F325 Acids, bases and buffers

Acids, Bases and Buffers

Brnsted-Lowry acids and bases describe an acid as a species that can donate a proton and a base as a species that can accept a proton illustrate, using ionic equations, the role of H+ in the reactions of acids with metals, carbonates, bases and alkalis describe and use the term conjugate acidbase pairs Strong and weak acids explain qualitatively, in terms of dissociation, the differences between strong and weak acids explain that the acid dissociation constant, Ka, shows the extent of acid dissociation deduce, for weak acids, expressions for Ka and pKa pH and [H+(aq)] define pH = log[H+]; [H+] = 10pH state and use the expression for the ionic product of water, Kw calculate pH from [H+(aq)] and [H+(aq)] from pH for: (i) strong monobasic acids (ii) weak monobasic acids (assume: [H+(aq)] = [A-(aq)] and equilibrium [HA] = undissociated [HA]) (iii) strong bases, using Kw calculate Ka for a weak acid, given appropriate data Buffers:action, uses and calculations describe a buffer solution as a system that minimises pH changes on addition of small amounts of an acid or a base state that a buffer solution can be made from a weak acid and a salt of the weak acid, eg CH3COOH/CH3COONa explain the role of the conjugate acidbase pair in an acid buffer solution in the control of pH calculate the pH of a buffer solution, from the Ka value of a weak acid and the equilibrium concentrations of the conjugate acidbase pair explain the role of carbonic acid hydrogencarbonate (H2CO3/HCO3) as a buffer present in blood plasma, in the control of blood pH between 7.35 and 7.45 Neutralisation for acidbase titration pH curves for strong and weak acids and bases: (i) interpret, or sketch, their shapes (ii) explain the choice of suitable indicators for acidbase titrations, given the pH range of the indicator define and use the term enthalpy change of neutralisation and calculate enthalpy changes from appropriate experimental results

Describing acids
We need to be able to use the terms 'strong', 'weak', 'concentrated' and 'dilute' correctly. We will use square brackets to mean "the concentration of" e.g. [H+] = 0.5 mol dm-3 Concentrated: many acid particles/molecules per dm3 of solution Dilute: few acid particles/molecules per dm3 of solution e.g. 10M HCl is concentrated, with 10 moles of HCl per dm3 of acid solution Strong: dissociated fully to produce hydrogen ions in aqueous solution

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F325 Acids, bases and buffers Weak: partially dissociated to produce hydrogen ions in aqueous solution e.g. HCl is a strong acid: HCl(g) H+(aq) + Cl-(aq) when dissolved in water so if 1 mole of HCl is dissolved in 1 dm3 of water, the [H+] will be 1 mol dm-3 CH3COOH is a weak acid: CH3COOH(aq) H+(aq) + CH3COO-(aq) so if 1 mole of CH3COOH is dissolved in water, the [H+] will be much less than 1 mol dm-3 and most of the CH3COOH molecules will remain undissociated. Definitions of acid behavior Arrhenius' definition: an acid produces H+ ions in aqueous solution, is useful in many cases, but not all. e.g. HCl(g) + NH3(g) NH4Cl(s) (note the state symbols no solutions) Here the hydrogen chloride molecule is producing an H+ to donate to the ammonia molecule, but none of this is happening in solution. Bronsted and Lowry generated the more general definition: Acid = proton donor can donate H+ Base = proton acceptor can accept H+ Alkalis are soluble bases, supplying OH- ions in aqueous solution. Acids are neutralized by bases, but not all bases are alkalis (only the soluble ones).

Representing acid behaviour The reactions of acids are best shown using ionic equations as these focus on the essential reactants and ignore the spectator ions. The reactions of acids are the reactions of the H+ ion. Steps: 1) Write a full balanced equation 2) Split up anything aqueous into its component ions 3) Cancel any ions which are unchanged on both sides of the equation (spectator ions) Reaction of acids with metals e.g. General equation metal + acid salt + hydrogen Balanced equation Mg(s) + 2HCl(aq) MgCl2(aq) + H2(g) Split and cancel Mg(s) + 2H+(aq) + 2Cl-(aq) Mg2+(aq) + 2Cl-(aq) + H2(g) Ionic equation Mg(s) + 2H+(aq) Mg2+(aq) + H2(g) i.e. any acid reacts with magnesium to produce magnesium ions in solution and bubbles of hydrogen Reaction of acids with metal oxides (bases) e.g. General equation metal oxide + acid salt + water Balanced equation CuO(s) + H2SO4(aq) CuSO4(aq) + H2O(l) Ionic equation CuO(s) + 2H+(aq) Cu2+(aq) + H2O(l) i.e. any acid reacts with copper oxide to give copper ions in solution Reaction of acids with metal hydroxides (alkalis) e.g. General equation metal hydroxide + acid salt + water

