MCAT Intensive Review Draft Version Ogan Gurel 14 June, 1993The lonic Bond ¢ you know, metal atoms are relatively lectropositive — they have low ionization energies and low Secon Se thcr and thus tend to give up their outer electrons. On the other hand, non-metals are electronegative iad their high electron affinities allow them to readily accept electrons. Thus the energies involved in forming anionic bond between a metal atom (A) and a non-metal atom (B) include the following: Only elements with smal ionization energies such as those onthe far left of the periodic able really Form Such positively-charged cations. In a similar ut opposite sense, only elements with lange clectron affinities such Wiese eth lg ight ofthe periodic table easily form thelr corresponding negatively charged anions, The mutual tacton Paras te two oppositely charged ions is always favorable and is thus accompanied by a negative energy char. whe oumation of an ionic bond is favored when the net energy change resulting from all three processes is negative, ‘Lot's consider a specific example — that of sodium chloride — and try to calculate this overall energy change. ‘This type ofealeulation is called the Born-Haber cycle and you will encounter these and related energy caleuatons throughout the MCAT. Sodium is a metal — a group I clement yz Dhak readily gives up is loosely-held outer electron. Its relatively Tear jonlaalion enengy of +119 Keal/mol means that only 119 lecl/mole of energy has to be added to remove the outer electrons ffomamole of sodium. On the other side of the periodic table, we fave chlorine which is a group VIE non-metal with an electron Minty of 83 keal/mole. ‘This means that 88 kcal/mole is released aifiity ofS Karendded to a mole of chlorine. Still speaking, because energy is released (eg. the final anion state rae ery than the inal neutral atom), the energy change is -&3 Keal/mole. By a separa calelation Cree in te comentary changes quae, dgre with a bond dance of 1=236A ino the electric enesy anyone ind tat the atactive energy (140 kcal/mole (Try it). The calculation is summarized below: ‘What is the meaning of this last value of -104 kcal/mol? It's the calculated net energy change that results from the formation of a mole of lonically bonded NaCI molecules. ‘The negative value indicates that the final products {NaCl are ata lower energy than the slated atoms (Na & CI), Tn other words, sodium and chloride would rather be {Ogether than apart. Let’ look ati from the other direction: how much energy would be required to breaks NaC info itecelated atoms? ‘Since breaking a bond is opposite from forming it, the energy required would be +104 kcal/mole, ‘This, of course, s the bond dissociation energy (BDE). It turns out that the experimental value for the BDE of gas: phase NaCl Is actually. +98 kcal/mole which is quite close to our simple calculation above, The rensons for the Eiscrepancy are complicated but they include the fact that repulsive terms and polarization factors (partial covalent bonding) were not included in this simplified analysis. ‘What about solid NaCl — eg. table salt? Tonic erystals are not composed of isolated NaCI molecules but are actually arrays of cations and anions distributed in a way that maximizes thelr attractive interactions. In table salt for ‘Sample, each Na* eation is surrounded by six CI” anions, not fust one Cl° anion; likewise each CI" anion is ‘Surrounded by six Na* cations. ‘Thus the energy required to tear apart a lattice the lattice enthalpy) of NaCl is larger than +98 keal/ mole and has been experimentally determined to be +188 kcal/mole. The additional stabilization of 90 kcal/mole results from the additional electrostatic attractions found in the soli lattice, 188 keal/mole is quite a large dissociation energy which explains many of the properties of ionic crystals. For ‘ample, ionic crystals are very hard and also have high melting points. These macroscopic properties are 2 direct Corscfaence of the extraordinary strength of ionic bonds, particularly n the context of a regular erytaline array, You Size Kiow that ionic erystals are quite brittle — if you force them enough they will easily break. ‘This results from the net that once the lattice is only slightly disrupted many of the attractive interactions will be lost and repulsive forces ray, in fact, dominate. The important point is that the understanding of both atomic-level and macroscopic phenomena depends on a clear analysis of both structure and energy.~ OY) ¢ CCouombie (lectrostal) ietoracton ‘onstisios the nie bond. srupvqonsrranysiy) 1, /oncbords ee store and ionic crystals relatively hard. How is it then that many ionic solids such as table salt so readily dissolve in water? Something or some process ‘must be supplying the energy to break the ionic bonds stabilizing the solid. What is i? 2. The side chains of some amino acids are changed at physiological pH. List the positively charged (basic) amino acids and the negatively charged (acidic) amino acids. These amino acids are ordinarily on the surface of protein molecules, Why? Under what conditions might one find charged amino acids situated in the interior of a protein molecule? 3. Only one-half of a typical chromosome is composed of DNA. The other half is composed of protein molecules called histones that bind tightly to the DNA. What do you think is the most distinguishing feature of these proteins? ‘Some proteins such as those involved in gene regulation bind only to specific DNA sequences. How is it that these histones can bind in a general fashion to almost all of the DNA and not just to any particular sequence? 4. The melting point of KCI (770°C) is less than that for NaCl (801°C). What do you thinkis the major reason for this difference? Hint: study the Coulombic interaction equation carefully.