing values and then calculate the remaining unknown energy (dont forget the correct sign and units). Simply move around the cycle in one direction, adding up the energies. Its exactly the same as using a Hess cycle remember, when going in the direction of an arrow use the same sign as the energy; going against the arrow, use the opposite sign.
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Using the BornHaber cycle, the lattice energy for CaCl2 is given by: DH lat [CaCl2(s)] 5 [2(2698) 2 244 21145 2 590 2 178 2 796]kJ mol21 5 22255 kJ mol21 This is very large and indicates the strength of ionic forces of attraction between ions.
Worked Example
Why is calcium chloride CaCl2, and not CaCl or CaCl3?
Enthalpy change in the process, DH /kJ mol21 Ca(s) Ca(g) Ca(g) Ca1(g) 1 e2 Ca1(g) Ca21(g) 1 e2 Ca21(g) Ca31(g) 1 e2
1 _ Cl (g) 2 2
Cl(g) 3Cl(g)
Cl2(g) 2Cl(g)
3 _ Cl (g) 2 2
Cl(g) 1 e2 Cl2(g) 2Cl(g) 1 2e2 2Cl2(g) 3Cl(g) 1 3e2 3Cl2(g) Ca1(g) 1 Cl2(g) Ca1Cl2(s) Ca21(g) 1 2Cl2(g) Ca21(Cl2)2(s) Ca31(g) 1 Cl2(g) Ca31(Cl2)3(s)
Summary of BornHaber data for CaCl, CaCl2 and CaCl3
The theoretical enthalpy change of formation for each compound is found by adding the energies in each of the columns. Using the data, the enthalpy changes of formation for the three compounds are: 1 Ca(s) 1 _ Cl (g) CaCl(s) DHf 5 2170 kJ mol21 2 2 Ca(s) 1 Cl2(g) CaCl2(s) DHf 5 2796 kJ mol21 3 _ Ca(s) 1 2 Cl2(g) CaCl3(s) DHf 5 11341 kJ mol21 The most stable compound is that with the most exothermic enthalpy of formation, CaCl2(s). The formation of CaCl3 is highly endothermic, because the very high 3rd ionization enthalpy cannot be provided by the extra lattice energy.
Quick Questions 1 2 How do you find the enthalpy change for the formation of the Al31(g) ion from the element? What does the general size of lattice energies tell us about ionic bonding?
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Topic 4: Bonding
The different methods of obtaining the lattice energies for the sodium halides produce very similar results. But this is not the case for the silver halides their lattice energies are more exothermic (more negative and more stable) than theory would predict. Coulombs law assumes that the ions are completely separate and spherical (not distorted). Experiment therefore suggests there is a degree of electron sharing, i.e. covalency, in the silver halides, while the sodium halides show (almost) pure ionic bonding. This is supported by lower melting temperatures for silver halides than sodium halides.
Polarization of ions
Polarization of an ion is the distortion of its electron cloud away from completely spherical: a cation will distort an anion a cation has polarizing power an anion is polarizable.
Watch out!
Cations polarize. Anions are polarized.
(a)
(b)
(c)
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The polarizing power of a cation depends on its charge density: a small cation is more polarizing than a larger one the positive nucleus has more effect across the small ionic radius a cation with a large charge is more polarizing than one with a small charge a large charge has more attraction than a small one. The polarizability of an anion depends on its size alone: a large anion is easily polarized its electron cloud is further from the nucleus and is held less tightly than on a smaller anion. As shown above, for some ionic compounds the ionic model is good BornHaber lattice energies agree well with theoretical values. For some ion pairs the bonds have considerable covalent character the agreement between experimental and theoretical lattice energies is poor. The figure shows: a completely spherical and separate ions; b an anion distorted by a cation; and c distortion so great that the electron density resembles a covalent bond. This idea is developed further in Unit 2, see page 66.
Thinking Task
When is an ionic bond not an ionic bond?
Quick Questions 1 2 3 4 What affects the polarizing power of a cation? Why is a large anion polarizable? How can an ionic bond have some covalent character? What evidence is there to suggest that the bonding in silver iodide has some covalent character?
Thinking Task
At what point does an ionic bond become covalent, rather than just having some covalent character?
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Topic 4: Bonding
Covalent bonding
Formation of covalent bonds
A covalent bond is formed when a pair of electrons is shared between two atoms. This happens when two atoms approach each other and their electron clouds overlap and electron density is greatest between the nuclei. This region of high electron density (the covalent bond) attracts each nucleus and therefore keeps the atoms together. Covalent bonding is a strong electrostatic attraction between the nuclei of the bonded atoms and the shared pair of electrons between them. The distance between the two nuclei is the bond length. It is the separation at which the energy of the system is at its lowest.
