TITLE: DETERMINE AN EQUILIBRIUM CONSTANT INTRODUCTION

Equilibrium state occurs when the rate of forward reaction is same with the rate of backward reaction. Besides, at equilibrium condition the concentration of reactant and product are same. Equilibrium constant can be determined by using the formula where ratio of product concentration divided to the ratio of reactant concentration. Besides, equilibrium constant is also known as law of the action of mass. For this experiment, the reaction between ethanoic acid and ethanol are used to produce ethyl ethanoate in order to determine the state of equilibrium. The reactants used in this experiment are ethanoic acid and ethanol while the products formed are water and an ester which is ethyl ethanoate. Ethyl ethanoate is a solvent widely used in industry and was produced by the esterification reaction. Esterification reaction that involves organic catalyst is comparatively slow reaction as it involves the breaking of strong covalent bonds and the number of effective collision is low. Therefore, for reversible equation to occur in shorter period of time, a catalyst should be used. Catalyst is a substance that increases the rate of reaction and provide alternative pathway with lower activation of energy. In the process of manufacturing ethyl ethanoate Hydrochloric acid has been used to speed up the rate of forward and backward reaction. Thus, allow the reaction to occur in fast and short period of time without causing any effect on the Kc value or the position of equilibrium as it only affects the rate of reaction. Equilibrium constant also shows how the reaction will continue to react at a particular given temperature. When value of Kc is greater than 1, it indicates that the products will exceed the reactants at equilibrium constant state and the reaction had completed. However, the reactants will exceed the product when the Kc is less than 1 and when Kc value is too less than 1 there will be high probability that the reaction might not happen. Concentrations of solutes in the solution of this experiment are expressed in terms of molarity, M. Molarity is defined as number of moles is dissolved in one litre of solution. Based on the Le Chatelier's Principle, in dynamic equilibrium the change of pressure, concentration of reactants and product and presence of catalyst will not affect the value of Kc. When the pressure or concentration of reactants and products were altered there will only be changed in position of equilibrium. This means that the equilibrium position may be shifting to the left or the right. Therefore, the equilibrium constant is only changed when the temperature is change. Example of equilibrium constant can be shown in the following reaction aA + bB ->c C + dD where a, b, c and d are to represent coefficients and A, B, C and D represent reactants and products. Meanwhile the expression for the equilibrium constant in this experiment is as follows: Kc = [CH3COOC2H5 ] [H2O] [CH3COOH] [C2H5OH]

HYPOTHESIS
The equilibrium constant value of the reaction between ethanoic acid and ethanol to produce ethyl ethanoate and water with the help of catalyst is approximately 4.00.

VARIABLES
Independent Variable : Concentration of reactants and products. Dependant Variable : Value of equilibrium constant. Fixed Variable . : Concentration of Hydrochloric acid (HCl)

OBJECTIVES
1. To determine the equilibrium constant between the reaction CH3COOH+C2H5OH CH3COOC2H5 +H2O 2. To use the skills that has been developed by doing volumetric analysis to determine the equilibrium constant. 3. To deduce an expression for equilibrium constant ,KC . 4. To calculate the value for Kc from concentration of substances at equilibrium from the experiment. 5. To able to draw up a table from the results of the calculations of equilibrium constant. 6. To develop the skill of titration techniques through the titration between NaOH and HCl. 7. To be aware of the importance in the uses of control in the experiment.

MATERIAL AND APPARATUS

Glacial ethanoic acid (CH3COOH), water, hydrochloric acid (HCl), sodium hydroxide solution (NaOH), phenolphthalein, ethyl ethanoate (CH3COOC2H5), ethanol (C2H5COOH), deionised water, boiling tubes with stoppers, pipette, pipette filler, volumetric flasks, conical flasks, bucket, burette, measuring cylinder, dropper, retort stand and clamp.

