ࡱ> '`  bjbj{P{P .::74 )))) *<Bx*****K4K4K4@@@@@@@$DhxF`AA{51zK4{5{5A**RB>>>{5b**@>{5@>>>** 1Xg):>7@hB0B>F=F>F>K4>4,>4$4K4K4K4AAu> K4K4K4B{5{5{5{5d~#$~#$tJ 4.4 How far?  entropy 4.4a spontaneous endothermic reactions Acids and alkalis react together spontaneously. They react straight away, on mixing. H+(aq) + OH-(aq) ---> H2O(l) (Honeut) = -57kJmol-1 Exothermic reactions with a -ve enthalpy change often proceed spontaneously. The reaction proceeds in the direction of lowest energy. H+(aq) + OH-(aq) | | | /\Honeut = -57kJmol-1 | ! H2O(l) Some endothermic reactions also proceed spontaneously. NH4Cl(s) + 100H2O(l) ( NH4Cl(aq,100H2O) ; H = +14kJmol-1 There must be another factor in play. It is called entropy. Activity 4.4a Add a spatula measure of Mg powder to 10cm3 of 2M HCl in a boiling tube. Add a spatula measure of sodium hydrogen carbonate to 10cm3 of 2M citric acid. Add a spatulas measure of ammonium nitrate to 10cm3 of water. Add a spatula measure of ammonium carbonate to 10cm3 of ethanoic acid. Grind separate samples of barium chloride and ammonium chloride using a pestle and mortar. Mix the solids in a boiling tube. Record the temperature rise in each case. Explain why both reactions are spontaneous. Task 4.4a Concentrated sulphuric acid and water form one layer and become very hot when mixed. Glucose dissolves spontaneously in water and feels cold when it has done so. Explain why these processes might be feasible reactions. 4.4b Molecules energy quanta and entropy Entropy is a measure of disorder. Molecules and other species can be ordered (low entropy) or disordered (high entropy). Atoms and other species can hold amounts of energy. This can be in electronic orbitals or as vibrational, rotational or translational energy. Each portion of energy is present in a fixed amount called a quantum. Many quanta of energy can be held in many ways (high entropy). Few quanta can only be held in a few ways (low entropy). Activity 4.4b Using students to represent molecules and pennies to represent quanta of energy arrange the students on your bench into low and high entropy states. Task 4.4b Draw diagrams to illustrate high and low entropy states. 4.4c Entropy in solids liquids and gases Statistics shows us that the more particles and the more quanta of energy present the greater the number of arrangements and the greater the entropy. Just 5 quanta spread between two molecules can have 32 arrangements. More quanta are available at higher temperatures so leading to more arrangements and higher entropy. Increasing temperature therefore leads to an increase in the entropy of a system. An increase in temperature is also likely to lead to the melting and boiling of a substance with accompanying increase in disorder and so entropy. Perfect crystals have no impurities and all particles in exactly the right position so have low entropy. If the temperature of a crystal falls to absolute zero, (-273oC or 0K) then its entropy is zero, in theory. However the Heisenberg uncertainty principles states that we cannot be certain about both the energy and the position of a particle at the atomic level. This means that even perfect crystals at absolute zero have some entropy. Task 4.4c.1 Draw diagrams with 6 circles for atoms and dots for energy quanta to show copper as (a) a perfect crystal at absolute zero, (b) a crystal at room temperature, (c) copper just below its melting point, (d) copper above its melting point but below its boiling point, (e) copper above its boiling point. Task 4.4c.2 Sketch a graph of entropy against temperature for copper showing any changes of state. 4.4d Molecule complexity and entropy Single atoms have limited entropy. They are symmetrical so are the same from all angles.  Bigger molecules become more complex and less symmetrical so even their position in a fixed space leads to some entropy because different orientations are possible.  Molecules also have bonds which can vibrate. The more bonds, the more vibrations that are possible and the greater the entropy.    Large molecules can even bend into different shapes which introduces even more entropy. Task 4.4d Draw diagrams using chemical symbols to show increasing complexity and hence entropy in hydrogen atoms, hydrogen molecules, water molecules, butane molecules and brombutane molecules. 