9.3 THE ACIDIC ENVIRONMENT 1. Indicators were identified with the observation that the colour of some flowers depends on soil composition. 1.2.1 – Classify common substances as acidic, basic or neutral. 1.2.2 – Identify that indicators such as litmus, phenolphthalein, methyl orange and bromothymol blue can be used to determine the acidic or basic nature of a material over a range, and that the range is identified by change in indicator colour. 1.3.2 – Identify data and choose resources to gather information about the colour ranges of a range of indicators. Chemical substances can be classified as acidic, basic or neutral. This classification is usually based on the concentration of hydrogen ions produced when the substance is dissolved in water. The concentration of hydrogen ions can be determined by change in colour of dyes called indicators. Examples of indicators include litmus, phenolphthalein, methyl orange and bromothymol blue. Methyl orange Bromophenol Blue Bromocresol Blue Methyl Red Bromothymol Blue Phenol Red Thymol Blue Phenolphthalein Red – Yellow Yellow – Blue Yellow – Blue Pink – Yellow Yellow – Blue Yellow – Red Yellow – Blue Colourless – Red pH 3.1 – 4.4 pH 3.0 – 4.6 pH 3.8 – 5.4 pH 4.4 – 6.0 pH 6.2 – 7.6 pH 6.8 – 8.4 pH 8.0 – 9.6 pH 8.3 – 10 1.2.3 – Identify and describe some everyday uses of indicators including the testing of soil acidity/basicity. Everyday uses of indicators include the monitoring of the pH-level of fish-tank environments, garden soil and swimming pools. 1.3.1 – Perform a first-hand investigation to prepare and test a natural indicator. 1.3.3 – Solve problems by applying information about the colour changes of indicators to classify some household substances as acidic, neutral or basic. A natural indicator is the dye in red cabbage leaves. The leaves were shredded and the dye extracted by placing the shredded leaves into minimal hot water. The clear purple solution was strained. A small amount of the solution was applied to test tubes containing sodium hydroxide (reference base); hydrochloric acid (reference acid); ‘Windex’ (window cleaner); white vinegar; generic shampoo; lemon juice and milk. The colour of the reference base became green, then clear yellow after the introduction of the indicator; the reference acid became a clear hot pink. ‘Windex’ went from a clear light blue to a clear deep green (basic). White vinegar, lemon juice and shampoo all became pink (acidic). Milk was unable to be determined. -I- 2. While we usually think of the air around us as neutral, the atmosphere naturally contains acidic oxides of carbon, nitrogen and sulfur. The concentrations of these acidic oxides have been increasing since the Industrial Revolution. 2.2.1 – Identify oxides of non-metals which act as acids and describe the conditions under which they act as acids. 2.2.2 – Analyse the position of these non-metals in the Periodic Table and outline the relationship between the position of elements in the Periodic Table and acidity/basicity of oxides. Non-metal oxides include sulfur dioxide, carbon dioxide, nitrogen dioxide and nitrous dioxide. They act as acids when they ionise water. Generally, non-metallic oxides are acidic. However, some non-metallic oxides are neutral. 2.2.3 – Define Le Chatelier’s principle. Le Chatelier’s Principle states: ‘when a change is made to an equilibrium system, the system moves to counteract the imposed change and restore the system to equilibrium’. 2.2.4 – Identify factors which can affect the equilibrium in a reversible reaction. Factors which will affect equilibrium include concentration, gas pressure and temperature. If the temperature increases, the endothermic reaction will be favoured. If the temperature decreases, the exothermic reaction will be favoured. If the concentration of a certain reactant of the equation is increased, the system will shift to convert that reactant into product(s). Vice-versa, if the concentration is decreased, the system will shift to convert products back into the reactant. If the pressure of a system increases, the shift will be towards the reaction with the least number of moles. 