PROCEDURE
Five different boiling tubes were set up with different concentration of various reactants and products. The volumes of the reactants were added based on the table shown below. Glacial ethanoic acid was used in this experiment. The boiling tubes were closed with the stopper, labelled (A, B, C, D and E) and left for a week. Then, the boiling tubes were immersed in a bucket of water. The boiling tubes was kept in reasonably constant temperature to allow the equilibrium to be achieved. After a week past, boiling tube A was taken out from the bucket of water. The entire content of boiling tube A was poured into a 100.0 cm3 volumetric flask and was made up into 100.0 cm3 by adding deionised water into the flask. The boiling tube was washed twice with a little of deionised water. Then, the washing was transferred again into the volumetric flask and was labelled as flask A.

After that, the entire content of volumetric flask A is poured into a 250cm3 conical flask. The volumetric flask was rinsed twice with a little deionised water and the washings were transferred into a conical flask. Phenolphthalein indicator was added. The solution in the conical flask was titrated with Sodium Hydroxide solution. The titration was done by adding 0.5cm3 of NaOH solution at a time until the indicator changes its colour. Then, boiling tube B was taken out from the water bucket. The reaction in the boiling tubes needed to be quenched after being left for a week in order to prevent the position of equilibrium of the solution to change. This can be done by diluting the solution and adding water into the boiling tube. By this way, catalytic effect of the hydrochloric acid in the solution could be stopped. 10.0 cm 3 of the solution was taken out from boiling tube B by using a pipette and pipette filler into a conical flask. Furthermore, in the flask, the solution was made up until 100 cm3 by using deionised water. The pipette was washed once with a little of deionised water and twice with a slight volume of liquid in the boiling tube. The flask was labelled as flask B to correspond to the original boiling tube. Next, the solution in volumetric flasks B was withdrawn using a clean pipette and pipette. The liquid was then transferred into a conical flask and two or three drop of phenolphthalein indicator was added. By filling up a burette with 0.1moldm-3 Sodium Hydroxide solution, the solution in the boiling tube was titrated. Rough titration was done followed by two accurate readings that agree within 0.1cm3. All the experiment that was using for boiling tube B was then repeated by using boiling tubes C, D and E.

Volume of Liquid (cm3) Boiling Tubes Hydrochloric Acid, HCl (1mol dm-3) Glacial Ethanoic Acid CH3COOH Ethanol C2H5COOH Ethyl Ethanoate CH3COOC2H5 0 6 6 6 0 H2O

A (control) 2 0 0 B 2 6 6 C 2 0 6 D 2 6 0 E 2 6 6 Table 1. Volume of the Solutions in Boiling Tubes A, B, C, D and E

18 0 6 6 6

Retort stand with clamp

Burette containing 0.1M Sodium Hydroxide solution (NaOH)

Conical flask containing mixture of glacial ethanoic acid (CH3COOH), ethanol (C2H5OH), ethyl ethanoate (CH3COOC2H5) and water

Figure 1. The titration of the mixture of glacial ethanoic acid (CH3COOH), ethanol (C2H5OH), ethyl ethanoate (CH3COOC2H5) and water by 0.1M of Sodium Hydroxide solution (NaOH)

RESULT

Volume of NaOH Solution in cm3 (0.1 M ) Boiling Tubes 1st reading 18.50 37.20 17.00 15.00 D 3.70 (2M NaOH solution) 38.80 14.50 15.50 2nd reading 37.10 3rd reading Average 18.50 37.15

A B C

38.70

38.60

3.70 38.60

Table 2. Volume of 0.1M Sodium Hydroxide solution (NaOH) needed to neutralise the acid in boiling tubes A, B, C, D and E. The average volume of 0.1M Sodium Hydroxide, NaOH solution that can neutralise the ethanoic acid and hydrochloric acid in boiling tube A is 18.5cm3. While, the average volume of of Sodium Hydroxide, NaOH solution that can titrate the acids in boiling tube B and C were 37.15 cm3 and 15.50 cm3 respectively. In addition, the average volume of Sodium Hydroxide, NaOH solution needed to neutralise ethanoic acid and hydrochloric acid in boiling tube D and E were 3.70 cm3. Based on the result, the boiling tube E used 38.6 cm3 of 0.1M Sodium Hydroxide solution to change the colourless phenolphthalein indicator into light pink in colour.