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F325 Acids, bases and buffers Balanced equation 2KOH(aq) + H2SO4(aq) K2SO4(aq) + 2H2O(l) Split and cancel 2K+(aq) + 2OH-(aq) + 2H+(aq) + SO42-(aq) 2K+(aq) + SO42-(aq) + 2H2O(l) Ionic equation 2OH-(aq) + 2H+(aq) 2H2O(l) i.e. any acid neutralises any hydroxide, producing water Reaction of acids with metal carbonates e.g. General equation metal carbonate + acid salt + water + carbon dioxide Balanced equation Na2CO3(aq) + 2HNO3(aq) 2NaNO3(aq) + H2O(l) + CO2(g) Ionic equation: CO32-(aq) + 2H+(aq) H2O(l) + CO2(g) i.e. any carbonate reacts with any acid to produce carbon dioxide and water

Conjugate acids and bases

When an acid donates its proton, the remaining species is a proton acceptor i.e. a base because the reverse reaction can take place. Similarly when a base accepts a proton, the species formed is a proton donor i.e. an acid since it can donate the proton in a reverse reaction. We call these conjugate acid/base pairs. Definitions: The base formed when an acid loses its proton is called the conjugate base of that acid. e.g. Cl- is the conjugate base of HCl The acid formed when a base gains a proton is called the conjugate acid of that base. e.g. NH4+ is the conjugate acid of NH3 We can identify conjugate acid/base pairs in the reactions of acid with bases:

Consider how acid and alkali solutions are formed: When ammonia gas is bubbled through water:

This explains why an ammonia solution is alkaline (contains OH- ions). When hydrogen chloride is bubbled through water:

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F325 Acids, bases and buffers

Here we have shown the H3O+ ion, (called the hydronium or hydroxonium ion) which is how hydrogen ions exist when they are in water. We usually just represent this as H+(aq), but we should be aware that hydrogen ions (protons) are never found isolated, they are always bonded to something because they are 10,000 times smaller than any other chemical species and their small size and positive charge gives them an intense electric field, attracting any nearby lone pair to form a dative bond. We have also just shown water acting as an acid, and water acting as a base like amino acids, water is AMPHOTERIC.

Ionic Product of Water

Water molecules can react with each other when they collide a very small proportion of them exchange a proton to form ions: H2O + H2O H3O+ + OHalthough we could write H2O(l) H+(aq) + OH-(aq) Kc = [H+(aq)][OH-(aq)] units: mol dm-3 [H2O(l)]

We can write an equilibrium constant expression for this:

The position of equilibrium lies very far over to the left very few water molecules form ions. Because of this, the concentration of water remains effectively constant. We therefore choose to define Kw = [H+(aq)][OH-(aq)] units: mol2 dm-6 Because it tells us how ionized the water molecules are, Kw is called the IONIC PRODUCT OF WATER. Like any equilibrium constant, Kw does not vary with anything except temperature. At room temperature it has a value of 1 x 10-14 mol2 dm-6. In pure water, all the H+ and OH- are formed by water molecules splitting, so [H+] = [OH-] This means that Kw = [H+]2 so [H+] = Kw = 10-7 If we relate this to pure water having a pH of 7, we can begin to see the basis of the pH scale, which is a measure of the concentration of H+ ions in a solution. We should also be aware that Kw increases with temperature, so at higher temperatures, more water molecules are split into ions (which we'd expect on the basis of more frequent energetic collisions). This means that the concentrations of both H+ and OH- are higher in hotter water. If the concentration of H+ is higher, the pH is lower (more acidic) than 7. The water is still neutral, but the neutral point on the pH scale has moved to lower pH as the temperature increased !

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F325 Acids, bases and buffers The pH scale Invented by Soren Sorensen of Carlsberg Institute for measuring acidity in brewing: Definition: pH = -log10[H+] e.g. [H+] 1.00 1 x 10-2 1 x 10-4 1 x 10-7 pH 0 2 4 7 [H+] = 10-pH

We also need to be able to turn a pH into a concentration of H+ ions.

Getting a feel for the pH scale: the smaller the pH, the higher the concentration of H+(aq) pH 0 corresponds to a [H+] of 1 mol dm-3 pH 14 corresponds to a [OH-] of 1 mol dm-3 (note that even in a very alkaline solution such as this there will still be a [H+] of 10-14 mol dm-3) a difference of 1 pH unit corresponds to a ten-fold difference in acidity. pH 2 is ten times more acidic than pH 3. Practice: 1) HBr is an acid. What is its conjugate base ? 2) OH- is a base. What is its conjugate acid ? 3) Identify the conjugate acid/base pairs in HNO3 + OH- NO3- + H2O 4) In a solution, [H+(aq)] = 10-4 mol dm-3. What is [OH-(aq)] ? (Kw = 1 x 10-14 mol2dm-6) 5) An acid produces an [H+(aq)] of 0.1 mol dm-3. What is its pH ? 6) An acid has a pH of 3.0 What is the [H+(aq)] ? Finding the pH of strong acids These are fully dissociated, so [acid] = [H+] We simply use the pH definition: pH = -log10[H+]

e.g. I have a 0.02 mol dm-3 solution of HCl. What is its pH ? [HCl] = 0.02 mol dm-3 HCl is a strong acid, so [H+] = 0.02 mol dm-3 pH = -log10(0.02) = 1.70 (N.B get into the habit of giving pH to 2 decimal places) It is possible to have an acid which produces more than one proton when it dissociates. If an acid produces more than one H+ ion when it dissociates, this should be made clear in the question. For example H2SO4 2H+(aq) + SO4-2(aq) So [H+] = 2 x [H2SO4] ! e.g. I have a 0.02 mol dm-3 solution of H2SO4. What is its pH ? [H2SO4] = 0.02 mol dm-3 and H2SO4 is a strong acid so [H+] = 2 x 0.02 = 0.04 mol dm-3 pH = -log10(0.04) = 1.40