2.2.5 – Describe the solubility of carbon dioxide in water under various conditions as an equilibrium process and explain in terms of Le Chatelier’s principle. The solubility of carbon dioxide in water under various conditions can be understood under Le Chatelier’s principle. The equilibria involved are: CO2(g) CO2(g) + H2O(l) CO2(aq) + H2CO3(aq) heat + heat As the pressure of the system increases, more carbon dioxide is dissolved, because the equilibrium will favour the reaction with least amount of moles of products. As the pressure decreases, carbon dioxide escapes (into the air); the system counteracts this by evolving more carbon dioxide gas from solution. As the temperature of the system increases, the endothermic reaction is favoured. Therefore, more carbon dioxide gas will be formed. As the temperature decreases, the exothermic reaction is favoured; therefore more carbon dioxide is dissolved. The solubility will increase in the presence of a base such as hydroxide ions. Hydroxide ions (OH –) will decrease the concentration of hydrogen ions (H +) formed by carbonic acid (H2CO3(aq)). Therefore the system will shift to produce more acid and dissolve more carbon dioxide. - II - 2.2.6 – Identify natural and industrial sources of sulfur dioxide and oxides of nitrogen. 2.2.7 – Describe, using equations, examples of chemical reactions which release sulfur dioxide and chemical reactions which release oxides of nitrogen. 2.3.2 – Analyse information from secondary sources to summarise the industrial origins of the above gases and evaluate reasons for concern about their release into the environment. Industrial origins: The sulfur dioxide in the air comes from the burning of coal in coal-powered/oil-fired power stations. The smelting of metals such as zinc, copper and lead also produces sulfur dioxide from their ores. Sulfur is oxidised into sulfur dioxide by the following equation: –S–(s) Sulfur in Compound + O2(g) Oxygen in air → SO2(g) Sulfur Dioxide The incomplete combustion of fossil fuels releases large amounts of carbon-monoxide. The fact that the air is not 100% O2 contributes to incomplete combustion in closed or unventilated environments. Carbon monoxide is formed by cars and other combustion reactions with the following equation: –C–(l) + → ½O2(g) CO(g) Due to the high temperatures of an internal combustion engine, and the rapid cooling of exhaust gas, NO(g) is prevented from decomposing. Nitrogen dioxide is formed by a secondary reaction of nitrogen oxide with oxygen: 2NO(g) + → O2(g) 2NO2(g) Reasons for Concern: Sulfur dioxide and the oxides of nitrogen, along with carbon dioxide, are largely responsible for acid rain: + H2O(l) → Water H2SO3(aq) Sulfurous Acid 2NO2(g) + Nitrogen dioxide H2O(l) → Water HNO3(aq) Nitric Acid CO2(g) + Carbon dioxide H2O(l) → Water H2CO3(aq) Carbonic Acid SO2(g) Sulfur dioxide + HNO2(aq) Nitrous Acid The introduction of acidic solutions into rain water can cause it to drop in pH to about pH2. Long term exposure to this is damaging to flora, since they continually absorb acid rain via diffusion. To freshwater animals, the pH can release toxic metal ions which will kill them. To the built environment, acid rain can attack structures made of marble, metal and sandstone. For example, bridges are subject to corrosion in this way: Fe(s) Iron in bridge + H2CO3(aq) → Carbonic Acid FeCO3(s) + Oxidation of Iron H2(g) Hydrogen Further damage is caused with an increase of photochemical smog and respiratory problems. Evaluation: - III - It is clearly seen that the introduction of non-metal oxides into the atmosphere contributes to the destruction of the natural and built environment. If unchecked, the devastation will only continue to grow as the burning of fossil fuels increases. Therefore, the release of non-metal oxides needs to be restricted and, if possible by further industrial reactions, eliminated completely. 2.2.8 – Assess the evidence which indicates increases in the atmospheric concentrations of these gases. The evidence which indicates increases in atmospheric concentrations of these gases have been gathered from measurements on bubbles of ancient air trapped in ice sheets of Antarctica and Greenland. This is then compared to more modern levels. This evidence is supported because the bubbles of air remain unchanged. Concentration of air is constant around the world. The only problem which may arise is slow diffusion of gases may occur in the air pockets. 