DISCUSSION
Stage 1 Number of Moles of Each Solution (mol) Boiling Tubes A (control) B C D E Glacial Ethanoic Acid (CH3COOH) 0 0.1050 0 0.1050 0.1050 Ethanol (C2H5OH) 0 0.1030 0.1030 0 0.1030 Ethyl Ethanoate (CH3COOC2H5) 0 0.0627 0.0627 0.0627 0 Water (H2O) 1.0000 0 0.3333 0.3333 0.3333

Table 3. Number of Moles of the Solutions in Each Boiling Tubes.

Glacial Ethanoic Acid (CH3COOH) Mass = volume density Mass CH3COOH = 6.0 cm3 1.05 gcm-3 =6.3g Molar Mass CH3COOH= 2(12) + 3(1) + 12 + 2(16) + 1 = 60 gmol-1 Mole = mass molar mass Mole CH3COOH = 6.3 g 60gmol-1 = 0.1050 mol

Ethanol (C2H5OH) Mass = volume density Mass C2H5OH = 6.0 cm3 0.79 gcm-3 = 4.74 g Molar C2H5OH = 2(12) + 6(1) + 12 = 46 gmol-1 Mole = mass molar mass Mole C2H5OH = 4.74g 46 gmol-1 = 0.1030 mol

Ethyl Ethanoate (CH3COOC2H5) Mass = volume density Mass CH3COOC2H5 = 6.0 cm3 0.92 gcm-3 =5.52g Molar Mass CH3COOC2H5 = 12 + 3(1) + 12 + 2(16) + 2(12) + 5(1) = 88gmol-1 Mole = mass molar mass Mole CH3COOC2H5 = 5.52 g 88 gmol-1 = 0.0627 mol

Water (H2O) For boiling tube A Mass = volume density Mass H2O = 18.0 cm3 1 gcm-3 =18g Molar Mass H2O= 2(1) + 16 = 18gmol-1 Mole =mass molar mass Mole H2O = 18.0 g 18.0 gmol-1 = 1.0000 mol For boiling tubes C, D and E Mass = volume density Mass H2O =6.0 cm3 1 gcm-3 =6.0 g Molar Mass H2O = 2(1) + 16 = 18 gmol-1 Mole = mass molar mass Mole H2O =6.0 g 18.0 gmol-1 =0.3333 mol

Stage 2 HCl 2ml = 2cm3 = (21000) dm3 = 0.002 dm3 Mole = Molarity volume Mole HCl = 1M 0.002 dm3 = 0.002mol NaOH HCl : NaOH V1M1 = V2M2 2ml 1M = V NaOH 0.1M V NaOH expected to add = 20 ml

Stage 3

Boling Tubes Number of Moles of H+ (aq) Present (mol)

B 0.003715

C 0.00155 0.0310 0.0290

D 0.0074 0.1480 0.1460

E 0.00387 0.0774 0.7540

Number of Moles of H+ (aq) Present in Each Original Equilibrium Mixture (mol) Number of Moles of H+ (aq) in Ethanoic Acid (CH3COOH) In Equilibrium (mol)

0.0743 0.0723

Table 4. Number of Moles of H+ present in the Sample, Original Mixture and Ethanoic Acid in Equilibrium of Boiling Tubes B, C, D and E

(a) The number of moles of H+ (aq) present: (B) 37.15 mL = 37.15 cm3 = 0.03715 dm3 0.1 M = mole / 0.03715 dm3 Mole OH- = 0.003715 mol From the equation, H+ : OH1 : 1 0.003715 : 0.003715 Mole H+ = 0.003715 mol (C) (17+15+14.5)/3 mL = 15.5mL = 15.5 cm3 = 0.0155 dm3 0.1 M = mole / 0.0155 dm3 Mole OH- = 0.00155 mol From the equation, H+ : OH1 : 1 0.00155 : 0.00155 Mole H+ = 0.00155 mol (D) 3.7 mL = 3.7 cm3 = 0.0037 dm3 2 M = mole / 0.0037 dm3 Mole OH- = 0.0074 mol From the equation, H+ : 1 : 0.0074 : Mole H+ = 0.0074 mol

