EXPERIMENT 5 : DETERMINATION OF CHEMICAL EQUILIBRIUM

Introduction

Generally, many chemical reactions happen reversibly where the forward and reverse reactions
might occur simultaneously. Since the rates for forward and reverse reactions are equal, there are no net
changes in the concentrations of the reactant(s) and product(s). This state is known as dynamic
equilibrium. Equilibrium is defined as a state where there will be no changes is observed on the reaction
as time goes by as long as the reaction stay undisturbed. At equilibrium, the ratio of concentration of
products to the concentration of reactants is known as Equilibrium Constant, Kc.

When an external stress is applied to a chemical reaction at equilibrium, the reaction will react
in a way to minimize the effect of the external stress. Several factors may be considered as the external
stress e.g. increasing or decreasing of concentration of reactants or products, change of temperature,
change of pressure and change of volume. These factors will be minimized according to the Principle
of Le Chatelier. In this experiment, the effect of concentration on different chemical systems (solution
equilibria and complex ion equilibria) will be studied.

The second part of the experiment is about the determination of Kc value for the hydrolysis of
ethyl acetate according to the reaction below.

CH3COOCH2CH3 (aq) + H2O (l) ↔ CH3CH2OH (aq) + CH3COOH (aq)

Ethyl Acetate Water Ethanol Acetic Acid
(EtAc) (EtOH) (HAc)

The equilibrium expression for the reaction is written as :

[EtOH] [HAc]
Kc =
[EtAc] [H2O]

In order to calculate the equilibrium constant, Kc for a reaction, it is necessary to know the initial
concentrations of the reactants and products and to be able to determine the equilibrium concentration
of one of the reacting species. By using the concept of ICE table, the changes in the concentrations of
reactants and products could be determined and later will be used to determine their equilibrium
concentrations.

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 Normally the concentration of a pure liquid such as water does not appear in the equilibrium
expression because its concentration does not vary significantly during the course of the reaction.
However, in this experiment water is present in a concentration that does change as the reaction
progresses and therefore must be included in the equilibrium expression.

The hydrolysis of ethyl acetate is usually a very slow reaction. So, a fix amount of hydrochloric
acid is added to the mixture and is used as the catalyst, but it concentration does not appear in the
equilibrium expression.

Objective
a) To study the effects of solubility and complex ion on the equilibrium position and relate with
the Le Chatelier’s Principle.
b) To determine the equilibrium constant, Kc for hydrolysis of ethyl acetate.

Materials
Part A: The effect of solubility and complex ion on equilibrium position
1. Saturated sodium chloride solution
2. 6 M Hydrochloric acid (HCl)
3. 1 M Hydrochloric acid (HCl)
4. Complex ion solution of [FeSCN]2+
5. 0.1 M Ferric chloride (FeCl3)
6. 0.1 M Potassium thiocyanate (KSCN)
7. 0.1 M Silver nitrate (AgNO3)

Part B : Determination of Equilibrium Constant

1. 1 M Sodium hydroxide (NaOH)
2. 3 M Hydrochloric acid (HCl)
3. Ethyl acetate solution
4. Phenolphthalein indicator

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Equipment / Apparatus
Part A: The effect of solubility and complex ion on equilibrium position
1. Test tubes
2. Pipette 5 ml
3. Dropper

Part B : Determination of Equilibrium Constant

1. Erlenmeyer flask 100 ml
2. Burette 50 ml
3. Erlenmeyer flask 50 ml
4. Pipette 5 ml
5. Small beaker
6. Dropper
7. Retort stand and clamps

Procedure
Part A: The effect of solubility and complex ion on equilibrium position
i) Effect of Solubility
1. Obtain two dry test tubes and label as Test tube 1 and Test tube 2.
2. Pipette 5 ml of saturated sodium chloride solution into each of the test tube.
3. Add 3 ml of 6 M HCl into the Test tube 1 and 3 ml of 1 M HCl into the Test tube 2.
4. Let the mixture in both test tubes to stand for 30 minutes while observing the changes.
5. Discard the mixture and record the observation.

ii) Effect of Complex Ion

1. Obtain four dry test tubes and label as A, B, C & D.
2. Pipette 5 ml of complex ion solution of [FeSCN]2+ into each of the test tube.
To be prepared by the Technician:
- Mix 2 ml of 0.1 M FeCl3 solution with 2 ml of 0.1 M KSCN solution. Then dilute the solution
to 100 ml with distilled water in 100 ml volumetric flask.
3. For test tube A : Pipette 1 ml of 0.1 M FeCl3 solution and observe the changes.
4. For test tube B : Pipette 1 ml of 0.1 M KSCN solution and observe the changes.
5. For test tube C : By using a dropper, slowly add 0.1 M AgNO3 solution until no further change
is observed.
6. For test tube D : This tube will act as a control for comparison of color intensity with test tube
A, B & C.
7. Discard the mixture in the test tubes. Record the observation in a proper table.

