Activity 1.

1 An investigation of acidbase indicators

Information and advice
1 This is an excellent opportunity for students to be reminded of how to use a pipette and burette correctly and how to accurately perform an acidbase titration. This activity also provides an opportunity to investigate acidbase indicators, in preparation for their study of volumetric analysis. It will show students how critical the choice of indicator is, since it will greatly affect the experimental value of the titre. It also will enable them to observe which indicators give sharp end points. It is very worthwhile to demonstrate a titration to remind students of the finer points of controlled use of the pipette and burette. Some students may benefit from practising with water first. This activity also can give students an opportunity to become used to technology such as pH probes. A very worthwhile introductory demonstration is to add 20 mL of the 0.1 M NaOH to about 780 mL of water in a 1000 mL beaker, stir, and then add enough universal indicator to make the solution bright purple. Then add a small piece of dry ice. This will result in white fumes and colour changes over several minutes and will have students fascinated with indicators. They can be challenged to suggest an explanation for the pH changes.

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List of chemical solutions to be prepared

Small dropper bottles of each of the following solutions for each group:

0.1 M hydrochloric acid (10 mL concentrated HCl per L of solution) 0.1 M nitric acid (7 mL concentrated HNO3 per L of solution) 0.1 M ethanoic (acetic) acid (6 mL glacial CH3COOH per L of solution) 0.1 M ammonia solution (7 mL 15 M NH3 solution per L of solution) 0.1 M sodium hydroxide solution (4.0 g solid NaOH per L of solution) de-ionised water 0.1 M ammonium chloride solution (5.4 g solid NH4Cl per L of solution) 0.1 M sodium carbonate solution (10.6 g solid anhydrous Na2CO3 per L of solution) 0.1 M sodium ethanoate (sodium acetate) solution (8.2 g solid CH3COONa per L of solution) 0.1 M sodium chloride solution (5.9 g solid NaCl per L of solution) 0.1 M sodium phosphate solution (16 g solid anhydrous Na3PO4 per L of solution)

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Student Activity Manual solutions and information, Chapter 1

Each group should also be provided with: small dropper bottle of one of the indicators listed in Table 1.2, page 3 of the Student Activity Manual* bottle containing 100 mL freshly prepared 0.1 M sodium hydroxide (4.0 g solid NaOH per L of solution) bottle containing 100 mL freshly prepared 0.1 M hydrochloric acid (10 mL concentrated HCl per L of solution) *Note: A range of indicators should be tested across the class. The group(s) testing universal indicator should also be supplied with the matching pH chart.

Expected results
Part A
The colours observed will depend on the indicators supplied (see Table 1.2, page 3 of the Student Activity Manual) and on the actual concentrations of the supplied solutions. But the following approximate pH values should be observed. Solution(s)
0.1 M HCl and 0.1 HNO3 0.1 M CH3COOH 0.1 M NH4Cl De-ionised water and 0.1 M NaCl 0.1 M Na3PO4 0.1 M CH3COONa 0.1 M NH3 and 0.1 M Na2CO3 0.1 M NaOH

Approximate pH
1 3 5 7 8 9 1112 13

Part B
The colour changes observed will depend on the indicators supplied, as in Part A (see Table 1.2, page 3 of the Student Activity Manual). But since the base is being added to the acid, the pH should start at 1 and reach 7 at the equivalence point, which should occur when 20.00 mL of the base has been added if the concentrations of the acid and base are precisely 0.1000 M. The pH should then rise with the addition of more NaOH. Thus those indicators for which the colour change occurs at a pH below 7 will change colour before the equivalence point is reached and will give a lower titre than the true result. Those that change colour at a pH above 7 will give a higher titre than the true result. The higher the pH range over which the indicator changes colour, the greater will be the titre. The students should also find that the indicators commonly used in school laboratoriesmethyl orange and phenolphthaleingive sharp end points.