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F325 Acids, bases and buffers Finding [H+] for a strong acid given the pH We use the formula [H+] = 10-pH to calculate this directly. e.g. What is the [H+] is a solution of hydrochloric acid with a pH of 0.7 ? [H+] = 10-0.7 = 0.20 mol dm-3 Practice: 7) What is the pH of a solution of nitric acid of concentration 0.50 mol dm-3 ? 8) What is the [H+] in a nitric acid solution with a pH of 2.5 ? Finding the pH of strong alkalis Here we know the alkali is fully dissociated so [OH-] = concentration of the alkali in solution. We have to use the ionic product of water: Kw = [H+][OH-] to work out [H+].
(The value of Kw will be given, usually 1.00 x 10-14 mol2dm-6).

Then we can calculate pH as before. e.g. I have a 0.2 mol dm-3 solution of NaOH. What is its pH ? [NaOH] = 0.2 mol dm-3 and NaOH is a strong alkali, so [OH-] = 0.2 mol dm-3 Kw = [H+][OH-] and so 1.00 x 10-14 = [H+] x 0.2 so [H+] = 10-14 / 0.2 = 5 x 10-14 pH = -log10(5 x 10-14) = 13.3 We can get to this same result a slightly different route: pH = 14 + log10[OH-] = 14 + log10(0.2) = 14 0.7 = 13.3 (This is actually the same calculation, substituting Kw and [OH-] for [H+] in the pH equation and simplifying it) Finding [OH-] if we are given pH We use the pH to get [H+], then we use Kw to get [OH-]. e.g. What is the [OH-] in a solution of potassium hydroxide with pH = 11.3 ? [H+] = 10-pH = 10-11.3 = 5.01 x 10-12 Kw = [H+][OH-] so 1.00 x 10-14 = 5.01 x 10-12 x [OH-] [OH-] = 1.00 x 10-14 / 5.01x10-12 = 0.00200 Practice: 9) Calculate the pH of a 0.05 mol dm-3 solution of potassium hydroxide. 10) What is the [OH-] in a sodium hydroxide solution with pH 9.0 ?
(Kw = 10-14 mol2 dm-6) (Kw = 10-14 mol2 dm-6)

Finding the pH of weak acids Recall that a weak acid is only partially dissociated, so [H+] is less than [HA] where the acid is represented by the formula HA. In order to work out what the [H+] will be, we need to know how much of the acid has split up into ions. The equilibrium constant tells us this. For weak acids we call this the acid dissociation constant, Ka: HA(aq) H+(aq) + A-(aq)

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F325 Acids, bases and buffers Ka = [H+(aq)]eqm[A-(aq)]eqm [HA(aq)]eqm units: mol dm-3

The larger Ka is: - the more the acid dissociates into ions - the stronger the weak acid is - the more [H+] in the solution - the lower (more acidic) the pH Using Ka we can work out [H+] and then use it to work out the pH: The H+ ions have been formed by HA splitting up, so for every H+ ion, there is an A- ion. This means [H+] = [A-] at equilibrium, so we can substitute [H+] for [A-] in the Ka equation: Ka = [H+(aq)]eqm[H+(aq)]eqm [HA(aq)]eqm = [H+(aq)]2eqm so [H+(aq)]2eqm = Ka x [HA(aq)]eqm [HA(aq)]eqm and [H+(aq)]eqm = (Ka x [HA(aq)]eqm) We know Ka, but we don't know [HA]eqm. We do, however, know [HA]initial, and we know that for a weak acid only a very few acid particles dissociate into ions. It is therefore a valid approximation for weak acids that [HA]eqm = [HA]initial. Thus for a weak acid: [H+] (Ka x [HA]) where [HA] is the concentration of the acid BEFORE any dissociation is taken into account.

Once we have [H+] we can calculate pH using the normal equation. e.g. Calculate the pH of a 0.1 mol dm-3 solution of ethanoic acid. (Ka for ethanoic acid = 1.7x10-5 mol dm-3) [HA] = 0.1 mol dm-3 [H+] (Ka x [HA]) = (1.7x10-5 x 0.1) = 0.0013 pH = -log10(0.0013) = 2.88 Practice: 11) calculate the pH of 0.0200 mol dm-3 of ethanoic acid. Ka = 1.74 x 10-5 mol dm-3 12) calculate the pH of 0.0100 mol dm-3 butanoic acid. Ka = 1.51 x 10-5 mol dm-3 13) calculate the pH of 0.500 mol dm-3 chloroethanoic acid. Ka = 1.38 x 10-3 mol dm-3 Finding [H+] for a weak acid, given pH Don't get caught out! It doesn't matter that the acid is weak. We can still use the pH equation directly. e.g. A solution of ethanoic acid has a pH of 3.0 What is the concentration of [H+] in the solution ? [H+] = 10-pH = 1 x 10-3 mol dm-3

