Friday, 28 October 2016

Equilibrium (2) Calculations involving Kc and Kp

Edexcel A level Chemistry (2017)
Topic 11: Equilibrium II:
Here is the second learning objective:
11/II/2. To be able to calculate a value, with units where appropriate, for the equilibrium constant (Kc and Kp) for homogeneous and heterogeneous reactions, from experimental data

If you have been following this blog recently with the posts on calculation of Kc and Kp then the following examples should help you develop your understanding of this topic.

Example 1:

5 moles ethanol, 6 moles ethanoic acid, 6 moles ethyl ethanoate and 4 moles of water were mixed together in a stoppered bottle at 15℃.

After equilibrium had been reached the bottle was found to contain only 4 moles of ethanoic acid.

Calculate Kc for this reaction

CH3CH2OH    +    CH3COOH         CH3COOCH2CH3    +   H2O


CH3CH2OH
CH3COOH
CH3COOCH2CH3
H2O
Initial number of moles
5
6
6
4
Change in number of moles
–2
–2
+2
+2
Equilibrium number of moles
3
4
8
6

   

after substitution of the equilibrium values   Kc  =  4

Now suppose that 1 mole of ethanol, 1 mole of ethanoic acid, 3 moles of ethyl ethanoate and 3 moles of water are mixed together in stoppered flask at 15℃.

How many moles of each reagent exist in the bottle at equilibrium given that Kc  =  4.

Consider:


CH3CH2OH
CH3COOH
CH3COOCH2CH3
H2O
Initial number of moles
1
1
3
3
Change in number of moles
+𝝰
+𝝰
𝝰
𝝰
Equilibrium number of moles
1+𝝰
1+𝝰
3–𝝰
3–𝝰
Actual mole values at equilibrium
1.33
1.33
2.67
2.67

where  𝝰 is the degree of dissociation of ethyl ethanoate and water.  Since both these compounds are in the larger concentration the effect will be to push the equilibrium position to the left.  The concentrations of water and ethyl ethanoate will decrease.  Therefore these two species concentrations fall by the degree of dissociation 𝝰 where as the two reactants concentrations increase by the degree of dissociation, according to Le Chatelier’s principle.  






  taking roots






giving a value of   𝝰 =  0.333



Example 2:

At 200℃, Kc for the reaction:

PCl5(g)       PCl3(g)      +     Cl2(g)     ΔH  =  +124kJ

is  8 ×  10–3  mol.dm–3

A sample of pure PCl5(g) was introduced into an evacuated vessel at 200℃.  When the equilibrium had been reached the concentration of PCl5(g) was 0.2 ×  10–1  mol.dm–3

What are the concentrations of PCl3(g) and Cl2(g) at equilibrium?

Equation:  PCl5(g)       PCl3(g)      +     Cl2(g)     ΔH  =  +124kJ

From this we see that [PCl3(g)]  =  [Cl2(g)] because for every mole of Cl2(g) formed a mole of PCl3(g) also forms.

Kc = 8 ×  10–3   =     

At equilibrium [PCl5]  = 0.2 ×  10–1  mol.dm–3 

  [PCl3(g)]  ×  [Cl2(g)]  =  [PCl5(g)]  × 8 ×  10–3   
                                    =    0.2 × 10–1 × 8 ×  10–3   

[PCl3(g)]  =  [Cl2(g)]  =  √0.2 ×  10–1 × 8 ×  10–3   

                                             = 1.265 mol.dm–3 

Example 3:  (More difficult)

This is taken from Chemistry in Context p331.

At 488K the equilibrium constant for the reaction:

COCl2 (g)        CO(g)    +    Cl2(g)

is    2 × 10–6  atm

Assuming that the total pressure at equilibrium is P and the degree of dissociation of COCl2 (g) is 𝜶 , deduce a relationship between Kp,  𝜶 and P.

(Degree of dissociation (𝜶) is the fraction of COCl2(g) dissociated)

Let’s assume we have 1 mole of COCl2(g) initially in the reaction vessel.



After simplifying



The equation can be simplified further and a quadratic solution avoided since when 𝜶 is very small 1– 𝜶 or 1+ 𝜶 approximate to 1.

Therefore  Kp    P𝜶2

So at 1atm pressure P = 1atm

Then 𝜶  =   √Kp   =    2 × 10–6    =   1.414 × 10–3  

which as you can see is very small.

Example 4:

(From Selvaratnam and Frazer: Problem Solving in Chemistry)

Calculate the degree of dissociation when 0.500 mol of phosphorus pentachloride is maintained at 573K and 2.00 × 105 Pa.  The equilibrium constant for this homogenous gas dissociation is 2.3 × 10–3 mol.dm–3 at 573K.

The previous problem provides a template with which to solve this example.



And finally if you have become proficient in calculating Kp, Kc   𝛂  the next question to ask is what does the value mean, what significance does it hold?

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