4.4e Entropy on rearranging crystalline solids Collision theory predicts that reactions occur when randomly moving particles meet in a collision. If particles from a solution react with particles in a solid the low entropy arrangement of the solid is changed to a higher entropy more random arrangement in the solution, E.g. calcium ions in marble move from their ordered crystal lattice to a disordered position moving through the solution in the equation below. In this case the appearance of a gas hugely increases disorder and hence entropy. CaCO3 + 2HCl(aq) ( CaCl2(aq) + H2O(l) +CO2(g) Low entropy system high entropy system Task 4.4e Write equations for reactions stating whether you expect the change to be to or from high entropy. 4.4f Entropy and the direction of natural change The direction of natural change for a process is in the direction of increased entropy. I.e. S = positive. Task 4.4f Label these processes as having positive or negative S and give reasons: gases spread spontaneously through a room, NaCl dissolving in water, a solid crystallising from solution. 4.4g Experiments relating disorder and enthalpy changes i dissolving a solid, eg adding ammonium nitrate crystals to water Spontaneous reaction. Solution cools. ii gas evolution, eg reacting ethanoic acid with ammonium carbonate Spontaneous reaction. Solution cools. iii exothermic reaction producing a solid, eg burning magnesium ribbon in air iv endothermic reaction of two solids, eg mixing solid barium hydroxide, Ba(OH)2.8H2O with solid ammonium chloride Dry solids become damp, smells of ammonia and the mixture cools. Task 4.3g Explain why each reaction is spontaneous and write an equation for each. 4.4h Entropy change (S) in the system and the surroundings The system is the chemicals reacting but can include the container (copper) or not include the container (plastic). In open containers the chemicals in the system are normally the solids and liquids present. Closed containers will include gases but energy changes are now not enthalpy changes. The surroundings include the atmosphere around the reaction vessel and the rest of the universe! Stotal = Ssystem + Ssurroundings 4.4h(i) calculate the entropy change in the system for a reaction, substanceC(s)O2(g)Cl2(g)CO2(g)N2(g)H2(g)NaCl(s)NH3(g)So/Jmol-1K-15.720522321419113172.4192Entropy changes in a system can be calculated using standard entropies as above. E.g. What is the entropy change for the system forming 1 mole of ammonia? N2(g) + 3H2(g) ( 2NH3(g) Sosystem[2mol] = Soproducts -Soreactants = (2*192Jmol-1K-1)  ((191Jmol-1K-1 + 3*131Jmol-1K-1) = -199Jmol-1K-1 Sosystem[1 mol] = -199 Jmol-1K-1 /2 = -99.5 Jmol-1K-1 Task 4.4h(i).1 calculate the entropy change for the system when 1 mol NaCl forms from sodium and chlorine. Task 4.4h(i).2 calculate the entropy change for the system when 1mol carbon dioxide forms from carbon and oxygen. Task 4.4h(i).3 calculate the entropy change for the system when 1 mol hydrogen chloride forms from hydrogen and chlorine. Answers 1. -90.3 Jmol-1K-1, 2. 3.3 Jmol-1K-1, 3. +9.8 Jmol-1K-1 4.4(j) Calculating Ssurroundings and Stotal The entropy change in the surroundings is due to heat transfer. The more energy quanta transferred the greater the entropy increase. Also, the lower the temperature the greater the effect will be. Ssurroundings =- H/T What is the entropy change in the surroundings if 1 mol NaCl is formed from its elements at 25oC. (Hf [NaCl)]= -411kJmol-1) Ssurroundings =- H/T = - (-411kJmol-1) / (25+273)K = + 1379J mol-1K-1 Task4.4(j).1 What is the entropy change in the surroundings if 1 mol ammonia is formed from its elements at 25oC. (Hf ammonia= -46kJmol-1) Task4.4(j).2 What is the total entropy change if 1 mol ammonia is formed from its elements at 25oC. Task4.4(j).3 What is the total entropy change if 1 mol sodium chloride is formed from its elements at 25oC. Task4.4(j).4 What is the total entropy change for the combustion of methane with measurements made under standard conditions. Answers: 1. +154.36J mol-1K-1 , 2.