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F325 Acids, bases and buffers Finding Ka for a weak acid We might also be expected to work out Ka for a weak acid, given its pH and the concentration of the undissociated acid. We can use the assumptions we used before, that [H+] = [A-] and that [HA]eqm = [HA]undissociated. e.g. A 1.0 mol dm-3 solution of ethanoic acid has a pH of 2.38. What is the value of Ka? [H+] = 10-pH = 10-2.38 = 0.00417 Ka = [H+]eqm[A-]eqm / [HA]eqm but [A-] = [H+] and [HA]eqm = [HA] = 1.0 mol dm-3 so Ka = [H+]2 / 1.00 = (0.00427)2 = 1.74 x 10-5 mol dm-3 Note also that Ka (like any equilibrium constant) changes with temperature, so we really ought to state the temperature at which the pH values were measured, and quote the value of Ka at this temperature.

pKa
The numeric values of Ka for weak acid are somewhat cumbersome, so sometimes pKa is quoted instead for weak acids. It relates to Ka in the same way as pH does to [H+]. pKa = -log10Ka or, rearranging Ka = 10-pKa

The smaller the value of pKa is, the larger the value of Ka and therefore the more ionized the weak acid is and so the stronger the weak acid is. e.g. acid chloroethanoic benzoic ethanoic hydrocyanic Ka 1.3x10-3 6.3x10-5 1.7x10-5 4.9x10-10 pKa 2.88 4.20 4.77 9.31 strongest weakest

e.g.

What is the pH of a 0.1 mol dm-3 solution of a weak acid with pKa = 2.88 ? pKa = 2.88 so Ka = 10-2.88 = 1.3x10-3 [H+] (Ka x [HA]) so [H+] = (1.3x10-3 x 0.1) = 0.0114 pH = -log10[H+] = -log(0.0114) = 1.94

Practice: 14) What is the pH of a 0.01 mol dm-3 solution of an acid with pKa = 4.20 ?

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F325 Acids, bases and buffers

Buffer Solutions
Definition: A buffer solution minimizes (or resists) changes in pH when a small amount of acid or alkali is added. The key ideas here are: i) it minimizes or resists the pH change not "maintains a constant pH, or cancels out the change". The pH does change, but only by a small amount not as much as it would if the small amount of acid/alkali were added to a solution which wasn't a buffer. ii) a small amount of acid or alkali can be added, but the buffering effect does not cope with the addition of large amounts of acid or alkali. Buffers are very important systems including in biochemistry. - blood is a buffer solution. - many skincare products are buffered at pH 5.5 (the pH of normal healthy skin) - citric acid and sodium citrate are often used in foods, listed as "acidity regulators" - detergents and shampoos are often buffered to stay slightly alkaline Buffers are made by dissolving a weak acid along with its conjugate base. A soluble salt of the acid (usually the sodium or potassium salt, but the ammonium salt may also be used) provides the supply of conjugate base ions. e.g. ethanoic acid is a weak acid: the conjugate base is the ethanoate ion. A good source of ethanoate ions would be sodium ethanoate. Ionic salts like this dissociate fully in aqueous solution, so the buffer solution could be made by dissolving ethanoic acid and sodium ethanoate in the solution. Another way of making the same buffer would be to start with an ethanoic acid solution, and to partially neutralize the solution using sodium hydroxide. This would form some sodium ethanoate in the solution, and so long as some of the ethanoic acid remained in excess, a buffer would be formed. What is in a buffer ? A buffer made from weak acid HA and conjugate base A- will contain: i) a high concentration of HA because most of the weak acid molecules remain undissociated HA(aq) H+(aq) + A-(aq) The equilibrium lies far to the left. ii) a high concentration of A- (the conjugate base) because as well the few A- from the dissociated HA, we also add A- ions in the form of e.g. the sodium salt. iii) a low concentration of [H+] from the few dissociated HA molecules, and because the added A- ions shift the position of the HA H+ + Aequilibrium further to the left.

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F325 Acids, bases and buffers How does a buffer resist changes in pH ? The buffer solution works because the position of equilibrium can move left or right: HA(aq) H+(aq) + A-(aq) If acid is added to the buffer, this is dealt with by the conjugate base A- ions. the concentration of H+(aq) increases due to the added acid the position of equilibrium shifts to the left to use up the added H+ ions to minimize the effect of the change (Le Chatelier) this is done by the conjugate base, A-(aq) reacting with the H+(aq) to form more HA(aq) If an alkali is added to the buffer, this is dealt with by the weak acid, HA. the concentration of OH-(aq) is increased the small concentration of H+ reacts with the OH- ions, neutralizing them: H+(aq) + OH-(aq) H2O(l) because of the decrease in H+(aq) concentration, the position of equilibrium moves to the right, dissociating more HA and replacing (most of) the H+ ions in the solution (minimizing the effect of the change Le Chatelier) There is a limit to how much buffering a solution can do: It cannot buffer against OH- ions any more once the HA has all been dissociated It cannot buffer against H+ ions any more once all the A- has been used up Calculating the pH of a buffer The pH of a buffer can be calculated using the equilibrium constant expression for the weak acid: Ka = [H+]eqm [A-]eqm [HA]eqm and as before we can approximate [HA]initial [HA]eqm

