F325 Equilibria How Far ?

- The Equilibrium Constant, Kc

Equilibrium calculate, given appropriate data, the concentration or quantities present at equilibrium deduce, for homogeneous reactions, expressions for the equilibrium constant Kc calculate the values of the equilibrium constant Kc including determination of units explain the effect of changing temperature on the value of Kc for exothermic and endothermic reactions state that the value of Kc is unaffected by changes in concentration or pressure or by the presence of a catalyst You will not be required to solve quadratic equations.

In chemistry we encounter reversible reactions which can establish a dynamic equilibrium a state of constant change, with the observable properties remaining constant. Features of a dynamic equilibrium, which can only be established in a closed system (nothing added or removed): - rates of forward and reverse reactions are the same (and non-zero !) - can be achieved from either direction - concentrations of reactants and products remain constant e.g. H2(g) + I2(g) 2HI(g)

It doesn't matter whether we start by mixing H2 and I2, or whether we start with a container of HI. When equilibrium has been reached, the contents of the reaction vessel will be identical. The mixture won't necessarily contain 50% H2 and I2 and 50% HI. The relative amounts will depend on the reaction conditions. We use the idea of the position of equilibrium: if we have more H2 and I2 then the position of equilibrium lies to the left, and if we have more HI the position of equilibrium lies to the right. We know that the position of equilibrium changes in response to changes in temperature, concentrations etc. What we need is a quantitative approach so we know HOW MUCH of the reactants and products there are at equilibrium. Kc is called the equilibrium constant, and tells us the relative concentrations of reactants and products at equilibrium. If Kc > 1010 we say the reaction has gone to completion (and we would show this with a single arrow, not reversible) If Kc < 10-10 we say that the reaction doesn't happen.

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F325 Equilibria The equilibrium law tells us how Kc is calculated: for a reaction then Kc = aA + bB cC + dD [C]c[D]d [A]a[B]b where [C] = equilibrium conc. of C etc.

This means that the value of Kc can be worked out - so long as we work with concentrations AT EQUILIBRIUM - so long as the temperature doesn't change (because Kc changes with temp) Examples: We may be asked to write expressions for Kc given a balanced equation to work from: H2(g) + I2(g) 2HI(g) 2NO2(g) N2O4(g) Kc = [HI]2 [H2][I2] Kc = [N2O4] [NO2]2

Kc has units which depend on the equilibrium law expression. We can find the units of Kc by substituting the units of concentration (mol dm-3) and cancelling top and bottom. e.g. Kc = [N2O4] [NO2]2 Units: mol dm-3 _ -3 -3 mol dm x mol dm = dm3 mol-1

[Note: the convention is to put positive indices first] Kc = [HI]2[H2][I2] Units: mol dm-3 x mol dm-3 mol dm-3 x mol dm-3

In some cases all the units cancel in this case Kc has no units, its just a number. Practice: 1) Write the Kc expressions and give the units of Kc for the following reactions: a) N2 + 3H2 2NH3 b) c) d) 2NO + O2 2NO2 N2O4 2NO2 CH3COOH + CH3OH CH3COOCH3 + H2O

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F325 Equilibria Working with Kc - examples General hint: Use the same number of significant figures in your answer as are given in the question. Working out Kc when given concentrations at equilibrium This is just a case of plugging the values into the Kc expression. e.g. CH3COOC2H5 + H2O CH3COOH + C2H5OH Equilibrium conc. / mol dm-3 ethyl ethanoate water ethanoic acid ethanol = 4.33 x 4.33 15.4 x 5.27 15.4 5.27 4.33 4.33 = 0.231 no units

[CH3COOH][C2H5OH] [CH3COOC2H5][H2O]