2.2.9 – Calculate volumes of gases given masses of some substances in reactions, and calculate masses of substances given gaseous volumes, in reactions involving gases at 25°C and 100kPa. 2.3.1 – Identify data, plan and perform a first hand investigation to decarbonate soft drink and gather data to measure the mass changes involved and calculate the volume of gas released at 25°C and 100kPa. A 390mL soft drink was heated in water until it was approximately 25°C. It was then weighed and mass recorded on the triple beam balance. The soft drink was agitated by shaking and opened to release carbon dioxide gas. Subsequent weighing, shakings and recordings of mass were done until the mass reached a constant. To calculate the volume of CO2(g) released, the mass of CO2(g) was recorded (by subtraction). It was then substituted into the following formula: n(CO2) = = ≈ m(CO2) 3.7 0.084 moles ÷ ÷ Mm(CO2) 44 v(CO2) = = = n(CO2) 0.084 2.06 litres × × SLC 24.47 2.2.10 – Explain the formation and effects of acid rain. The formation of acid rain is in the evolution of non-metal oxides such as the production of SO 2(g) by the burning of coal, the production of CO2(g) and CO(g) by the combustion of fossil fuels and the production of NO2(g) by the combustion of coal, oil and petrol. Nitrogen dioxide also is formed by soil processes, volcanic activity and lightning. These gases, when reacted with water in the atmosphere, result in acidic solutions, and as rain, acid rain. For example: SO2(g) Sulfur dioxide + H2O(l) → Water H2SO3(aq) Sulfurous Acid The effects of acid rain include the destruction of plants, which roots are constantly bathed in acid rain through diffusion; the destruction of fresh water animals, whose metabolism and well-being are affected by their limited water environment and pH-change intolerance; the destruction of the human built environment, such as buildings with sandstone, limestone, marble and metals. For example, a marble statue can be eroded by acid rain: CaCO3(s) + Calcium carbonate Acid Rain → - IV - Ca(HCO3)2(aq) Calcium hydrogen carbonate (soluble) 3. Acids occur in many foods, drinks and even within our stomachs. 3.2.1 – Define acids as proton donors and describe the ionisation of acids in water. Acids can be defined as proton donors because they contribute a proton (a hydrogen ion) to water when they ionise. For example: CH3COOH(aq) Acetic acid + H2O(l) Water H3O+(aq) + Hydronium ion CH3COO–(aq) Acetate ion 3.2.2 – Identify acids including acetic (ethanoic), citric (2–hydroxypropane–1, 2, 3–tricarboxylic), hydrochloric and sulfuric acid. Acetic Acid: (Ethanoic acid) CH3COOH(aq) Citric Acid: (2–hydroxypropane–1, 2, 3–tricarboxylic acid) (COOH)CH2CH(OH)(COOH)CH2COOH(aq) Hydrochloric Acid (Hydrochloric acid) HCl(aq) Sulfuric Acid (Sulfuric acid) H2SO4(aq) 3.2.3 – Describe the use of the pH scale in comparing acids and bases. 3.2.5 – Identify pH as –log10[H+] and explain that a change in pH of 1 means a ten-fold change in [H+]. The pH scale is used to compare acids and bases, based on the concentration of [H +] in solution. pH is measured from 0 to 14 (acidic to basic). The pH scale is a logarithmic relationship, the formula being: pH = –log10[H+] The pH of a base is derived by the following: pOH pH = = –log10[OH–] 14 – pOH where [OH–] is the concentration of hydroxide ions in the solution. 3.2.4 – Describe acids and their solutions with the appropriate use of the terms strong, weak, concentrated and dilute. 3.2.6 – Compare the relative strengths of equal concentration of citric, acetic and hydrochloric acid and explain in terms of the degree of ionisation of their molecules. Acids ionise in water and become proton donors, forming [H +] ions in water. The greater the concentration of [H+], the greater is the strength of the acid. The negative logarithmic relationship only works for strong acids, those which ionise completely in water. A weak acid is an acid which only partially ionises in solution. A concentrated acid can be either strong or weak. Concentration and weakness refer to the level of dilution of the solution using a solute, usually water. Between hydrochloric, acetic and citric, the strong acid, hydrochloric, is strongest. The weakest acid is the weak acid, acetic, and citric acid is between the strengths of the two. 3.2.7 – Describe the difference between a strong and weak acid in terms of an equilibrium between the intact molecule and its ions. -V- In a strong acid, such as hydrochloric acid, an equilibrium is formed during ionisation: HCl(aq) + Hydrochloric acid H2O(l) Water H3O+(aq) + Hydronium ion Cl–(aq) Chloride ion In the equilibrium of the strong acid, the equation completely lies on the right side (near 100% ionisation). The molecule of the strong acid completely ionises. In a weak acid, such as acetic acid, an equilibrium is formed during ionisation: CH3COOH(aq) Acetic acid + H2O(l) Water H3O+(aq) + Hydronium ion CH3COO–(aq) Acetate ion In the equilibrium of the weak acid, the equation lies mostly on the left (partial ionisation). The molecule of the weak acid is in solution with few of its ions. 3.3.1 – Solve problems and perform a first-hand investigation to use pH meters/probes and indicators to distinguish between acidic, basic and neutral chemicals. 