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Student Activity Manual solutions and information, Chapter 1

Suggested solutions to pre-lab activity: focus questions

1 a b An acid is a substance that donates a proton to a base and a base is a substance that accepts a proton from an acid. (Students may quote a variety of examples.) A strong acid is one that has a strong tendency to donate a proton to a base and is 100% ionised when added to excess water. A weak acid is one that has a weak tendency to donate a proton to a base and is less than 100% ionised or reacted when added to excess water. (Examples of strong acids are HCl, HNO3 and H2SO4. Examples of weak acids are H2CO3 and CH3COOH.) A strong base is one that has a strong tendency to accept a proton from an acid, while a weak base is one that has a weak tendency to accept a proton from an acid. (Examples of strong bases are NaOH and KOH. Examples of weak bases are NH3 and CH3COO.) HIn(aq) + H2O(l) H3O+(aq) + In(aq) Note that we cannot expect students to answer in terms of equilibrium principles, so the following answers to parts b and c would be reasonable at this stage. H3O+(aq) + In(aq) HIn(aq) + H2O(l) HIn(aq) + OH(aq) H2O(l) + In(aq)

b c 3

Table 1.1 The pH of some solutions

Solution
HCl HCl HCl HCl NaOH NaOH NaOH NaOH

Concentration (mol L1)

1.0 0.10 0.010 0.0010 1.0 0.10 0.010 0.0010

[H+] (mol L1)

1.0 = 10
0 1.0 2.0 3.0

pH
0 1.0 2.0 3.0 14 13 12 11

0.10 = 10

0.010 = 10

0.0010 = 10 10 10 10 10
14 13 12 11

a b

HCl(aq) + NaOH(aq) NaCl(aq) + H2O(l) Since n(NaOH) = n(HCl) = 0.10 0.020 00 mol = 0.002 000 mol, and since their mole ratio in the equation is 1 : 1, neither reactant is in excess. Thus, at the equivalence point, only NaCl and water will be present and the pH of the solution will be 7. Possible steps in the flow chart are shown. Note: This refers specifically to this activity and assumes that the burette already has been thoroughly washed after previous use, otherwise it would first be washed with water. 1 Rinse burette with NaOH solution, then secure burette in burette stand. 2 Check burette is vertical and adjust if necessary.

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Student Activity Manual solutions and information, Chapter 1

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Check burette tap is closed. Fill burette with NaOH to just below the zero mark, ensuring you have run some down to occupy the section below the tap assembly. Measure out 20.00 mL aliquot of the acid and transfer to a conical flask using 20 mL pipette. Add 34 drops of indicator. Remove funnel, then take initial burette reading. Slowly add base to flask until indicator just changes colour. Take final burette reading. Repeat Steps 27 until three concordant results are obtained. Drain the burette and thoroughly rinse with water. Wash the burette with soapy water, then fresh water, then drain.

Suggested solutions to discussion questions

1 HCl: HCl(aq) + H2O(l) H3O+(aq) + Cl(aq) CH3COOH: CH3COOH(aq) + H2O(l) H3O+(aq) + CH3COO(aq) NH4Cl: NH4+(aq) + H2O(l) H3O+(aq) + NH3(aq) NH3: NH3(aq) + H2O(l) NH4+(aq) + OH(aq) Na2CO3: CO32(aq) + H2O(l) HCO3(aq) + OH(aq) Sources of experimental uncertainty include: The subjective nature of detecting a colour change and the fact that a certain concentration of a coloured species must build up before we can detect it. The indicator changing colour before or after the equivalence point. The indicator is a mixture of a weak acid and weak base, therefore interferes with the reaction to a small extent. Parallax error reading the burette scale or in judging when the meniscus was on the etched mark in the pipette. Instrumental error. Also see the list of sources of experimental uncertainty in the Appendix of the Student Activity Manual (pages 21617). To ensure that the NaOH is not diluted but is present at the correct concentration; also helps remove any impurities. The indicator will need to be one colour in one of the acids and a different colour in the other. If the indicator changes colour in a pH range that is above or below the pH of both solutions, it will be the same colour in each acid. Thymol blue or orange IV should be suitable, since the pH of 0.1 M HCl should be 1 and so these indicators should be red in it and yellow in the very weak acid. From stoichiometry, the NaOH would be in excess by 1.000 104 mol. Hence its concentration would be 2.439 103 mol L1, which means [OH] = 2.439 103 mol L1 = 102.613 mol L1. Thus [H+] = 1011.39 mol L1 and the pH of the solution should be 11.39.

