Acids and Bases

Definitions
An acid is a proton donor, e.g. HCl. For example, consider the reaction between HCl and H2O. HCl + H2O Acid H3O+ + Cl-

In this reaction, HCl donates a proton to H2O. A base is a proton acceptor, e.g. NH3

For example, consider the reaction between NH3 and H2O. NH3 + H2O Base NH4+ + OH-

In this reaction, NH3 accepts a proton from H2O.

Conjugate acid-base pairs

When an acid loses a proton, the resulting species is its conjugate base. For example, CH3CO2H Acid NH4+ Acid CH3CO2Conjugate base NH3 Conjugate base + + H+ H+

Its called the conjugate base because if you imagine the reaction going backwards, it would be the species acting as a base (whether the reaction is actually an equilibrium or not!) When a base gains a proton, the resulting species is its conjugate acid. For example, NH3 + H+ Base OH- + H+ Base NH4+ Conjugate acid H2O Conjugate acid

In an exam, you will most likely be asked to label both pairs of conjugate acids and bases in a given equation. CH3CO2H Acid1 + H2O Base2 CH3CO2Con base1 + H3O+ Con acid2

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Acids and bases The terms conjugate acid and conjugate base are useful for describing certain situations, for example A solution of the conjugate base of a weak acid will be alkaline A solution of the conjugate acid of a weak base will be acidic A buffer can be made by mixing a solution of a weak acid with a solution of its conjugate base

Label the conjugate acid-base pairs in the following reactions, using appropriate symbols CH3CO2H + HCl CH3CO2H2+ + Cl-

HNO3

H2SO4

H2NO3+

HSO4-

HCl

HF

Cl-

H2F+

HCO3-

H2O

CO32-

H3O+

NH3

H3O+

NH4+

H2O

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Acids and Bases

Strong and weak

The terms strong and weak when applied to an acid or base indicate whether all or some of the molecules dissociate in aqueous solution. A strong acid fully dissociates in aqueous solution. HCl + H2O H3O+ + Cl-

For example,

The important point here is that if, for example, you make up a 0.2 mol dm-3 solution of hydrochloric acid, the concentration of H3O+ will also be 0.2 mol dm-3. We are interested in knowing the concentration of H3O+ so we can work out pH of acidic solutions. A strong base also fully dissociates in aqueous solution. NaOH Na+ + OH-

For example,

Again, this means we know the concentration of OH- ions if we know the concentration of the solution of NaOH, they will be the same. We are interested in knowing the concentration of OH- because it is related to the concentration of H+, so if we know it we can work out the pH of alkaline solutions. A weak acid does not fully dissociate in aqueous solution, even at high dilution. CH3CO2H + H2O CH3CO2- + H3O+

For example,

In this case, we cannot work out the concentration of H3O+ ions directly form the concentration of CH3CO2H, we also need to know the equilibrium constant for the acid dissociation. (To give an indication of what is going on in this situation, in a 0.1 mol dm-3 solution of ethanoic acid for example, it turns out that only 1.34% of the acid molecules are dissociated. The rest can dissociate, for example when it is neutralised by a base, also the reaction is in dynamic equilibrium, so isnt always the same 1.34% of molecules that are dissociated at any one time). A weak base also does not fully dissociate, even at high dilution. NH3 + H2O NH4+ + OH-

For example,

As above, we cannot work out the concentration of OH- (and therefore H3O+) without knowing the equilibrium constant for the above reaction. The point about even at high dilution is that if a weak acid or base is diluted, they do dissociate a little more, but they never manage to dissociate fully.

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Acids and bases

The p function
The topic acids and bases involves lots of small numbers, which have to be written in exponential form, such as 1 x 10-3. To make life easier (!) chemists often talk about the p function of a value rather, than the value itself. The p function of any value is the log10 of it. What is the p value of 1.00 x 10-3?

Answer = 3.00 Most commonly, you will be using the p value of the concentration of H3O+ ions, which is known as pH. However, you will need to be comfortable using the p value of other things, such as pOH, pKw, pKa, pKb and pKin If a solution has a concentration of H3O+ ions of 0.400 mol dm-3, calculate the pH of this solution.

Answer = 0.398 If the value of Kw at 398K is 1.20 x 10-14, calculate pKw at this temperature.

Answer = 13.9 You also need to be able to work back from a p value to the original value itself. What you do is change the sign of the p value work out the inverse log10 of the p value

What is the value of Kw at 298 K if pKw is 14.0?

Answer = 1.00 x 10-14 mol2 dm-6 What is the value of [H3O+] if the pH of a solution is 1.00?