OH1 0.0074

(E) (38.8+38.7+38.6)/3 mL = 38.7 cm3 = 0.0387 dm3 0.1 M = mole / 0.0387 dm3 Mole OH- = 0.00387 mol From the equation, H+ : OH1 : 1 0.00387 : 0.00387 Mole H+ = 0.00387 mol

(b) The number of moles H+ (aq) in each original equilibrium mixture. (B) 0.003715 mol 20 = 0.0743 mol (C) 0.001550 mol 20 = 0.0310 mol (D) 0.007400 mol 20 = 0.1480 mol (E) 0.003870 mol 20 = 0.0774 mol (c) The number of moles of ethanoic acid (CH3COOH) in equilibrium. (B) 0.0743 mol 0.002 mol = 0.0723 mol (C) 0.0310 mol 0.002 mol = 0.0290 mol (D) 0.1480 mol 0.002 mol = 0.1460 mol (E) 0.0774 mol 0.002 mol = 0.7540 mol

Stage 4

Boiling tube B Number of moles reacted = 0.0327 mol Glacial Ethanoic Ethanol Acid (C2H5OH) (CH3COOH) Moles at start 0.1050 0.1030 (mol) Moles at 0.0723 0.1030 - 0.0327 Equilibrium = 0.0703 (mol) Concentration at 0.0723 0.02 0.0703 0.02 Equilibrium = 3.6150 = 3.5150 (mol dm-3)

Ethyl Ethanoate (CH3COOC2H5) 0.0627 0.0627 + 0.0327 = 0.0954 0.0954 0.02 = 4.7700

Water (H2O) 0 0 + 0.0327 = 0.0327 0.0327 0.02 = 1.6350

Boiling tube C Number of moles reacted = 0.0290 mol Glacial Ethanoic Ethanol Acid (C2H5OH) (CH3COOH) Moles at start 0 0.1030 (mol) Moles at 0.0290 0.1030 + 0.0290 Equilibrium = 0.1320 (mol) Concentration at 0.0290 0.02 0.1320 0.02 Equilibrium = 1.4500 = 6.6000 (mol dm-3)

Ethyl Ethanoate (CH3COOC2H5) 0.0627 0.0627 0.0290 = 0.0337 0.0337 0.02 = 1.6850

Water (H2O) 0.3333 0.3333 - 0.0290 = 0.3043 0.3043 0.02 = 15.2150

Boiling tube D Number of moles reacted = 0.0410 mol Glacial Ethanoic Ethanol Acid (C2H5OH) (CH3COOH) Moles at start 0.1050 0 (mol) Moles at 0.1460 0 + 0.0410 Equilibrium = 0.0410 (mol) Concentration at 0.1460 0.02 0.0410 0.02 Equilibrium = 7.3000 = 2.0500 -3 (mol dm )

Ethyl Ethanoate (CH3COOC2H5) 0.0627 0.0627 - 0.0410 = 0.0217 0.0217 0.02 = 1.0850

Water (H2O) 0.3333 0.3333 - 0.0410 = 0.2923 0.2923 0.02 = 14.6150

Boiling tube E Number of moles reacted = 0.0296 mol Glacial Ethanoic Ethanol Acid (C2H5OH) (CH3COOH) Moles at start 0.1050 0.1030 (mol) Moles at 0.0754 0.1030 - 0.0296 Equilibrium = 0.0734 (mol) Concentration at 0.0754 0.02 0.0734 0.02 Equilibrium = 3.7700 = 3.6700 (mol dm-3)