Practice: 2) In a closed system, N2, H2 and NH3 exist in an equilibrium: N2 + 3H2 2NH3 The equilibrium concentrations are [N2] 1.20 mol dm-3, [H2] 2.00 mol dm-3, and [NH3] 0.876 mol dm-3. Calculate the value of Kc under these conditions. Working out Kc when given amounts (moles) rather than concentrations The method is the same as above, but we have to work out the concentrations before plugging into the Kc expression: e.g. "At equilibrium 0.40 moles of N2O4 and 3.2 moles of NO2 were present in a reaction volume of 2dm3. N2O4 2 NO2 Calculate Kc under these conditions:" conc = moles / vol (in dm3): [N2O4] = 0.40/2 = 0.2 mol dm-3 [NO2] = 3.2/2 = 1.6 mol dm-3 Kc = (1.6)2 / 0.2 = 12.8 = 13.0 mol dm-3 (to 2 sf)

BEWARE: in situations where Kc would have no units, the volumes will cancel top and bottom just like the units did. In such situations the volume may not be specified in the question even though amounts in moles, rather than concentrations are given. If we use 'V' to represent the volume, we can see that it cancels in the Kc expression: e.g. "The equilibrium mixture contained 0.25 moles of ethanol and 0.25 moles of ethanoic acid. 0.61 moles of ethyl ethanoate and 0.44 moles of water remained unreacted."

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F325 Equilibria Convert moles to [] first, [CH3COOH] = 0.25/V mol dm-3 [C2H5OH] = 0.25/V mol dm-3 [CH3COOC2H5] = 0.61/V mol dm-3 [H2O] = 0.44/V mol dm-3 = 0.233

Kc =

0.125 x 0.125 V V__ 0.305 x 0.220 V V

Practice: 3) In an experiment, N2O was heated in a 0.5dm3 container until equilibrium was reached. 2N2O 2N2 + O2 At equilibrium there was found to be 0.1 moles of N2O, 0.9 moles of N2 and 0.45 moles of O2. Calculate Kc. Working out the concentration of a component at equilibrium, given the value of Kc: e.g. "A mixture of SO2 and O2 was allowed to come to equilibrium 2SO2 + O2 2SO3 At equilibrium the concentrations of SO2 and O2 were 0.020 mol dm-3 and 0.010 mol dm-3. If the value of Kc is 1.28 x 104 mol-1 dm3, what was the equilibrium concentration of SO3?" Kc = [SO3]2 [SO2]2[O2] so [SO3] = (Kc [SO2]2[O2]) = 0.0512 = 0.23 mol dm-3

Working out Kc given initial concentrations and one component at equilibrium You may be given initial concentrations and enough information to work out the concentrations remaining at equilibrium. The key is to remember that the mole ratios from the balanced equation tell you how many moles of each product are made for every mole of reactant used. e.g. "1.5 mol of ethanol is mixed with 1.0 mol of ethanoic acid in a solution with volume 1dm3. C2H5OH + CH3COOH CH3COOC2H5 + H2O. At equilibrium it is found by titration that 0.33 moles of ethanoic acid remained. Calculate Kc" A table format helps to organise the necessary information. Start by writing down the initial moles, from the question (including the fact that there were no products there at the start this may not always be the case!) Then write down the one amount at equilibrium that you know. By subtraction, if you know the moles of this substance you started with, and the moles present at equilibrium, you can work out how much has been used/made. I've shown this value in blue below. Now use the mole ratios from the balanced equation to write down how many moles of each other substance will have been used or made (in this case the mole ratio is 1:1:1:1 so 0.67 moles of everything reacts or is made (red values). Finally work out how much of everything else is there at equilibrium. Subtract the amounts of reactants used from the initial amounts, and add the amounts of products made to the initial amounts. These values are in green.

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F325 Equilibria ethanol ethanoic acid ethyl ethanoate water Initial moles 1.5 1.0 0.0 0.0 Used/Made 0.67 0.67 0.67 0.67 Moles at Eqm 0.83 0.33 0.67 0.67 Now we have all the moles at equilibrium we can convert the equilibrium moles to concentrations and calculate Kc. (we don't need to here because the volumes will cancel Kc has no units). Kc = 0.67 x 0.67 / 0.83 x 0.33 = 1.6 (to 2 sf).

