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<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">I got a question from someone dealing with sections 13.1 and 13.3. I've<o:p></o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">changed it slightly.<span style="mso-spacerun:yes">
</span>"Why is the ion-solvent attractive force greater for a<o:p></o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">smaller ion, such as Mg^2+ compared to Ca^2+?" Related to this would<o:p></o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">be "Which is more soluble in H2O, NaCl or Fe2O3?”.<o:p></o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif"><o:p> </o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">This has to do with the form of the ion-ion interaction energy and the form of<o:p></o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">the ion-dipole interaction energy. The equations for the energy due to these<o:p></o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">interactions are very similar.<o:p></o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif"><o:p> </o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">The lattice energy (LE) is the energy required to separate the ions in order<o:p></o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">for them to dissolve in solution.<o:p></o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif"><o:p> </o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">LE (for ionic
<span class="SpellE">cmpds</span>) = (Q+)(Q-)/d<o:p></o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif"><o:p> </o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">Q is charge on an ion<o:p></o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">d is the distance between the ions (measured center-to-center)<o:p></o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif"><o:p> </o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">The ion-dipole (ID) energy is the energy released when ions from an ionic<o:p></o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">solid dissolve and are solvated (surrounded) by the solvent. This is due to<o:p></o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">the ion-solvent interaction. This term (energy) is negative since it's energy<o:p></o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">released when attractive forces are formed.<o:p></o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif"><o:p> </o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">ID energy (ions in polar solvent) = (Q+)(u)/d^2<o:p></o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif"><o:p> </o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">Q is charge on an ion<o:p></o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">u is dipole moment of the polar molecule<o:p></o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">d is the distance between the particles (measured center-to-center)<o:p></o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif"><o:p> </o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">Look at both equations just in terms of these variables and what they tell us<o:p></o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">about these energies.<o:p></o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif"><o:p> </o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">If the value for Q (the charge on an ion) inc. then both types of energies inc.<o:p></o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">The more polar the solvent (large dipole moment) the greater the ID energy.<o:p></o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">The smaller the ions or molecules the shorter the distance between them. A<o:p></o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">smaller distance means greater energy for both LE and ID energy.<o:p></o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif"><o:p> </o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">Thus, as the charge on the ions inc. the greater the LE and ID energy.<o:p></o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">The smaller the ions the greater the LE and ID energy.<o:p></o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif"><o:p> </o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">In terms of solubility of an ionic
<span class="SpellE">cmpd</span> dissolved in a polar solvent, both terms<o:p></o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">increase as the charges on the ions inc. and the size of the ions (and solvent<o:p></o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">molecules) dec. This is the "charge density" in my notes and I spoke about in<o:p></o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">class (charge per unit volume or charge/distance). So why does the solubility<o:p></o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">of ionic
<span class="SpellE">cmpds</span> decrease as charges inc. and the ions get smaller if both terms<o:p></o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">inc.? That's due to the form of the two eqns. As the charge density inc. (larger<o:p></o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">charges and smaller ions) the LE inc. more than
<span class="GramE">does</span> the ID energy. Thus, the<o:p></o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">delta(H)_<span class="SpellE">soln</span> becomes more positive (more endothermic,
<span class="GramE">i.e.</span> the energy gap<o:p></o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">between the solute/solvent and solution gets bigger). As this occurs the<o:p></o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">delta(H)_<span class="SpellE">soln</span> can become so positive that not enough disorder, entropy, can be<o:p></o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">created during the solution formation to overcome this uphill energy difference.<o:p></o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif"><o:p> </o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">Think about the energy diagrams I covered in lecture. The first step would be<o:p></o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">to separate the ions in the ionic solid from each other. The energy required to<o:p></o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">do this is related to the lattice energy, LE. The third step is due to the
<span class="GramE">formation</span><o:p></o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">of attractive forces between the ions and the solvent molecules (let’s say H2O)<o:p></o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">and is the ion-dipole, ID,
<span class="GramE">energy</span> and energy is released in this step. Both steps<o:p></o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">are relatively large. The second step would be the energy req. to separate the<o:p></o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">H2O molecules, del(H_2) (this is approx. zero, very small compared to the<o:p></o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">energies of the first and third steps).<o:p></o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif"><o:p> </o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">So, let’s say we're talking about comparing the solubility of two ionic
<span class="SpellE">cmpds</span> in<o:p></o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">which one of them has larger charges.<span style="mso-spacerun:yes">
</span>For simplicity I’ll use an ionic <span class="SpellE">cmpd</span> with<o:p></o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">charges of +1 and -1 and an ionic