Ethyl Ethanoate (CH3COOC2H5) 0 0 + 0.0296 = 0.0296 0.0296 0.02 = 1.4800

Water (H2O) 0.3333 0.3333 + 0.0296 = 0.3629 0.3629 0.02 = 18.1450

Stage 5 KC = [CH3COOC2H5] [H2O] [CH3COOH] [C2H5OH] Percentage error =

Boiling Tubes B
Equilibrium Constant = 0.6138 Percentage Error (%) = 84.66 = 33.03 = 73.51 = 2.6789 = 1.0596 = 1.9409

Average 1.5733

100%

100%

60.72

= 51.48

Table 5. Equilibrium Constant and Percentage Error in Boiling Tubes B, C, D and E

The percentage error of this experiment was high might be because of the large concentration of Sodium Hydroxide solution used in the experiment which was 0.1M. Sodium Hydroxide solution is a strong base and it was used in the experiment to titrate ethanoic acid which was a weak acid. This was why 0.1M of Sodium Hydroxide solution can be considered a high concentration of alkali. In order to reduce the percentage error and get a more accurate result (Kc value is closer to 4.0), a larger quantity and more dilute Sodium Hydroxide solution should be used as it can gave more precise number of moles of H+ present in the solution.

Besides that, ethanoic acid is a weak acid and only ionise partially in water. This means that the amount of ethanoic acid which was ionised into H+ ions and CH3COOH- ions is lesser than the amount of undissociated ethanoic acid. The undissociated ethanoic acid will not react with ethanol to form ethyl ethanoate and water due to the bonds was not being broken down. Since only the ionised H+ ions and CH3COOH- ions can react with ethanol, lesser products were formed and this was totally different from the predicted amount. This inaccurate concentration of product formed would cause the equilibrium constant value (Kc) to be deviated from the calculated theoretical value. Moreover, after subtracting the amount of hydrochloric acid which was the catalyst in Stage 3, the volume of Sodium Hydroxide that was used to neutralise the solution was small. This had contributed in smaller quantity of ethanoic acid in the solution compared to the theoretical value expected. This might be due to Sodium Hydroxide that acts as a strong alkali, while ethanoic acid as a weak acid that do not fully ionise. Therefore, the concentration of ethanoic acid calculated from the experiment is lower than the real concentration of the acid, causing the equlibrium constant (Kc) value to be further from 4.00. In this experiment, a very small concentration up to 3 or 4 decimal places of acid and base were used. The technique of titration which used the concept of controlling the precise quantity of fluid released from burette into a container containing the reactants; might not be accurate enough to measure the concentration of Sodium Hydroxide solution used to neutralise ethanoic acid. This is because the burette consists of large tube bore and that do not gave a very accurate volume of Sodium Hydroxide, which should be titrated up to the volume that have 3 or 4 decimal places. Therefore, a more accurate technique such as using 1 ml measuring cylinder with volumetric pipette can gave a more accurate volume of Sodium Hydroxide. In addition, the standard equilibrium constant is calculated based on an experiment which was held in a standard condition, where the temperature is 25C (298K). While, in the laboratory where the experiment was held, the room temperature might be different from the standard one as there was air-conditioning. This can be related to Le Chatelier's principle of equilibrium dynamics which said that different in temperature can bring a shift in the calculated equilibrium constant. The temperature in the laboratory could be slightly less than 25C and brought to more exothermic reaction occurred due to more products formed. Besides, phenolphthalein indicator which had been used to identify whether the solutions in the boiling tubes had completely undergo neutralisation; has a transition pH from 8 until 9.6. This can change the amount of Sodium Hydroxide solution used to titrate the acids, as neutral has a pH of 7 and it cannot be detected by the indicator. The real end point of the complete reaction cannot be indicated although such a small amount of Sodium Hydroxide had to be added into the mixture in the boiling tube. This can fully change the calculated the equilibrium constant for the experiment and higher the percentage error of the experiment. Therefore, an indicator with transition pH closer to value of 7 can be used to improve the result.