Practice: 4) "1.00 moles of HI is allowed to dissociate in a 0.5dm3 vessel at 440C. At equilibrium only 0.78 moles of HI remained. Calculate Kc." And finally, we may get all sorts of attempts to complicate matters below is a kind of synoptic question (drawing together various different parts of your knowledge). Practice: 5) Consider the reaction PCl5 PCl3 + Cl2 Kc = 1.9 mol dm-3 A sample of PCl5 is heated in a 2.0 dm3 container until equilibrium is established. The mixture is found to contain 4.170g of PCl5. i) Calculate the concentration in g dm-3 of Cl2 present in the equilibrium mixture. ii) Calculate the mass of the original sample of PCl5 What affects the value of Kc ? Kc IS affected by changes in temperature Kc is NOT affected by changes in pressure, concentration, or presence of a catalyst but that doesn't mean the position of equilibrium can't shift !! Effect of temperature on Kc We know the effect a change in temperature has on the position of equilibrium because we learned LeChatelier's principle at AS, and we used the sign of H to predict how the position of equilibrium would change. For a reaction which is exothermic in the forward direction i.e. H is ve. increasing temperature moves the PoE in the endothermic (backward) direction which means the [reactants] increases and the [products] decrease so Kc decreases For a reaction which is endothermic i.e. H is +ve increasing temperature moves the PoE in the forward direction which means the [reactants] decreases and [products] increases # so Kc increases We should be able to look at a change in Kc with temperature and decide if the forward reaction is endothermic or exothermic: p.5

F325 Equilibria

e.g. "When the temperature was increased from 500K to 800K the value of Kc decreased from 5000 to 0.3 Give the sign of H for the forward reaction." Ans: Decreasing Kc with increasing temperature shows the PoE is shifting to the reactants/left. This must therefore be the endothermic direction. The forward reaction is exothermic, so H is ve. Practice: 6) When the temperature of a system at equilibrium was increased from 500K to 800K the value of Kc changed from 4.5x10-2 to 2.8x103. Explain how you can tell that the forward reaction is endothermic. Effect of concentration on Kc We have already stated that changing the concentration or pressure of a reactant or product has no effect on the value of Kc. If we change the concentration of a reactant or product, the concentrations of the other reactants or products must change to keep the value of Kc constant. This results in a change in the position of equilibrium (even though Kc has not changed its value). e.g. N2O4 2NO2 equilibrium concentrations are 1.60 mol dm-3 of NO2 0.200 mol dm-3 of N2O4

We can show that Kc = (1.6)2/0.2 = 12.8 mol dm-3 What happens if we double the concentration of N2O4 to 0.400 mol dm-3? i) we no longer have an equilibrium the closed system has been disturbed ii) the system will proceed to establish a new equilibrium Kc remains the same, but increasing [N2O4] makes the position of equilibrium move to the right to use some of this up, making more NO2, in accordance with LeChatelier's principle. A new equilibrium is established. We know the value of Kc and we know the new concentration of N2O4, so we can work out the new [NO2]: Kc = [NO2]2/[N2O4] so 12.8 = [NO2]2 / 0.400 => [NO2] = (12.8 x 0.400) = 2.26 mol dm-3 Changes in pressure: Le Chatelier's principle tells us that if we increase the pressure, the position of equilibrium will shift in the direction of fewer moles of gas in order to minimise the effect of the change. For the example above, N2O4(g) 2NO2(g) , we can predict that increasing the pressure will shift the position of equilibrium to the left (backward direction) making more N2O4. p.6

F325 Equilibria We have stated that the value of Kc is NOT affected by a change in pressure. If the pressure is doubled, then the concentrations of both NO2 and N2O4 will have doubled (same number of moles of either in half the volume). So [NO2]2/[N2O4] becomes (2 x 1.6)2 / 2 x 0.2 = 25.6 mol dm-3