Similarly because we have added a lot of [A-] ions, the additional [A-] ions generated by the dissociation of HA will be insignificant, so [A-]eqm = [A-]initial Therefore rearranging, [H+] = Ka x [HA] [A-]

Where [HA] is the concentration of the acid from which you made the buffer and [A-] is the concentration of the salt of that acid (conjugate base) that you used to make the buffer. Once you know [H+] the pH is simply calculated as normal: pH = -log10[H+]

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F325 Acids, bases and buffers Examples: 1) The concentration of ethanoic acid in a buffer was 0.2 mol dm-3 and the concentration of sodium ethanoate was 0.1 mol dm-3 in the solution. What pH will the buffer have ?
(Ka for ethanoic acid = 1.7 x 10-5 mol dm-3)

[H ] = 1.7 x 10 x 0.2 0.1 pH = -log10(3.4x10-5)

-5

= 3.4 x 10 = 4.5

-5

2) A buffer is made up by adding 200cm3 of 0.1 mol dm-3 benzoic acid solution to 500cm3 of 0.1 mol dm-3 sodium benzoate solution. What pH will the buffer have ? (Ka of benzoic acid = 6.3 x 10-5 mol dm-3) moles of benzoic acid = 0.1 x (200/1000) = 0.02 moles of sodium benzoate = 0.1 x (500/1000) = 0.05 total volume of solution = 200cm3 + 500cm3 = 700cm3 [benzoic acid] = 0.02/0.7 = 0.0276 mol dm-3 [sodium benzoate] = 0.05/0.7 = 0.0714 mol dm-3 [H+] = 6.3x10-5 x 0.0276 = 2.43 x 10-5 0.0714 pH = -log10(2.43x10-5) = 4.61 3) 250cm3 of 0.1M sodium hydroxide solution of are added to 750cm3 of ethanoic acid solution of 0.1M concentration. What will be the pH of the resulting buffer ? (pKa for ethanoic acid = 4.8) moles of NaOH = 0.25 x 0.1 = 0.025 moles of CH3COOH = 0.75 x 0.1 = 0.075 In the neutralization, NaOH + CH3COOH CH3COO-Na+ + H2O So 0.025 moles of NaOH are used to neutralize 0.025 moles of CH3COOH, creating 0.025 moles of sodium ethanoate, and leaving 0.050 moles of ethanoic acid The total volume of the solution is now 250cm3 + 750cm3 = 1000cm3 (1dm3) So [CH3COOH] = 0.050 x 1.0 = 0.05 mol dm-3 [CH3COO-] = 0.025 x 1.0 = 0.025 mol dm-3 Ka = 10-pKa = 10-4.8 = 1.58x10-5 [H+] = 1.58x10-5 x 0.05 = 3.16x10-5 0.025 pH = -log10(3.16x10-5) = 4.5 Practice: 15) Calculate the pH at 25C of a buffer solution containing 0.05 mol dm-3 ethanoic acid and 0.10 mol dm-3 sodium ethanoate. (Ka for ethanoic acid = 1.7 x 10-5 mol dm-3 at 25C) 16) 4.42g of sodium methanoate, HCOO-Na+, is dissolved in 1.0dm3 of methanoic acid of concentration 0.15 mol dm-3 at 25C. What will the pH of the resulting buffer be ?
(Ka = 1.6 x 10-4 mol dm-3 for methanoic acid at 25C)

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F325 Acids, bases and buffers Designing a buffer for a given pH We may need to use this method "in reverse" to go from a specified pH to a "recipe" for HA and Aconcentrations to use to make a buffer of a specific pH. Example: Suggest concentrations of ethanoic acid and sodium ethanoate which would result in a buffer solution with a pH of 4.07 at 25C. (Ka for ethanoic acid = 1.7x10-5 mol dm-3 at this temperature). [H+] = 10-pH Ka = [H+][A-] [HA] [HA] = [H+] x [A-] Ka so [H+] = 10-4.07 = 8.51x10-5 mol dm-3 We know Ka and [H+], so we can rearrange this: in this case [HA] = 8.51x10-5 x [A-] 1.7x10-5

[HA] = 5.00 x [A-] Therefore we need a concentration of the acid which is five times the concentration of the salt of the weak acid. We can make the buffer using any concentrations we like, so long as they are in this ratio. Perhaps 0.5M HA and 0.1M A- would be chosen.

Buffering in blood
Healthy blood plasma requires a pH between 7.35 and 7.45. If the pH drops below 7.2 or above 7.6 the body is in serious trouble. A buffering system is therefore needed within the body to deal with small amounts of acid or alkali entering the bloodstream. The pH of blood is controlled by a mixture of buffers. The most important of these is the carbonic acid hydrogencarbonate ion buffer. Carbonic acid is formed in the blood when carbon dioxide dissolves in water. It is a weak acid: H2CO3(aq) H+(aq) + HCO3-(aq) The hydrogencarbonate ion, HCO3- is its conjugate base, and is present in blood in significant concentrations from our diet. Any increase in [H+(aq)] in the blood is dealt with by the HCO3- ions (the conjugate base) - the added H+ ions react with the hydrogencarbonate ions in the blood to form H2CO3 - moving the position of equilibrium to the left to remove the H+ which was added (Le Chatelier) Any increase in [OH-(aq)] in the blood is dealt with by the H2CO3 (the weak acid) - the added OH- ions react with the few H+ ions in the blood to form H2O - the position of equilibrium moves right, dissociating H2CO3 to replace (most of) the H+ ions in the blood. A common question is to calculate the concentrations of carbonic acid and hydrogencarbonate ions in blood. The ratio of HCO3-: H2CO3 can be calculated using the Ka value for carbonic acid (4.17 x 10-7 mol dm-3), and the pH of the blood in exactly the same way as previously.