3.3.2 – Plan and perform a first-hand investigation to measure the pH of identical concentrations of strong and weak acids. 4.3.2 – Choose equipment and perform a first-hand investigation to identify the pH of a range of salt solutions. The three dot points were simultaneously completed by a pH recording of a range of acids, bases and salts using a pH probe connected to a data-logger and various indicators. It was clearly seen that the acidic solutions have their pH below 7. This was shown accurately by the probe and qualitatively by the indicators. The results for pH were accurate and registered the 0.1M solutions of strong acids (HCl, H2SO4 and HNO3) at about pH 1. The results also clearly showed the difference in pH between strong and weak acids. Since they were in identical concentration, the difference in ionisation levels attributes to a difference in pH. The pH of salts was tested with 0.1M solutions. The ‘neutral’ salts were identified (NaCl, Na 2SO4 and KNO3) and were neutral because of the inert nature of their ions. A basic salt, CH3COONa, was identified. It is basic because of the presence of hydroxide ions during its dissociation: CH3COONa(aq) → CH3COO–(aq) + CH3COO–(aq) H2O(l) → - VI - + Na+(aq) CH3COOH(aq) + OH–(aq) 4. Because of the prevalence and the importance of acids, they have been used and studied for hundreds of years. Over time, the definitions of acids and base have been refined. 4.2.1 – Outline the historical development of ideas about acids including those of: – Lavoisier, –Davy, – Arrhenius. 4.2.2 – Outline the Brönsted-Lowry theory of acids and bases. 4.3.1 – Gather and process information from secondary sources to trace development in understanding and describing acid/base reactions. The first definition of acids and bases were derived from our taste of them. Acids tasted sour, hence it was derived from the Latin word: ‘acer’, meaning sharp. Bases, to humans, tasted bitter. In 1776, the Frenchman Antoine Lavoisier discovered that many compounds with oxygen (nonmetallic oxides) developed acidic properties in solution. He defined an acid as a non-metal compound containing hydrogen. In 1810, Humphry Davy showed that HCl has acidic properties and contained no oxygen. He redefined an acid as a substance containing hydrogen. In 1894, Svante Arrhenius redefined the theory to explain that acids contain H + ions which are liberated in solution. A base, he said, is a substance which contains OH – ions in solution. However this theory does not account for all bases, such as sodium carbonate (Na2CO3). In 1923, the Danish scientist Johannes Brönsted and Englishman Thomas Lowry proposed independent theories that an acid is a proton donor, a base a proton acceptor. 4.2.3 – Describe the relationship between an acid and its conjugate base and a base and its conjugate acid. 4.2.5 – Identify conjugate acid/base pairs. When Brönsted and Lowry proposed their theories they established a relationship between acids, bases and their conjugate pairs. This definition recognised the important role of the solvent in determining acidity or basicity. Acids ionise in water due to interaction with water molecules. The acidic proton is donated to the water molecule (a base) to form the hydronium ion (the conjugate base). For example: HCl(aq) ACID + H2O(l) BASE → H3O+(aq) CONJUGATE ACID + Cl–(aq) CONJUGATE BASE Each acid has a conjugate base, and each base a conjugate acid. 4.2.6 – Identify amphiprotic substances and construct equations to describe their behaviour in acidic and basic solutions. In Brönsted-Lowry theory some substances are capable of behaving as either acids or bases. Such substances are said to be amphiprotic (either accepting or donating a proton). An example of this is: HCO3–(aq) + H3O+(aq) → H2CO3(aq) + H2O(l) BASE ACID ACID BASE HCO3–(aq) ACID + OH–(aq) BASE → - VII - CO32–(aq) BASE + H2O(l) ACID Water, HSO4– and HPO4– are also amphiprotic. Amphoteric substances are those which react with both acids and bases. 