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Student Activity Manual solutions and information, Chapter 1

Suggested alternative questions to pre-lab focus questions

1 Phenolphthalein indicator is a chemical with the overall molecular formula C20H14O4. The structure of this molecule changes, depending on the pH of its environment. In acidic solutions the molecule changes to a form that is colourless, and in basic solutions it changes to a form that is pink, although at high concentrations it appears purple. We shall represent the formula of the colourless form as HIn, since this form is weakly acidic, and the pink form as In. a Write the balanced ionic equation for the reaction of HIn with water. b Phenolphthalein solution is usually colourless. When a few drops of this indicator is added to hydrochloric acid, it remains colourless, but when a few drops of the indicator are added to sodium hydroxide, it turns bright purple-pink. Write a balanced ionic equation for the reaction that occurs, which can explain this colour change. a Calculate the pH of nitric acid of concentration 0.005 mol L1. b Use Table 1.2 in the Student Activity Manual (page 3) to predict the colour of each of the following indicators in this solution: i methyl violet ii thymol blue iii methyl orange iv bromothymol blue Calculate the pH of a mixture of 25.00 mL of nitric acid of concentration 0.1000 mol L1 and 25.00 mL of potassium hydroxide of concentration 0.1000 mol L1. Show your calculations. Read the Appendix on how to correctly prepare and use a pipette and design a simple flow chart to summarise the procedure. Examine the material safety data sheet on sodium hydroxide provided by your teacher and use it to answer the following questions. a Is it flammable or explosive? b What does carcinogenic mean? Is it carcinogenic? c Why is it classified as hazardous? d What chemicals should be kept away from it? e By what routes can it be absorbed? f What would happen if water were added to NaOH pellets? g What first aid should be given if someone ingests some NaOH? h What first aid should be given if someone gets some NaOH on their skin? i What first aid should be given if someone gets some NaOH in their eyes?

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Suggested solutions to alternative pre-lab focus questions

1 a HIn(aq) + H2O(l) H3O+(aq) + In(aq) Note that we cannot expect students to answer in terms of equilibrium principles, so the following answer to part b would be reasonable at this stage. HIn(aq) + OH(aq) H2O(l) + In(aq)

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Student Activity Manual solutions and information, Chapter 1

a b

2.3 i blue ii turning from red to yellow, so probably orange iii red iv yellow Since n(KOH) = n(HNO3) = 0.1000 0.025 00 mol = 0.002 500 mol, and since their mole ratio in the equation is 1 : 1, neither reactant is in excess. Thus, at the equivalence point, only KNO3 and water will be present and the pH of the solution will be 7. Possible steps in the flow chart are shown. Note that this refers specifically to this activity and assumes that the pipette already has been thoroughly washed after previous use; otherwise it would first be washed with water. 1 Attach the pipette filler to the top of the pipette. 2 Add about 40 mL of the acid to a clean dry 100 mL beaker and inserting the pipette well below the surface, draw some up into the pipette and swirl to just above the etched mark. 3 Discard rinse solution. 4 Add about 50 mL of acid to the beaker. 5 Fill pipette with acid to just above the etched mark. 6 Slowly let out the acid until the bottom of its meniscus just sits on the etched mark. 7 Holding the pipette almost vertical and placing its tip against the inside surface of the neck of the reaction flask, deliver the acid into the flask. 8 When the acid stops flowing, remove the pipette. 9 Repeat Steps 48 until three concordant results obtained in the titration. 10 Thoroughly rinse pipette with water. 11 Wash pipette with soapy water, then water, then drain. The following answers were obtained from one sample MSDS for this substance. The teacher would need to check the MSDS provided to students to check that their answers are consistent with the data they are given. a No b Carcinogenic substances are those that can cause cancer. It is not known to be carcinogenic. c It is corrosive to all tissues exposed to it and can cause serious burns. d Carbohydrates, aluminium, zinc, tin, acids, nitrogen-containing organics, explosives, phosphorus, organic peroxides, halogen compounds e Skin, eyes, inhalation, ingestion f A large amount of heat is evolved on dilution, which will cause boiling and spattering. h They should immediately drink large quantities of water, unless they are unconscious or having convulsions. Vomiting must not be induced. An ambulance should be called immediately. i Any affected clothing should be removed immediately. The skin should be immediately flushed with large quantities of water for at least 15 minutes and a physician should be called.