Answer = 0.100 mol dm-3

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Acids and Bases

The auto-ionisation of water

Water reacts with itself, reaching dynamic equilibrium with aqueous protons and hydroxide ions. H2O + H2O H3O+ + OH-

The equilibrium constant for this reaction, Kw is 1.0 x 10-14 mol2 dm-6 at 298K NB it is a different value at different temperatures! The equilibrium expression for this reaction is Kw = [H3O+][OH-]

The pH of pure water In pure water, there is no additional source of protons or hydroxide ions. From the top equation, you can see that for every aqueous proton, there will also be an aqueous hydroxide ion, so their concentrations will be equal. In pure water, the concentrations of [H3O+] and [OH-] are the same Therefore, Kw = [H3O+]2 and Kw = [OH-]2

The concentration of [H3O+] and [OH-] is the square root of the Kw value

Calculate the pH of pure water at 298K, where Kw is 1.00 x 10-14 mol2 dm-6

Answer = 7.00 Calculate the pH of pure water at 398K, where Kw is 1.1 x 10-14 mol2 dm-6

Answer =6.98 What would be the pOH?

Answer = also 6.98. pH and pOH are equal in pure water to each other whatever the temperature. Using 14-pH only works at 298K.

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Acids and bases Auto-ionisation of water, endothermic or exothermic? Based on the calculation on the previous page, you can deduce whether the autoionisation of water is endothermic or exothermic. When heated, the equilibrium constant increases, which means the position of equilibrium has shifted to the right-hand side Increased heat favours the endothermic pathway (Le Chatelier) Therefore the forward reaction is endothermic

NB you could refer to the decrease in pH as being evidence that the position of equilibrium has shifted to the right-hand side. Some important points In pure water, the [H3O+] = [OH-] What makes water neutral is that the concentrations of aqueous protons and hydroxide ions are the same, which makes the pH and pOH also the same For pure water at 298K, pH and pOH are both 7, which is neutral for this temperature. At different temperatures, for pure water, pH and pOH will be equal to each other, but not equal to 7

Acidic and alkaline solutions

An acidic solution has a greater concentration of aqueous protons than hydroxide ions. An alkaline solution has a greater concentration of aqueous hydroxide ions.

In any aqueous solution, whether neutral, acidic or alkaline, the Kw expression can relate the concentration of protons to hydroxide ions. To work out the pH of an acidic solution, once you have worked out the [H3O+] you simply work out the p value and that is the pH (see examples later). To work out the pH of an alkaline solution, you need to work out the [OH-] ions and then relate that to the [H3O+] using the Kw expression (see examples later). At 298K, [H3O+] = 1 x 10-14 or [OH-] or pH + pOH = 14. How you calculate the [H3O+] or[OH-] depends on whether you or dealing with a strong or weak acid or base.

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Acids and Bases

Strong acids
As we have seen, strong acids dissociate fully in aqueous solution, so it is very easy to work out the concentration of aqueous protons from the concentration of the acid. Calculate the pH of 0.200 mol dm-3 HNO3.

Answer = 0.699 Calculate the pH of 0.010 mol dm-3 HCl.

Answer = 2.00 Calculate the pH of 0.050 mol dm-3 H2SO4, assuming both protons fully dissociate.

Answer = 1.00 In reality, the dissociation of sulphuric acid is more complicated. The first proton fully dissociates, whereas the resulting HSO4- ion acts as a weak acid. H2SO4 + H2O HSO4- + H2O HSO4- + H3O+ SO42- + H3O+

The second dissociation is shifted backwards by the H3O+ ions in the first one, so does not dissociate as much as it would in the absence of the first reaction. This is an important point, it has come up in examinations. Another consequence of the fact that HSO4- is a weak acid is that a solution of sodium hydrogen sulphate will be acidic, due to the second reaction above. This fact enable HSO4ions to be distinguished from SO42- ions. Both form a white precipitate with BaCl2 solution but in the case of a hydrogensulphate ion being present the initial solution will be acidic to litmus paper.

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Acids and bases

Strong bases
Strong bases also fully dissociate, so the concentration of OH- ions can be worked out easily from the concentration of the base. Assume that the temperature is 298K. Calculate the pH of 0.200 mol dm-3 NaOH.

Answer = 13.3 Calculate the pH of 0.010 mol dm-3 KOH

Answer = 12.0 Calculate the pH of 0.050 mol dm-3 Ba(OH)2.