Work has to be done to push the nuclei together, so energy of H2 molecule rises Attraction Nucleus Shared electrons A covalent bond is a strong attraction between the nuclei and the shared pair of electrons between them
Cl
Separation
Cl Al Al Cl
Cl Cl
Energy
Cl
436 kJ mol
1
Cl Al Cl
Cl Al Cl
Cl Cl
Attractive and repulsive forces balance at this separation 0.074 nm The bond length in a hydrogen molecule is 0.074nm
Dative covalent bonding in Al2Cl6. The arrows show the electron pairs that have come from chlorine atoms.
Dative covalent bonds are formed when both the shared electrons come from just one of the atoms. For example, aluminium chloride, AlCl3, will form dimers (a combination of two identical molecules) of Al2Cl6. The aluminium atom in aluminium chloride is electrondeficient (only six electrons in its outer shell) but by forming dative covalent bonds the octet rule is fulfilled. Atoms can share more than one pair of electrons and form double or triple covalent bonds: a double bond results from two shared electron pairs e.g. in oxygen, O2, O5O a triple bond results from three shared electron pairs e.g. in nitrogen, N2, N;N.
Watch out!
Covalent bonds and dative covalent bonds are exactly the same once they have been formed.
Electron densities in electrons per cubic atomic length Electron density in the covalent bond between two hydrogen atoms, showing region of high electron density between the two atoms
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Cl Cl Cl Cl H H C H H H C H H H
H H
O O
H H
O O
O O
Lone pairs
In some molecules, not all the electrons in the outer shell may be involved in bonding. A non-bonding pair of electrons is called a lone pair. Lone pairs are shown on dot-and-cross diagrams on one atom only (not shared). Lone pairs affect the shape of molecules (see Unit 2, page 73).
Worked Example
Draw a diagram to show the bonding in silane, SiH4. This is simply asking you to draw the dot-and-cross diagram. Follow the stages shown in the diagram. When you have finished, check that each atom has the right number of its own outer shell electrons (4 for Si and 1 for each H) and a total of 8 electrons surrounding the Si, with 2 for each H.
H H Si H H Stage 1 H H Si H H Stage 2 Put in the hydrogen electrons H H Si H H Stage 3 The four Si electrons complete the diagram
Quick Questions 1 2 3 Why does a covalent bond hold a pair of atoms together? Draw diagrams to show the outer electrons in Cl2O, CO and Al2Cl6. How do the physical properties of diamond give evidence to support the theory of covalent bonding?
Thinking Task
Are all covalent bonds the same?
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Topic 4: Bonding
Metallic bonding
Metals consist of giant lattices of metal ions in a sea of delocalized electrons. The metal ions vibrate about fixed points in the solid lattice, being held in place by the electrons (also vibrating) around them. It is the outer electrons of the metal that have become delocalized they are no longer associated with one particular atom. Metallic bonding is the strong attraction between metal ions and the sea of delocalized electrons.
Watch out!
Sea of electrons, only some forces of attraction are shown
Be careful! Use the correct names for particles atoms in covalent bonds, but ions in ionic bonds.
The attraction between metal ions and electrons keeps the ions in place
The typical characteristics of metals can be explained using this simple model of metallic bonding. Electrical conductivity the delocalized electrons are free to move in the same direction when an electric field is applied to the metal; the movement of charged particles is an electric current. Thermal conductivity the delocalized electrons transmit kinetic energy (heat) through the metal, from a hot region to a cooler one, by colliding with each other. High melting temperatures the positive ions are strongly held together by the attraction of the delocalized electrons; it takes a lot of energy to break the metallic bonds and allow the particles to move around in the liquid state. Malleability and ductility metals can be hammered into shape (malleable) or stretched into wire (ductile) because the layers of positive ions can be forced to slide across each other while staying surrounded by the sea of delocalized electrons. Quick Questions 1 2 3 Why do metals generally have high melting temperatures? Explain why metals are good conductors of heat. What keeps the ions in a metal in place?
Thinking Task
Why do Group 1 metals have lower melting temperatures than the transition metals?
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Ionic bonding
Recall and interpret evidence for the existence of ions Describe the formation of ions in terms of electron loss or gain Draw dot-and-cross diagrams to represent electronic configuration of cations and anions Describe ionic crystals as giant lattices of ions Describe ionic bonding as the result of strong net electrostatic attraction between ions Recall the trends in ionic radii down a group and for a set of isoelectronic ions
Recall the stages involved in the formation of a solid ionic crystal from its elements Test the ionic model for ionic bonding by comparison of lattice energies from BornHaber cycles with values calculated from electrostatic theory Use values calculated for standard enthalpies of formation based on BornHaber cycles to explain why particular ionic compounds exist
1.6.1l
1.6.1i
Understand that the polarizing power of a cation 1.6.1j depends on its radius and charge, and the polarizability of an anion depends on its size Understand that polarization of anions leads to some covalency in an ionic bond Use values calculated for standard enthalpies of formation based on BornHaber cycles to explain why particular ionic compounds exist Covalent bonding Understand 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 from: (i) the physical properties of giant atomic structures (ii) electron density maps for simple molecules Draw dot-and-cross diagrams to represent electronic configurations of simple covalent molecules, including multiple bonds and dative covalent bonds Metallic bonding Understand that metals consist of giant lattices of metal ions in a sea of delocalized electrons Describe metallic bonding as the strong attraction between metal ions and the sea of delocalized electrons Use the models of metallic bonding to interpret simple properties of metals 1.6.1k 1.6.1l
1.6.2a
1.6.2b
1.6.3a 1.6.3b
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Topic 4: Bonding
(2)
Cl P Cl Cl
Basic answer: Many students can draw the correct number of electrons round each Cl atom. (1) However, they may forget to show the symbols for each atom.