4.2.7 – Identify neutralisation as a proton transfer reaction which is exothermic. Neutralisation is a proton transfer reaction in which an acid and a base react to form a salt and water. Neutralisation reactions are exothermic. The amount of heat liberated when neutralisation occurs depends on the strengths of the acid and the base. 4.2.8 – Describe the correct technique for conducting titrations and preparation of standard solutions. 4.3.3 – Perform a first-hand investigation and solve problems using titrations and including the preparation of standard solutions, and use available evidence to quantitatively and qualitatively describe the reaction between selected acids and bases. The volumetric analysis that was conducted was to find the molarity of an unknown sodium hydroxide solution. Firstly 250mL of primary standard of 0.05 mol L–1 sodium carbonate was needed. Anhydrous sodium carbonate was spooned into a 100mL beaker on a 2 decimal place zeroed electronic balance. The mass was calculated to be approximately 1.325 grams. Water was added and the solution was swirled to dissolve the sodium carbonate. It was then transferred to a volumetric glass. More water was added to the beaker by a wash bottle to ensure all of the sodium carbonate went into the volumetric flask. The volumetric flask was then swirled and filled to the 250mL mark. This was the primary standard. 0.05 mol L–1 0.05 × 0.0125 moles Molarity required of Na2CO3 In 250mL, n(Na2CO3) = = = Mass number of moles 0.0125 1.325 grams = = ≈ 0.25 × × Molar mass 105.99 The secondary standard was a solution of approximately 1 molar hydrochloric acid solution. The acid was diluted to make 250mL of approximately 0.1 mol L –1 hydrochloric acid solution. This was our secondary standard. A pipette and conical flask was rinsed with small amounts of the primary standard. 25mL of the primary standard was added by pipette to the conical flask. 2 drops of the indicator methyl red was added to the flask. A small amount of the secondary standard was used to rinse the burette. 50mL of the secondary standard was then added to the burette and used to titrate the primary standard. Titrating, it was found that 23.35mL of ~0.1M HCl reacted with 25ml of Na2CO3. CHCl × VHCl = 2 × CHCl = = 2 × (0.05) × (25) ÷ 23.35 0.107 mol L–1 CNa2CO3 × VNa2CO3 A fresh burette was rinsed with the unknown sodium hydroxide solution. 50mL of sodium hydroxide was then added to it. The secondary standard was used to rinse a new conical flask, and 10mL of it was added by pipette to the flask. 2 drops of phenolphthalein was used as indicator. - VIII - Titrating, it was found that 13mL of NaOH reacted with 10mL of HCl CHCl × VHCl = CNaOH × VNaOH = = VNaOH 10 × (0.107) ÷ 13 0.082 mol L–1 (3dp) By using volumetric analysis, titration and several indicators, the concentration of HCl could be standardised and thus unknown concentration NaOH. 4.2.9 – Qualitatively describe the effect of buffers with reference to a specific example in a natural system. A buffer solution is a solution which contains comparable amounts of a weak acid and its conjugate base and which is therefore able to maintain an approximately constant pH even when significant amounts of strong acid or strong base are added to it. The following buffer is found in human blood: H2CO3(aq) + H2O(l) H3O+(aq) + HCO3–(aq) If an acid is added the concentration of the H 3O+ ions suddenly rises. By Le Chatelier’s Principle, the equilibrium shifts to the left to counteract the change. This uses up the H 3O+ ions and returns the pH to where it was. If a base is added the concentration of the H 3O+ ions suddenly falls. The equilibrium shifts to the right to counteract the change. This uses up the OH – ions present in the base, and returns the pH to where it was. 4.3.3 – Perform a first-hand investigation to determine the concentration of a domestic acidic substance using computer-base technologies. This experiment was conducted similarly to the volumetric analysis experiment. A known concentration of sodium hydroxide solution was used to titrate vinegar (acetic acid). The pH probe and data-logger were set up and the program logged the pH by a chart and graph. As expected the pH of the equivalence point was greater than 7 in this weak acid/strong base titration. 