Answer = 13.0 NB At 298K [H3O+] = 1 x 10-14 / [OH-] pH + pOH = 14. thisisrevision.com

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Acids and Bases

Weak acids
Weak acids do not fully dissociate, in fact, the vast majority of a weak acids molecules are not dissociated in aqueous solution. for ethanoic acid CH3CO2H + H2O CH3CO2- + H3O+ = [CH3CO2-][H3O+] [CH3CO2H] units mol dm-3

the acid dissociation constant is Ka

When calculating the pH of a solution of a weak acid, we have to make the following assumptions the concentrations of [CH3CO2-] and [H3O+] are the same. This is true because for each aqueous proton we also get an ethanoate ion, and also the concentration of aqueous protons due to auto-ionisation of water is negligible (1 x 10-7 mol dm-3). there is no significant difference between the [CH3CO2H] at equilibrium and its concentration when the solution was made up. This is true because very few of the ethanoic acid molecules are dissociated at any one time. = [H3O+]2 [CH3CO2H]start

For calculations, the equation becomes Ka

If you are asked for a definition of Ka, give the top expression. When doing a weak acid calculation, use the equation above. Calculate the pH of 0.100 mol dm-3 ethanoic acid, given that Ka for ethanoic acid is 1.80 x 10-5 mol dm-3

Answer = 2.87 Calculate the Ka of propanoic acid, given that the pH of a 0.100 mol dm-3 solution is 3.40

Answer = 1.58 x 10-6 mol dm-3 Page 9 of 28 thisisrevision.com

Acids and bases

Inductive effects in weak acids

The relative strength of a weak acid is determined by the stability of the ion that is created when it loses its proton (its conjugate base). From the two examples on the previous page, how can you tell that propanoic acid is a weaker acid than ethanoic acid?

Hint: compare the Ka values and look at the Ka expression. Now Write equations to show the dissociation of ethanoic acid and propanoic acid.

indicate the electron releasing effect in propanoic acid.

this effect increases the strength of the O-H bond and destabilises the propanoate ion. which in turn makes protons less likely to be released by propanoic acid, so it is less acidic.

Electronegative atoms are electron withdrawing, such as Cl. How would you expect the Ka for chloroethanoic acid and the pH of a 0.100 mol dm-3 solution of it to differ to the case for ethanoic acid?

Ka would be bigger and the pH would be lower.

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Acids and Bases

Buffer solutions
A buffer solution is a solution that resists changes in pH when small amounts of acid, base or water are added to it. A buffer typically consists of a weak acid (e.g. CH3CO2H) whose dissociation is suppressed by a comparable concentration of its conjugate base (CH3CO2-). Addition of acid can be countered by the following reaction: CH3CO2H

CH3CO2- + H+

So, the added acid is replaced by undissociated ethanoic acid molecules. Addition of base can be countered by the following reaction: CH3CO2- + H2O

CH3CO2H + OH-

So, the added base is neutralised by undissociated ethanoic acid molecules. Calculations on buffers Doing past paper exam questions will show you that this kind of buffer can be made simply by mixing solutions of the weak acid, e.g. ethanoic acid and its conjugate base in the form a salt, e.g. sodium ethanoate. this kind of buffer is also formed when a weak acid is titrated with a base, as there will be a point in the titration when a mixture of the acid and the salt is formed.

Obviously it makes your life easier if you spot which of the above situations you are in! In either case, the Ka expression for the weak acid is still true, but it is no longer possible to say that the concentration of the aqueous protons and ethanoate ions are the same. Ka = [CH3CO2-][H3O+] [CH3CO2H]

which for a buffer is usually thought of as Ka = [Salt][H3O+] [Acid]

Some people prefer to use the equation in its log form, which is pH = pKa + log { [salt]/[acid] } See the next page for calculation examples.

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Acids and bases Buffers formed by mixing solutions of acid and salt molecules Calculate the pH of a buffer formed by mixing 6.00 g of ethanoic acid and 8.20g of sodium ethanoate in distilled water, made up to 500 cm3, given that Ka for ethanoic acid is 1.80 x 10-5 mol dm-3. calculate the moles of each substance present, by using their RMMs

calculate the concentration of ethanoic acid and sodium ethanoate present

using the Ka expression for buffers, calculate the [H+] and the pH

Answer = 4.74 Note from the above example, that when the concentration of salt and acid is the same, the pH of the buffer is simply the same as the pKa of the weak acid you are making it from. Also, a buffer works best at this special point, so by knowing the pKa values for a selection of weak acids you could choose the best one to make a buffer with a certain pH.

Sometimes you are given information about the relative amounts of salt and acid species. Calculate the pH of a buffer made from ethanoic acid and sodium ethanoate where the ratio of salt : acid concentrations is 2:3, given that Ka for ethanoic acid is 1.80 x 10-5 mol dm-3.