The reason why the experimental amount of Sodium Hydroxide solution used to titrate the solution in boiling tube A is different from the theoretical value calculated in Stage 2 might be because of the method of adding 0.5 cm3 of Sodium Hydroxide solution into the conical flask at one time during titration. This can cause an exceeding amount of the solution in the flask as the actual amount of Sodium Hydroxide solution might be slightly more or less than the obtained amount. In order to prevent this, a lower volume of Sodium Hydroxide solution should be added at time until the end point was reached to get a more accurate volume of the solution used. The percentage error also might be high due to misread of the calibration on the burette which brought to parallax error. This can bring to inaccuracy in the measurement of Sodium Hydroxide solution needed for titration and lead to miscalculating the H+ ions present in the solution. Besides, not all the experiments were repeated at least three times for each of the boiling tubes. So, the consistency of the result was not measured and the average value was not calculated. Therefore, a less accurate equilibrium constant might be obtained. During the experiment, safety glasses were worn so that the eyes can be protected from harmful gases. Also, gloves were worn so that hands can be protected if the hands accidentally touched the corrosive glacial ethanoic acid and hydrochloric acid. The boiling tube which was filled with solutions was shaken gently when titration was held in order for the solution to wholly react with Sodium Hydroxide solution. In the process of transferring the solution in boiling tube A into the volumetric flask, the tube was washed with deionised water twice, to make sure that all the solution had been transferred to the flask.

CONCLUSION
In conclusion, the average equilibrium constant between the reaction CH3COOH+C2H5OH CH3COOC2H5 +H2O was 1.5733 and the average percentage error in this experiment was 60.72 %. Also, the skills that have been developed when doing volumetric analysis was well applied in handling the experiment to determine the equilibrium constant, Kc . From this experiment, the expression of equilibrium constant of the reaction means that the ratio of concentration of products to the concentration of reactants when they reached equilibrium ( Kc=
[ [ ] [ ] [ ] ]

) is 1.5733. Moreover, based on the results

obtained, the concentration of ethanoic acid, ethanol, ethyl ethanoate and water at equilibrium were able to be calculated; thus, the value of Kc of this reaction can also be calculated. At the end of the experiment, a table of the calculations of the equilibrium constant can be drawn. Furthermore, boiling tube A act as a control in this experiment to show that the concentration of hydrochloric acid is maintained in the experiment. The hypothesis of this experiment is not supported. This is because of the high percentage error and the calculated equilibrium constant is not close to 4.00. .

APPENDICES
CH3COOH(l) ethanoic acid + C2H5OH(l) ethanol CH3COOC2H5(l) ethyl ethanoate + H2O(l) water

Figure A. Complete equilibrium equation of the reaction between ethanoic acid and ethanol to produce ethyl ethanoate and water

CH3COOH Density/ g cm
-3

C2H5OH 0.79

CH3COOC2H5 0.92

H2O 1.0

1.05

Table A. Density of glacial ethanoic acid, ethanol, ethyl ethanoate and H2O

moles at start moles at equilibrium

CH3COOH 0.105

C2H5OH 0.103

CH3COOC2H5 0.0627 0.0627 + (0.105 x)

H2O 0 0 + (0.105 x)

0.103 (0.105 x)

Figure B. Formula to find the moles at equilibrium of hydrochloric acid, glacial ethanoic acid, ethanol, ethyl ethanoate and H2O

REFERENCE
1. Clark, J. (2002). Equilibrium Constants: Kc. Retrieved November 30 from http://www.chemguide.co.uk/physical/equilibria/kc.html. 2. Slowwinski, E. (2006). Chemical Principles in the Laboratory. United States of America. Icc Mc Millan Inc. Retrieved November 30 from http://books.google.com.my/books?id=RaLpDwmEpF0C&printsec=frontcover#v=onepag e&q&f=false 3. Moore, J.W. (2010). Principle of Chemistry: The Molecular Science. United States of America. Mary Finch. Retrieved from http://books.google.com.my/books?id=ZOm8L9oCwLMC&printsec=frontcover#v=onepag e&q&f=true. 4. The Determination of an Equilibrium Constant. (2012). Retrieved November 30 from http://www.123HelpMe.com/view.asp?id=122075.html.