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F325 Acids, bases and buffers

When we do this we find that the concentration of hydrogencarbonate ions in healthy blood is more than ten times the concentration of carbonic acid, in order to buffer at the correct pH.

Reactions of weak acids

When a weak acid reacts, it reacts more slowly than a strong acid of the same concentration. This is because [H+] is much lower, so there are fewer successful collisions involving the [H+] ion. Every mole of the acid will react, however. As the [H+] ions are used up, more [HA] splits up to produce ions, attempting to restore the equilibrium (Le Chatelier's principle). Eventually all the HA molecules will have dissociated and all the H+ ions reacted. This means that the same volume of alkali neutralizes a strong and a weak acid of the same concentration. e.g. In a titration, 20cm3 of 0.1M NaOH were required to neutralize 25cm3 of a hydrochloric acid solution. A propanoic acid solution of the same concentration was prepared. What volume of 0.1M NaOH would be required to neutralize 25cm3 of it ? Ans: 20cm3. The same number of moles of acid will react. The important thing to realize here is that YOU CAN'T TELL A STRONG AND WEAK ACID APART BY TITRATION. e.g. A 1g chunk of calcium carbonate was added to 100cm3 of 0.5M hydrochloric acid. i) what is the [H+] in the acid ? 0.5 mol dm-3 i) which reactant is in excess ? RFM CaCO3 = 40 + 12 + 48 = 100 => 0.01 moles Moles of HCl = 0.1 x 0.5 = 0.05 excess (0.02 needed) ii) what would you observe ? effervescence calcium carbonate would all dissolve A similar 1g chunk of calcium carbonate was added to 100cm3 of 0.5M ethanoic acid. (Ka for ethanoic acid = 1.7x10-5 mol dm-3) i) what is the [H+] in the acid ? [H+] = (Ka x [HA]) = (1.7 x 10-5 x 0.5) = 0.003 mol ii) which reactant is in excess ? still the acid there are 0.05M of ethanoic acid even though there are only 0.0003 moles of H+ iii) what would you observe ? bubbles produced MORE SLOWLY all the calcium carbonate STILL dissolves

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F325 Acids, bases and buffers Determining the strength of an acid To measure the strength of an acid, we need to determine the extent to which it is dissociated. If we know the concentration of the acid, we can determine what the concentration of H+ ions should be if it were fully dissociated and thereby determine if it is strong or weak by measuring its pH and calculating its actual [H+]. We may also want to compare weak acids to see which is stronger. - We can compare the pH of each acid in a solution of the same concentration, either using a pH probe, or using indicators - we can compare the rate at which each reacts with the same mass of a metal carbonate, or with a reactive metal such as magnesium - we can compare the ease with which electricity is conducted. The more ionized an acid is, the more ions (and therefore the more charge carriers) there are in the solution, and the better the conductivity will be - we can determine the enthalpy change of neutralization (the energy released when the acid reacts with OH- ions) which will be less for a weak acid because the energy released when H+ ions and OHions form a bond is offset in weak acids by the energy needed to dissociate the HA molecule and produce the H+ ions Using enthalpy of neutralisation We can measure the enthalpy change when an acid is neutralized by an alkali in the same way as we measured enthalpy changes for other reactions: by measuring a temperature change and then using Q = mcT and H = -Q/moles Definition: The standard enthalpy change of neutralization is the enthalpy change that occurs when 1 mole of water is produced during the reaction of an acid with an alkali under standard conditions. e.g. HCl + KOH KCl + H2O HNO3 + NaOH NaNO3 + H2O Hneut = -57.9 kJ mol-1 Hneut = -57.6 kJ mol-1

In fact we find that for any strong acid and any strong alkali, the value is the same. This is not unexpected we can reduce all of these equations to ionic equations by removing the spectator ions. When we do we find they are all the same reaction taking place: H+(aq) + OH-(aq) H2O(l) Even if we use sulphuric acid, which produces two hydrogen ions in solution rather than one, the result is the same because the definition is not based on moles of acid or alkali but on 1 mole of water being formed: H2SO4 + NaOH Na2SO4 + H2O Hneut = -57.9 kJ mol-1

If we measure the standard enthalpy change of neutralization when a weak acid such as ethanoic acid reacts with a strong alkali, e.g. sodium hydroxide, we find that Hneut is smaller (-57.1 kJ mol-1) p.14

F325 Acids, bases and buffers

Since the reaction which is taking place is the same, the difference must lie in ethanoic acid being weak rather than strong. What we are seeing is the energy needed to dissociate the HA molecules to form H+ ions. CH3COOH CH3COO- + H+ H = +ve (only bond breaking, no making) As the H+ is neutralized by the alkali, the position of equilibrium moves to the right, and energy that would otherwise have been given out as heat has to be used to break H-A bonds. Similarly with a weak base (e.g. ammonia), energy needs to be supplied to dissociate the base and produce OH- ions, so the enthalpy change on neutralization is lower. Experiments of this type give some measure of how strong or weak acids or bases are, but they are not particularly accurate.