Answer = 4.56 Page 12 of 28 thisisrevision.com

Acids and Bases Buffers formed during titrations, by mixing acid and alkali solutions. Calculate the pH of a buffer made when 12.5 cm3 of sodium hydroxide is added to 25.0 cm3 of ethanoic acid, given that Ka for ethanoic acid is 1.80 x 10-5 mol dm-3, and both solutions are 0.100 mol dm-3. write the equation for the reaction

calculate the moles of ethanoic acid and sodium hydroxide present in each solution before mixing

calculate the moles of ethanoic acid and sodium ethanoate present in the solution after they are mixed and the reaction has taken place

moles of sodium ethanoate formed

moles of ethanoic acid remaining un-neutralised

calculate their concentrations

work out the pH of the solution using the Ka expression for buffers

Answer = 4.74 NB these questions are much faster if you spot that a 1:1 ratio of salt and acid would be formed, therefore pKa = pH. However, if it is not a 1:1 buffer, these methods will find you the right answer. This situation occurs when a weak acid is titrated with the alkali in the burette. Page 13 of 28 thisisrevision.com

Acids and bases Other buffering systems Amino acids can act as buffers, as they have an acidic and a basic group present in the same molecule. See Acids and Bases 2 for a full discussion. One of the reactions that buffers blood is a mixture of hydrogen carbonate and carbonate ions. The equations for this system are dissociation equation Ka expression HCO3- + H2O Ka = CO32- + H3O+

[CO32-][H3O+] [HCO3-] HCO3CO32- + H2O

when acid is added when base is added

CO32- + H+

HCO3- + OH-

Another buffer is formed during titration of NaHSO4. The HSO4- ion is a weak acid and its conjugate base SO42- formed the other part of the buffering system. A mixture of HCN (a weak acid) and CN- (its conjugate base) is often used in organic chemistry for addition of HCN to carbonyl compounds.

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Acids and Bases

Titration curves
In an acid-base titration, an acid and a base are reacted together. One goes in the burette, and the other goes in the conical flask. In acids and bases questions, we are concerned with plotting the pH variation during the titration versus the volume of solution added from the burette. To understand titration curves, it is very important to be able to visualise the contents of the conical flask, so you can understand how to work out or estimate the pH. The shapes of titration curves are categorised by the sorts of acids and bases that are reacting. The combinations are Hydrochloric acid and sodium hydroxide Ethanoic acid and sodium hydroxide Hydrochloric acid with ammonia Ethanoic acid with ammonia

Strong acid with strong base Weak acid with strong base Strong acid with weak base Weak acid with weak base

Each of the curves (except the last one) has a rapid change in pH (steep section) about the point at which moles of acid = the moles of base. The point at which moles of acid = moles of base is known as the equivalence point. The pH at the equivalence point is only seven for a strong acid with strong base titration, otherwise it will vary depending on what salt is formed in the conical flask when the acid and base have neutralised each other. At the equivalence point the mixture contains the salt that is produced when the acid and base neutralise each other. An indicator is a substance that changes colour over a particular pH range of about two units, for example phenolphthalein is colourless at pH 8 and below, but bright pink above pH 10. Different indicators have a different pH range about which they change colour. The indicator is chosen so that it changes colour about a pH which matches the point during the titration when the pH is changing rapidly. This way, the end point (when the indicator changes colour) will indicate the equivalence point (when the moles of acid = the moles of base). During titrations where one or more of the components is weak, a buffer will form. The buffer will be most effective when the moles of salt and acid molecules are equal. If the reaction equation is 1:1 between acid and base, and the concentration of acid and base solutions are the same, the volume at the equivalence point will be equal to the volume of solution that starts off in the conical flask. reality, the whole point of a titration is that usually one of the concentrations is unknown. By finding out what volume of a solution with a known concentration reacts with another volume of a solution of unknown concentration, you can work out the unknown concentration, as long as you know the equation! thisisrevision.com

In this topic you know the concentration of both the acid and alkali solutions. In

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Acids and bases

Strong acid versus strong base

A 25.0 cm3 sample of 0.100 mol dm-3 hydrochloric acid is titrated against 50.0 cm3 of 0.100 mol dm-3 sodium hydroxide solution. Sketch a curve of pH versus volume of sodium hydroxide added. This is a strong acid strong base curve, which makes things a little more simple than they might otherwise be, for two reasons. there will no buffer to worry about the pH at the equivalence point will be 7 (as NaCl does not affect the pH of water)