Excellent answer: To get the second mark, you need to show that there are three shared pairs and one lone pair of electrons round the P atom. (1) Answers missing out the pair of non-bonding electrons for P, or showing 8 electrons but not as three shared pairs plus one lone pair, would not gain credit. 2 Explain why beryllium chloride is covalent but magnesium chloride is ionic. Examiner tip This is all about the polarizing power of the Group 2 cations in relation to the chloride anion. The charges on the beryllium and magnesium ions are the same because they are in the same group. However, the Be21 ion has one fewer electron shells than the Mg21 ion and is very small. The answer is: The chloride ion is moderately polarizable. The Be
21
(3)
(1) (1)
2
ion would therefore be very polarizing and polarize the Cl2 ion to form a covalent bond. ion is larger and not sufficiently polarizing to form a covalent bond with Cl . (1)
The Mg
21
There is frequent confusion between polarizing power and polarizability. Take care not to get the explanation the wrong way round e.g. the chloride ion polarizes the Be21 ion is incorrect. Excellent answer: Keep your answers concise (short) and to the point (accurate) but ensure you answer fully. In the question about BeCl2 and MgCl2 you have to say something about all three types of ion and the clue is that there are three marks available. 3 Magnesium iodide is a compound of magnesium. The radius of the magnesium ion is 0.072 nm, whereas the radius of the iodide ion is much larger and is 0.215 nm. a Describe the effect that the magnesium ion has on an iodide ion next to it in the magnesium iodide lattice. Examiner tip The electrons around the iodide ion are drawn towards the magnesium ion/Mg21 polarizes I2 ions. (1)
(1)
Take care not to get confused between polarizing power and polarizability. Marks will also be lost if you refer to atoms instead of cations. you must say the Mg21 ion polarizes, not Mg21 polarizes, or that iodine/I2 is polarized. b What two quantities must be known about the ions in a compound in order to calculate a theoretical lattice energy? Examiner tip Radius/size (of ions), (1) charge/charge density. (1) (2)
Again, dont refer to atoms atomic radius is incorrect here. There are no marks for recalling that Coulombs law is used, unless you also give the terms in the Coulombs law formula.
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c Suggest how the value of the theoretical lattice energy would compare with the experimental value from a BornHaber cycle for magnesium iodide. Give a reason for your answer. Examiner tip The theoretical lattice energy would be less. (1)
(2)
Students have difficulty explaining why the theoretical value will be less. The theoretical value assumes a fully ionic model. However, the small, highly charged magnesium ion polarizes the iodide ion giving some covalent bonding character. However, the bonding is not fully covalent you will lose the mark for saying this. An acceptable answer would be simply covalent character, or the theoretical value assumes a fully ionic model. (Adapted from Edexcel Unit test 4 Q1, June 07)
Examiner tip
Read the question! This time you are to show all the electrons, not just those in the outer shell. It also reminds you to show the charges a big hint about the type of bonding check that your answers match the information given in the questions!
3 a Use the following data to complete the BornHaber cycle for potassium chloride and use it to calculate the electron affinity of chlorine. DH/kJmol21 1st ionization energy of potassium 1419 Enthalpy of atomization of potassium 189.2 K+(g) + e + Cl(g) Enthalpy of atomization of chlorine 1121.7 Enthalpy of formation of KCl(s) 436.7 - [Cl2(g)] Lattice enthalpy of potassium chloride 711 Hat -[Cl] He b Calcium is in the same period in the Periodic Table as + K (g) + e + Cl2(g) potassium. The lattice enthalpy of calcium chloride is 2258kJmol21. Explain why this is so different from + the value for potassium chloride given in (a). (2) K (g) + Cl (g) Hi- [K(g)] c Lattice enthalpies may be calculated based on an assumption about the structure of the solid, or found K(g) + Cl2(g) experimentally using data in this BornHaber cycle. The experimentally found lattice enthalpy of - [K(s)] Hat potassium chloride is 9kJmol21 more exothermic - [K+Cl(s)] Hlat than that calculated; for calcium chloride the K(s) + Cl2(g) experimental value is 35kJmol21 more exothermic than that calculated. + Suggest why the calculated and experimental values Hf-[K Cl (s)] are different in both compounds. (3)
1
+ K Cl (s)
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