Using indicators
The use of indicators (other than universal indicator) to compare strengths of acids may appear counter-intuitive. Surely an indicator would only tell you whether something is acidic or not? To see how this can be done we need to understand in more depth what indicators actually are, and how they work. Indicators have two colours, and change between these two colours depending on the pH. The pH at which an indicator changes colour is NOT (usually) pH 7.0 They change colour over a pH range (typically around 2 pH units). Over this range, the intensity of one colour is fading and the intensity of the other is increasing, so the colour is changing gradually. In the middle of the range, the colour is an equal mixture of the two. Indicators are weak acids, and therefore partially dissociated in aqueous solution. The undissociated acid is one colour in solution, and the conjugate base is the other colour. e.g. HIn H+ + Inmethyl orange red yellow If we add H+ (acid) to methyl orange, the position of equilibrium moves to the left to reduce the concentration of H+ and there is more of the red form and less of the yellow form i.e. the indicator turns red (Le Chatelier) If we add OH- (alkali) to methyl orange, this reacts with the H+ forming water and reducing the H+ concentration. The position of equilibrium moves right to create more H+, using up the red form of the indicator and creating more of the yellow form. Methyl orange has a published pH range of 3.2 4.4. This means that at pH lower than 3.2 it is red. From pH 3.2 to pH 4.4 it becomes less red and more yellow. It will be orange at pH 3.8 (the mid-range point).

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F325 Acids, bases and buffers By choosing different indicators, it is possible to "pin down" the pH of a weak acid solution to a range of pH values, and then using this suggested pH to calculate [H+] and, if the concentration of the acid is known, an estimate for Ka. Worked example: Bromocresol green has a pH range of 3.8 (yellow) to 5.4 (blue). Methyl orange has a pH range of 3.2 (red) to 4.4 (yellow). i) A solution of weak acid HA with 0.1 mol dm-3 concentration is tested with both indicators. With both indicators the colour is seen to be yellow. Suggest the pH of the acid solution. Answer: With bromocresol green the yellow indication tells us that the pH is less than the midpoint of the range. The midpoint is 4.6 (at which the colour will be green) so we can say that the pH of our acid is 4.5 or less. With the methyl orange the yellow indication tells us that the pH is higher than the midpoint of the range. The midpoint is at 3.8 so we can say that the pH of our acid must be 3.9 or more. We therefore suggest the pH of our solution is a value between 3.9 and 4.5, e.g. 4.2 ii) Using your suggested pH, find Ka for the acid HA. [H+] = 10-pH = 10-4.2 = 6.3x10-5 mol dm-3 Ka = [H+][A-] [HA] and for a weak acid solution [H+] = [A-] and [HA] is approx. the same at equilibrium as in the undissociated acid = 3.9x10-8 mol dm-3

Ka = 6.3x10-5 x 6.3x10-5 0.1

iii) Another acid, HZ, having the same concentration is also tested. It turns bromocresol green yellow, and methyl orange red. Suggest a pH for this acid. Answer: With bromocresol green, the yellow colour tells us our acid has a pH of 4.5 or less (midpoint = 4.6). With methyl orange the red colour tells us our acid has a pH of 3.7 or less (midpoint 3.8) Combining this data we know the pH is 3.7 or less, but how do we put a lower limit on the pH ? Remember this is a weak acid. If it were a strong acid its pH would be 1.0 (concentration of acid = 0.1mol dm-3), so the pH definitely can't be lower than 1.0 if our 0.1 mol dm-3 acid is only partially dissociated. One strategy is to choose a pH half way between these values: a pH of 2.35 would be half way between 3.7 and 1.0

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F325 Acids, bases and buffers

Acid-Base Titrations
When we add acid to an alkali, or vice versa, (e.g. during a titration) the pH does not change in a constant fashion. The way in which the pH changes as acid/alkali is added is shown using a pH curve. We need to be able to explain/interpret the shapes of these curves, and to sketch them. The shape is different depending on whether the acid and the alkali are strong or weak. Sketching pH curves 1) Strong acid, to which a strong alkali is added i) a gradual increase in pH from that of the original acid ii) a sudden sharp (vertical) change in pH iii) centre of the vertical part corresponds to pH 7 iv) a gradual increase in pH to that of the (diluted) alkali v) The vertical section corresponds to the addition of equal moles of acid (H+) and alkali (OH-)

Definition: The equivalence point is defined as the volume of added alkali (or acid) in a titration which is required to exactly neutralize the acid (or alkali). It therefore corresponds to the centre of the vertical section of the pH curve. 2) Strong acid, to which a weak alkali has been added i) The acidic part of the curve is the same as before ii) The vertical part extends over fewer pH units iii) The centre of the vertical section (equivalence point) corresponds to an acidic pH iv) pH increases more gradually throughout alkaline part v) finishing at the pH of the weak alkali