Since Kc is 12.8 mol dm-3, not 25.6 mol dm-3, the some of the NO2 has to turn into N2O4, reducing the value of [NO2]2/[N2O4] back to 12.8. The position of equilibrium is shifting to the left (which is in accordance with LeChatelier's principle). Effect of presence of a catalyst on Kc A catalyst has no effect on the value of Kc. Catalysts speed up the forward and backward reactions equally, so the position of equilibrium remains unchanged we just reach equilibrium more quickly. There is no change in position of equilibrium, or concentrations of reactants or products.

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F325 Equilibria Answers to Practice Questions 1) a) b) c) d) N2 + 3H2 2NH3 2NO + O2 2NO2 N2O4 2NO2 Kc = [NH3]2 [N2][H2]3 Units: dm6 mol-2

Kc = [NO2]2 Units: dm3 mol-1 [NO]2[O2] Kc = [NO2]2 [N2O4] Units: mol dm-3

CH3COOH + CH3OH CH3COOCH3 + H2O Kc = [CH3COOCH3][H2O] Units: none [CH3COOH][CH3OH] = (0.876)2 / (1.20 x 2.003) = 0.767 / 9.6

2) 3)

Kc = [NH3]2 / [N2][H2]3

= 7.99 x 10-2 dm6 mol-2

[N2O] = 0.1/0.5 = 0.20 mol dm-3 [N2] = 0.9/0.5 = 1.8 mol dm-3 [O2] = 0.45/0.5 = 0.90 mol dm-3 (1.8)2 x 0.90 / (0.20)2 H2 0 0.11* 0.11 = 3.24 x 0.90 / 0.04 = 72.9 mol dm-3 I2 0 0.11* 0.11

Kc = [N2]2[O2] / [N2O]2 = 4) Initial moles Used/made Eqm moles HI 1.00 0.22 0.78

*0.22 moles of HI have been used. The equation shows us that 0.22 moles of HI make 0.11 moles of H2 and 0.11 moles of I2. We'd now convert moles to concentration, but the volumes cancel in this example (Kc has no units). Kc = (0.11 x 0.11) / 0.782 = 0.020 5) Kc = [PCl3][Cl2] / [PCl5]

i) Mass of PCl5 = 4.170 and Mr of PCl5 = 208.5 moles PCl5 = 0.02 Concentration of PCl5 = 0.02 moles in 2dm3 = 0.01 mol dm-3 Since every mole of PCl5 which decomposes produces 1 mole of PCl3 and 1 mole of Cl2, and since there is no Cl2 or PCl3 present initially, [Cl2] = [PCl3] at equilibrium. Therefore Kc x [PCl5] = [Cl2]2 [Cl2] = (1.9 x 0.01) = 0.1378 mol dm-3 So concentration of Cl2 in g dm-3 = 0.1378 x 71 = 9.78 g dm-3 p.8

F325 Equilibria ii) Since [Cl2] = [PCl3] and the volume is 2.0dm3 we can state that 0.1378 x 2.0 mol of each is present in the vessel, and we can convert moles of each to mass of each: Converting each to mass: Mass of Cl2 = 0.2756 x 71 = 19.57g Mass of PCl3 = 0.2756 x 137.5 = 37.89g By law of mass conservation, mass of PCl5 which has reacted = 19.57g + 37.89g. To this we need to add the mass of PCl5 which remained unreacted at equilibrium: Original mass of PCl5 = 19.57 + 37.89 + 4.17 = 61.63g (to 4sf.) 6) The value of Kc changed from 4.5x10-2 to 2.8x103, so Kc has increased. This means the concentration of products has increased, and the concentration of reactants has decreased in other words the position of equilibrium has moved in the forward direction. This has happened with an increase in temperature, and Le Chatelier tells us that when temperature is increased, the position of equilibrium shifts in the endothermic direction. Hence the forward direction must be the endothermic direction.

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