<span class="SpellE">cmpd</span> with charges of +2 and -2 and sizes<o:p></o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">of the different ions about the same. I’ll also assume the dipole moment of the<o:p></o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">solvent is 0.5 (“charge” due to the dipole moment).<span style="mso-spacerun:yes">
</span><o:p></o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif"><o:p> </o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">Remember, del(H_1) is the LE, del(H_2) is approximately zero (very small<o:p></o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">compared to the first and third steps) and del(H_3) is the solvation energy<o:p></o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">(also called the del(<span class="SpellE">H_mix</span>).<span style="mso-spacerun:yes">
</span>The delta H of solution is given by,<o:p></o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">del(<span class="SpellE">H_soln</span>) = del(H_1) + del(H_2) + del(H_3) = del(H_1) + del(H_3) since<o:p></o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">del(H_2) ~ 0.<o:p></o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif"><o:p> </o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">As the charges on the ions inc. from +1/-1 to +2/-2 both the LE and ID<o:p></o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">energies increase for both ionic
<span class="SpellE">cmpds</span>. However, the inc. in del(H_1) <span class="GramE">
is</span><o:p></o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">bigger than the inc. in del(H_3).<span style="mso-spacerun:yes">
</span>The del(H_1) inc. by a factor of 4 while<o:p></o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">del(H_3) inc. by a factor of 2. This would mean the del(<span class="SpellE">H_soln</span>) for the<o:p></o:p></span></p>
<p class="MsoPlainText"><span class="SpellE"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">cmpd</span></span><span style="font-size:12.0pt;font-family:"Arial",sans-serif"> with bigger charges is more positive (greater) than the del(<span class="SpellE">H_soln</span>)<o:p></o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">for the
<span class="SpellE">cmpd</span> with smaller charges. This will tend to make the one with<o:p></o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">larger charges less soluble.<o:p></o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif"><o:p> </o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">In general, for ionic
<span class="SpellE">cmpds</span>, the bigger the charges on the ions and the smaller<o:p></o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">the ions (the greater the LE) the higher the melting pt. and the less soluble the<o:p></o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">ionic
<span class="SpellE">cmpd</span>. NaCl is very soluble in water while Fe2O3 is insoluble.<span style="mso-spacerun:yes">
</span>Also, in<o:p></o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">general, the process of an ionic solid dissolving in H2O is endothermic,<o:p></o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">del(<span class="SpellE">H_soln</span>) > 0.<span style="mso-spacerun:yes">
</span>That means an increase in entropy is necessary for the<o:p></o:p></span></p>
<p class="MsoPlainText"><span class="SpellE"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">cmpd</span></span><span style="font-size:12.0pt;font-family:"Arial",sans-serif">. to dissolve.<span style="mso-spacerun:yes">
</span>This isn’t always the case.<span style="mso-spacerun:yes"> </span>There are cases of ionic
<span class="SpellE"><span class="GramE">cmpds</span></span><o:p></o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">dissolving in water which have del(<span class="SpellE">H_soln</span>) < 0, exothermic
<span class="SpellE">soln</span> <span class="GramE">formation</span><o:p></o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">(which would mean an
<span class="SpellE">inc</span> in entropy is not necessary for the <span class="SpellE">
soln</span> to form).<o:p></o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif"><o:p> </o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">In a similar vein, I discussed a diamond dissolving in a liquid. Diamonds<o:p></o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">are a covalent-network solid (<span class="GramE">i.e.</span> a crystal of carbon atoms held together with<o:p></o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">covalent bonds). The first step would be separating the C atoms from each other<o:p></o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">(breaking a huge number of covalent bonds). A tremendous amount of energy<o:p></o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">is required to do this, even if you don't break
<span class="GramE">every last</span> C-C bond (del(H_1) is huge).<o:p></o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">Again, the energy req. to separate the solvent molecules (such as water, C6H14,<o:p></o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">etc.) is very small compared to the first step. The third step, the mixing (solvation)<o:p></o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">step would involve only London Forces between the C atoms/fragments and the<o:p></o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">solvent molecules. This del(H_3) would be very small compared to del(H_1).<o:p></o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">Thus, the del(<span class="SpellE">H_soln</span>) would be very large (very positive). Even though
<span class="SpellE">the</span><o:p></o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">del(<span class="SpellE">S_soln</span>) would be positive (there's an inc. in disorder, entropy, going from very<o:p></o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">ordered diamond to C atoms/fragments) not enough entropy can be created to<o:p></o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">overcome this large positive del(<span class="SpellE">H_soln</span>) so that a solution would form spontaneously.<o:p></o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">Diamonds are insoluble in just about any solvent even at relatively high temps,<o:p></o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">except in solvents in which they would react with the solvent to form a soluble<o:p></o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">product.<span style="mso-spacerun:yes">
</span>In class I stated it could be oxidized by concentrated HNO3. That actually<o:p></o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">wouldn’t even happen except maybe at elevated temps.<span style="mso-spacerun:yes">
</span>There are a few <span class="GramE">very</span><o:p></o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">strong oxidizing acids or combinations of oxidizing acids with other powerful<o:p></o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">oxidizing agents, which might dissolve a diamond due to a reaction.<span style="mso-spacerun:yes">
</span>Diamonds<o:p></o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">are almost indestructible unless they’re under extreme conditions because of the<o:p></o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">very strong covalent bonds between the C atoms.<o:p></o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif"><o:p> </o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">I hope this helps.<o:p></o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif"><o:p> </o:p></span></p>
<p class="MsoPlainText"><span style="font-size:12.0pt;font-family:"Arial",sans-serif">Dr. Zellmer<o:p></o:p></span></p>
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