3) Weak acid to which a strong alkali has been added i) The acidic part starts at the pH of the weak acid ii) pH increases steadily over acidic section iii) the vertical section extends over fewer pH units iv) The centre of the vertical section (equivalence point) corresponds to an alkaline pH v) pH only changes very gradually with further addition of alkali, finishing at the alkali's pH

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F325 Acids, bases and buffers

4) Weak acid to which weak alkali has been added i) The acidic part starts at the pH of the weak acid ii) pH increases steadily iii) there is an indistinct equivalence point (no vertical section) corresponding to approximately pH 7 iv) pH continues to rise steadily over alkaline part v) finishing at the pH of the weak alkali

Interpreting a pH curve: 1) Look for the nature of the equivalence point. - does it lack a clear vertical section ? (weak acid weak alkali) - is the equivalence point at pH 7 and distinct (strong acid strong alkali) - is the equivalence point at acidic pH (strong acid weak alkali) - is the equivalence point at alkaline pH (weak acid strong alkali) 2) Look for the volume corresponding to the equivalence point in order to work out how many cm3 of alkali have been added to the acid (or vice versa). Choosing indicators for titrations The choice of a suitable indicator for a given titration is not random. Definition: The endpoint of a titration is when the indicator is midway between its two colours, i.e. has equal concentrations of HIn and In-. This is the midpoint of the pH range for the indicator. In choosing an indicator for a titration, we need to know over what pH range the equivalence point will be. We want the indicator to change colour when we reach the equivalence point, so we want the endpoint and the equivalence point to coincide. e.g. if we have an equivalence point at acidic pH, we will need to choose an indicator with a endpoint pH range which is acidic too. In order to get a sharp endpoint i.e. for the indicator colour to change with the addition of only a drop of acid or alkali, then we need to ensure that the pH range for the indicator corresponds to the vertical portion of the pH curve for that titration. If not, the indicator will change colour gradually and we wont be able to determine accurately how much acid/alkali to add. Universal Indicator Universal indicator is a MIXTURE of several different indicators, each chosen so its colour change over a different pH range, so the colour of the universal indicator changes several times over a wide range of pH values. Universal indicator is therefore NEVER suitable for titrations !

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F325 Acids, bases and buffers

Answers to practice questions:

1) 2) 3) 4) 5) 6) HBr is an acid. What is its conjugate base ? BrOH is a base. What is its conjugate acid ? H2O Identify the conjugate acid/base pairs in HNO3 + OH NO3 + H2O acid base conj base conj acid In a solution, [H+(aq)] = 10-4 mol dm-3. What is [OH-(aq)] ? 10-10 mol dm-3 + -3 An acid produces an [H (aq)] of 0.1 mol dm . What is its pH ? 1.0 + An acid has a pH of 3.0 What is the [H (aq)] ? 0.001 mol dm-3 0.30 0.0032 mol dm-3

7) What is the pH of a solution of nitric acid of concentration 0.50 mol dm-3 ? 8) What is the [H+] in a nitric acid solution with a pH of 2.5 ?

9) Calculate the pH of a 0.05 mol dm-3 solution of potassium hydroxide. (Kw = 10-14) 10-14 = [H+] x 0.05 => [H+] = 10-14/0.05 = 2 x 10-13 pH = -log10(2 x 10-13) = 12.7 or pH = 14 + log10(0.05) = 14 1.30 = 12.7

10) What is the [OH-] in a sodium hydroxide solution with pH 9.0 ? (Kw = 10-14) [H+] = 10-9 so 10-14 = 10-9 x [OH-] so [OH-] = 1x10-5 mol dm-3 11) calculate the pH of 0.0200 mol dm-3 of ethanoic acid. Ka = 1.74 x 10-5 mol dm-3 12) calculate the pH of 0.0100 mol dm-3 butanoic acid. Ka = 1.51 x 10-5 mol dm-3 13) calculate the pH of 0.500 mol dm-3 chloroethanoic acid. Ka = 1.38 x 10-3 mol dm-3 14) What is the pH of a 0.01 mol dm-3 solution of benzoic acid ? 3.23 3.41 1.58

[H+] = 0.00079 so pH = 3.1

15) Calculate the pH at 25C of a buffer solution containing 0.05 mol dm-3 ethanoic acid and 0.10 mol dm-3 sodium ethanoate. (Ka for ethanoic acid = 1.7 x 10-5 mol dm-3 at 25C) [H+] = 1.7x10-5 x 0.05 = 8.5x10-6 0.1 pH = -log10(8.5x10-6) = 5.07

16) 4.42g of sodium methanoate, HCOO-Na+, is dissolved in 1.0dm3 of methanoic acid of concentration 0.15 mol dm-3 at 25C. What will the pH of the resulting buffer be ? (Ka = 1.6 x 10-4 mol dm-3 for methanoic acid at 25C) HCOONa = 1 + 12 + 32 + 23 = RFM 68 moles = 4.42/68 = 0.065 so [A-] = 0.065 mol dm-3 -3 [HA] = 0.15 mol dm So [H+] = 1.6x10-4 x 0.15 0.065 pH = -log10(3.69x10-4) = 3.69x10-4 = 3.43

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