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Student Activity Manual solutions and information, Chapter 1

The eyes should be immediately flushed with large quantities of water for at least 15 minutes, occasionally lifting the upper and lower eyelids. An ambulance should be called immediately.

Suggested alternative questions to discussion questions

1 For each of the substances tested in Part A, write an appropriate equation for its reaction with water molecules to explain why it is acidic or basic. a HNO3 b CH3COONa c Na3PO4 Identify the effect on the value of first titre obtained in Part B if: a the acid was more concentrated than stated on the label b the burette was washed with water instead of NaOH c the pipette was filled in such a way that the top of the meniscus sat on the etched line d the section of the burette below the tap assembly was not filled with NaOH before the initial reading was taken. State your reasoning in each case. a Calculate the pH of a mixture of 25.00 mL of nitric acid of concentration 0.1000 mol L1 and 22.46 mL of potassium hydroxide of concentration 0.1000 mol L1. Show your calculations. b If you were to add water to this mixture, in what way, if any, would it affect the pH of the solution? State your reasoning. Suggest reasons for the following: a Workers in industries in which NaOH is used in the processes must wear face shields, but safety glasses were considered to be sufficient eye protection while handling the NaOH in this experiment. b You should not induce vomiting if someone ingests NaOH. c You wash NaOH off skin with water and not acid.

Suggested solutions to alternative discussion questions

1 a b c a HNO3(aq) + H2O(l) H3O+(aq) + NO3(aq) CH3COO(aq) + H2O(l) CH3COOH(aq) + OH(aq) PO43(aq) + H2O(l) HPO42(aq) + OH(aq) Increase. There would be a greater amount of HCl in mol in the aliquot delivered to the flask, so a greater amount of NaOH would need to be delivered to react completely with it. Increase. The NaOH would be diluted by the water, so a greater volume will be needed to deliver the same amount of NaOH, in mol. Decrease. The pipette would deliver less than 20.00 mL and so the amount of acid in mol would be slightly less. Therefore slightly less NaOH would be required to react with it.

b c

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Student Activity Manual solutions and information, Chapter 1

b 4 a

b c

Increase. Some of the volume of NaOH would be used in filling the empty section, so there will be a greater difference between the initial and the final reading. It would appear that more base has been delivered to the flask than really was. From stoichiometry, the HNO3 would be in excess by 2.540 104 mol. Hence its concentration would be 5.352 103 mol L1, which means [H+] = 102.271 mol L1 and the pH of the solution should be 2.271. It would increase it, since [H+] will decrease because the added water will dilute the solution. The workers would be handling large quantities of the solid chemical and concentrated solutions, and these will cause far more serious injury than a dilute solution. Moreover, spills and splashes of the chemical are more likely. It is corrosive and will burn the mouth and oesophagus on the way down and even further on the way up if vomiting is induced. A large amount of heat would be given out if an acid is added, which would cause even more serious burns.

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Student Activity Manual solutions and information, Chapter 1