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Part B : Determination of Equilibrium Constant
i) Preparation of samples (to be prepared by the technician during pre-lab)
1. Prepare three different mixtures of HCI solution, distilled water and ethyl acetate according to
the following combinations.

Reagent Sample 1 Sample 2 Sample 3

3 M HCl solution 5 ml 5 ml 5 ml

Distilled water - 1 ml 2 ml

Ethyl acetate 5 ml 4 ml 3 ml

2. Cap the sample bottles immediately after adding the ethyl acetate and swirl the contents slowly.
Two immiscible layers will remain inside the bottles.

ii) Standardization of 3 M Hydrochloric Acid (HCI)

1. Obtain a dry 50 ml burette and clamp it on a retort stand. Fill the burette with 1 M NaOH
solution.
2. Obtain a clean 100 ml Erlenmeyer flask and pipette exactly 5 ml of 3 M HCl into it. Then add
20 ml of distilled water and 3 drops of phenolphthalein indicator. Swirl carefully to mix the
solution.
3. Titrate the HCI solution with NaOH solution until a persistence pale pink appears. Record the
volume of NaOH solution used.
4. Discard the mixture in the flask.

iii) Titration of samples with 1 M sodium hydroxide (NaOH)

1. Pipette 10 ml of Sample 1 (from Part B(i)) into a clean 100 ml Erlenmeyer flask and add 20 ml
of distilled water.
* the added water will not have a rapid effect on the reaction equilibrium and will not be included in
the calculation.
2. Then put 3 drops of phenolphthalein into the flask and swirl the solution carefully.
3. Titrate the sample in the flask with 1 M NaOH solution until a persistence pale pink appears
(same as the previous steps on the standardization of HCI).
4. Record the volume of NaOH solution used.
5. Repeat the steps 1 – 4 for Sample 2 and Sample 3.

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Observation and Data
1. State your observations when 6 M HCl and 1 M HCl were added into the sodium chloride
solution. Explain how that happened according to the Le Chaterlier’s Principle.
2. State your observations as the following ions were added into the complex ion solution of
[FeSCN]2+. Explain and relate with the Le Chaterlier’s Principle.
a) Addition of Fe3+ ions
b) Addition of SCN‾ ions
c) Addition of Ag+ ions

Calculation (for Part B)

a) Table 1 : Standardization of 3 M Hydrochloric Acid

Volume of NaOH used

No of moles of NaOH used
No of moles of HCl used ------- (a)
Mass of HCl in 5 ml HCl
Total mass of 5 ml HCl
Mass of H2O in 5 ml HCl
No of moles of H2O in 5 ml HCl -------- (b)

b) Table 2 : Titration of Samples

Sample 1 Sample 2 Sample 3

Volume of NaOH used
No of moles of NaOH used
[nNaOH = nAcids (HAc + HCl)]

c) Table 3 : Equilibrium concentration of all reacting species

Sample 1 Sample 2 Sample 3

Initial no of moles of ethyl acetate
(EtAc) used
Initial no of moles of H2O
[ pure + H2O added to HCl -------- (b) ]
Equilibrium no of moles of acids
(HAc + HCl) --------- (c)

Equilibrium no of moles of acetic acid

HAc --------- [ (c) – (a) ]

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 Equilibrium no of moles of ethanol
(EtOH)
Equilibrium no of moles of ethyl acetate
(EtAc)

*Density : HCl = 1.036 g/ml; EtAc = 0.902 g/ml

d) Calculate equilibrium constant, Kc for Sample 1, Sample 2 and Sample 3. Then find the average
of Kc for the hydrolysis of ethyl acetate.

Pre-lab Questions
1. Explain how a chemical system which is at equilibrium will react if additional of reactant or product
is added into the system.
2. Explain the purpose of standardization of HCl solution in this experiment.
3. Discuss the difference between reaction equilibrium constant Kc and reaction quotient Qc.

Post-lab Questions
1. Based on the average value of the Kc from this experiment, does the equilibrium favour the
formation of the ethanol and acetic acid or favour the starting reagents (ethyl acetate and water)?
Justify your answer.

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