4.3.4 – Analyse information from secondary sources to assess the use of neutralisation reactions as a safety measure or to minimise damage in accidents or chemical spills. Neutralisation can be used as a safety measure or to minimise damage in spills but only weak acids or bases should be used. An example of a weak base to clean up an acidic spill would be calcium carbonate in powder form. Calcium carbonate is a safe solid powder; powder has a larger surface area than chips, making it faster to react. The problem with neutralisation is that heat will be built up, causing more damage. - IX - 5. Esterification is a naturally occurring process which can be performed in the laboratory. 5.2.1 – Describe the differences between the alkanol and alkanoic acid functional groups in carbon compounds. 5.2.3 – Explain the difference in melting and boiling point caused by straight-chained alkanoic acid and straight-chained primary alkanol structures. Both alkanols and alkanoic acids are polar molecules due to the presence of the –OH groups and –COOH groups. The presence of hydrogen bonding in both types of molecules leads to higher melting and boiling points in these molecules. As the chain length increases, dispersion forces increase, leading to higher melting and boiling points. When alkanoic acids and alkanols of the same number of carbons are compared, the more extensive hydrogen bonding and an increase in dipole-dipole interactions mean that the alkanoic acid has a higher melting and boiling point than its respective alkanol. 5.2.2 – Identify the IUPAC nomenclature for describing the esters produced by the reactions of straightchained alkanoic acids from C1 to C8 and straight-chained primary alkanols from C1 to C8. 5.2.4 – Identify esterification as the reaction between an acid and an alkanol and describe, using equations, examples of esterification. 5.2.5 – Describe the purpose of using acid in esterification for catalysis. Esterification is the process where an ester is formed by an alkanol and an alkanoic acid. They are named as alkyl alkanoates, where the alkyl is the abbreviated form of the alkanol used and alkanoate the form of the alkanoic acid. For example: Methanol + Butanoic Acid Methyl Butanoate + Water A catalyst, concentrated sulfuric acid, is used to assist in the dehydration of water and to lower the activation energy. It has been shown that it is the OH of the alkanoic acid that joins with the H of the alkanol to produce water. 5.2.6 – Explain the need for refluxing during esterification. 5.3.1 – Identify data, plan, select equipment and perform a first-hand investigation to prepare an ester using reflux. About 15mL of 1–pentanol (C5H12O) and 15mL of ethanoic acid were added to a pear-shaped flask, and 10 drops of concentrated (30M) sulfuric acid and porcelain boiling chips were added. The flask was secured by a retort stand and bathed in a water bath. An inverted reflux condensing tube attached to the flask. The equipment was heated by a bunsen set on a blue flame for 15 to 20 minutes, when two layers were clearly visible. The solution was poured into a separating funnel and 100mL of water was added. The mixture was shaken vigorously and the lower aqueous layer was discarded by separation. Sodium carbonate was added to neutralise excess acid and the funnel was swirled gently. The plug was released to allow carbon dioxide to escape. Two layers again formed and the lower discarded. Sodium carbonate was added again and the procedure repeated. The remaining liquid, the ester, was poured into a conical flask and a teaspoon of calcium chloride was added to remove excess water. After a few minutes, the ester was decanted. The ester was then distilled with a distillation kit to further purify it. The volatility of the reagents of esterification means that the extended heating must be performed under reflux. As the flask is heated the components vapourise and are then condensed due to the cooling provided by the condensing tube. The reagents thus return to the flask and eventually -X- equilibrium is achieved without lost of material. The final product, pentyl-ethanoate (a bananaflavoured ester), was produced. 5.2.7 – Outline some examples of the occurrence, production and uses of esters. 5.3.2 – Process information from secondary sources to identify and describe the uses of esters as flavours and perfumes in processed foods and cosmetics. Esters are added in many products, such as perfumes and cosmetics. Esters are used to add an artificial ‘fruity smell’ to foods such as pentyl-ethanoate (banana), octyl-ethanoate (orange) and pentyl-butanoate (apricot). Esters also are used as solvents for polar and non-polar compounds and soaps. Aspirin (acetylsalicylic acid) is an example of an ester used in medicine. - XI -