+54.96 J mol-1K-1 , 3 J mol-1K-1. , 4. J mol-1K-1 4.4(k) Entropy and the feasibility of a reaction A reaction will proceed (is feasible) if the total entropy change, Stotal, is positive. Stotal = Ssystem + Ssurroundings Stotal = Ssystem - H/T As temperature increases Ssurroundings becomes less so has less effect on Stotal and so less effect on feasibility. Task4.4(k) Demonstrate that the reaction between ammonium chloride and barium hydroxide is feasible at 25.0oC if: Ssystem = +298.6Jmol-1K-1and Hreaction = +21.2kJmol-1 4.4(l) Thermodynamic stability and kinetic inertness One system is thermodynamically stable with respect to a second one if the first one is lower than the second on an enthalpy level diagram. e.g. Oxygen is energetically stable with respect to ozone. ozone (unstable) | | oxygen \/ (stable) Even if a system is thermodynamically unstable and is expected to react to form a stable one the system may not react. The system will not react if it is kinetically inert. This means that the reaction proceeds too slowly for any reaction to be seen. When a system is thermodynamically unstable but kinetically inert, the reaction is likely to be seen but only under favourable conditions. Sugar and oxygen is a system like this with respect to carbon dioxide and water. A bowl of sugar on the table does not react but if heated an exothermic reaction takes place. 4.4(m) Calculations to show that endothermic reactions can occur spontaneously at room temperature Standard molar entropies/Jmol-1K-1 : NH4NO3(s), NH4+(aq)=+113, NO3-(aq)+146, CH3COOH(aq)=160, (NH4)2CO3(aq), CH3COO-(aq)=86.6, H2O(l)=+69.9, CO2(g)=+214, Mg(s)=+32.7, O2(g)=+205, MgO(s)=+26.9, Ba(OH)2(s)99.7, NH4Cl(s)=+94.6, Ba2+(aq)=+9.60, Cl-(aq)=56.5, NH3(g)192. enthalpy formation MgO = -601.7kJmol-1 Show that S is positive for each of these endothermic reactions so making each one spontaneous: N,.06:R0 2 4 F H ^ ` l n p r z 2 Ƚsk_Q_Q_h%h%>*CJH*aJh%h%>*CJaJhn.CJaJ hn.hQCJOJQJ^JaJhn.hn.7CJH*aJhWhCJaJhn.hn.CJH*aJhn.hn.CJH*aJhn.hn.CJaJh%hn.CJaJh9hM!f5CJaJh9hQ5CJaJ hn.hM!fhn.h"5CJ aJ hn.hM!f5CJ aJ .00   ? 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It is the enthalpy change for the following process: M+(g) + X-(g) --->M+X-(s) ; enthalpy of reaction = DHlatt[M+X-(s)] The enthalpy of atomisation of an element is the enthalpy change when one mole of gaseous atoms of an element are formed from an element is its standard state. E.g. It is the enthalpy change for the following process: 1/2Cl2(g) ----> Cl(g) ; enthalpy change = DHa[1/2Cl2(g)] The enthalpy of hydration is the enthalpy change when 1 mol of aqueous ions is formed from gaseous ions. It is the enthalpy change for the following process: M+(g) + aq ---> M+(aq) ; enthalpy change = DHhyd[M+(g)] DHsol = DHhyd  lattice enthalpy Task4.4(n).1 Draw an energy cycle showing an ionic solid MX its gaseous and aqueous ions. Task4.4(n).2 Calculate the enthalpy of solution of NaCl given hydration enthalpies of Na+=-390kJmol-1, Cl-=-384Kjmol-1, lattice enthalpy of NaCl = -781kJmol-1. 4.4(o) demonstrate an understanding of the factors that affect the values of enthalpy of hydration and the lattice energy of an ionic compound The lattice enthalpy of an ionic compound is affected by the size and charge on the ions which make it up. A decrease in the size of any ion increases the lattice enthalpy. (more negative/exothermic) This is because small ions can be close together and the smaller distance of separation the larger the attractive force between the ions. An increase in charge also increases lattice enthalpy. (makes it more negative/exothermic) This is because the force of attraction between ions increases as the charge on the ion increases. Enthalpy of hydration is also affected by ion size and charge. The enthalpy of hydration becomes more exothermic if the size of the ion decreases or the charge on the ion increases. Both of these factors lead to increased charge density. Task 4.4o.1 Place the following pairs of ions with the ones with the most negative enthalpy of ionisation first: Na+ and K+, Na+ and Mg2+, Al3+ and Mg2+ Task 4.4o.2 Discuss the relative lattice enthalpies of the following compounds, NaCl, NaI, LiF, NH4I, NH4SO4, 4.4(p) use entropy and enthalpy of solution values to predict the solubility of ionic compounds. 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NH4Cl(s) + aq ( NH4+(aq) + Cl-(aq) Sosystem = Soproducts -Soreactants = So NH4+(aq) + So Cl-(aq) - So NH4Cl(s) = +113Jmol-1K-1 + 56.5 Jmol-1K-1 - (+94.6 Jmol-1K-1 ) = +74.9 Jmol-1K-1 Ssurroundings =- H/T = - (+16.3kJmol-1)/298K = -54.7 Jmol-1K-1 Stotal = Ssystem + Ssurroundings = +74.9 Jmol-1K-1 + (-54.7 Jmol-1K-1) = +20.2 Jmol-1K-1 Stotal is positive so ammonium chloride is soluble in water Task 4.4p Comment on the solubility of magnesium sulfate and copper sulfate given the following data. Enthapy of solution MgSO4 = -84.8kJmol-1, CuSO4 = -50kJmol-1, Molar entropy Cu2+(aq) = -99.6Jmol-1K-1, MgSO4= 91.6Jmol-1K-1, Mg2+(aq) =-138.1 Jmol-1K-1, SO42- (aq) = +20.1Jmol-1K-1. 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