Work out the pH in the conical flask before any sodium hydroxide solution has been added. The concentration of H+ ions is also 0.1 mol dm-3, because hydrochloric acid is a strong acid. So the pH is log[0.1] = 1. Work out the pH in the conical flask after 50 cm3 of the sodium hydroxide solution has been added. At this point in the reaction, the hydrochloric acid has been swamped with excess sodium hydroxide, so it is acceptable for a sketch to simply use the pH of the sodium hydroxide solution in the burette. The concentration of OH- ions is 0.1 mol dm-3 because sodium hydroxide solution is a strong base. The pOH is therefore log[0.1] = 1, so providing the solution is at room temperature the pH will be 14 - 1= 13. Sketch the curve below. pH Finish pH 14--log[0.1] 13

Start pH = -log[0.1] =1

Equivalence point Volume = 25 cm3 pH = 7 (strong acid-strong base)

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Acids and Bases

Weak acid versus strong base

A 25.0 cm3 sample of 0.100 mol dm-3 ethanoic acid is titrated against 50.0 cm3 of 0.100 mol dm-3 sodium hydroxide solution. Sketch a curve of pH versus volume of sodium hydroxide added. Ka for ethanoic acid is 1.80 x 10-5 mol dm-3. As this titration involves a weak acid, a buffer will form when the ratio of salt:acid is 1:1. To understand the curve, it is important to have a good idea about what is in the contents of the conical flask at various points during the titration. NB the reaction occurring is CH3CO2H + NaOH CH3CO2Na + H2O

At the start: there is only aqueous ethanoic acid in the conical flask. We can calculate its pH using the method for a weak acid. Show this

Answer = 2.87 After 12.5 cm3 of sodium hydroxide solution has been added: there is a mixture of sodium ethanoate formed by the above reaction (salt) and ethanoic acid that has not yet been neutralised because not enough sodium hydroxide has been added. This mixture of salt and acid is a buffer, so we can work out the pH at this point using the buffer equation. In fact, at this point the amounts of sodium ethanoate and ethanoic acid in the flask are exactly equal, so the pH turns out to be the same as the pKa value for the acid. Show this

Answer = 4.74 After 25 cm3 of sodium hydroxide solution has been added: the equivalence point has been reached and the salt formed in the conical flask is sodium ethanoate. Sodium ethanoate is the salt of a weak acid made with a strong base. The ethanoate ion is a weak base, so the solution of sodium ethanoate formed at the equivalence point has the following reaction occurring in it. CH3CO2- + H2O CH3CO2H + OH-

The creation of OH- ions in the solution makes the pH at the equivalence point above seven. There is a way of calculating exactly what the pH would be, but for a sketch it is good enough simply to use a pH of 9 for the equivalence point in a weak acid-strong base titration. After 50 cm3 of sodium hydroxide solution has been added: the ethanoic acid has been swamped by an excess of sodium hydroxide, so it is acceptable for a sketch to use the pH of the sodium hydroxide solution in the burette, i.e. 14--log[0.1] 13. Page 17 of 28 thisisrevision.com

Acids and bases

Weak-acid vs. strong-base curve weak acid in conical flask.

Sketch the curve for 0.100 mol dm-3 ethanoic acid vs sodium hydroxide (described above). pH

Finish pH

Buffer pH

Equivalence point pH

Start pH

25

Volume of NaOH added / cm3 50

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Acids and Bases Weak acid versus strong base continued A 25.0 cm3 sample of 0.100 mol dm-3 sodium hydroxide is titrated against 50.0 cm3 of 0.100 mol dm-3 ethanoic acid solution. Sketch a curve of pH versus volume of ethanoic acid added. Ka for ethanoic acid is 1.80 x 10-5 mol dm-3. This example is very similar to the previous one, only this time the acid is being added to the base. NB the reaction occurring is still CH3CO2H + NaOH CH3CO2Na + H2O

At the start: there is only sodium hydroxide solution in the conical flask, so the pH can be worked out using the method for a strong base. Show this

Answer = 13.0 As the reaction proceeds and ethanoic acid is added to the conical flask, it is converted into sodium ethanoate. The mixture of un-neutralised sodium hydroxide and sodium ethanoate formed is not a buffer. After 25 cm3 of ethanoic acid solution has been added: the equivalence point has been reached and the salt formed in the conical flask is sodium ethanoate. As in the previous example, the pH of the aqueous sodium ethanoate is above seven, due to the basic nature of the ethanoate ion. CH3CO2- + H2O CH3CO2H + OH-

After 50 cm3 of ethanoic acid solution has been added: there is a mixture of excess ethanoic acid and sodium ethanoate formed during the titration, and this mixture is a buffer. In fact, at this point the amounts of sodium ethanoate and ethanoic acid in the flask are exactly equal, so the pH turns out to be the same as the pKa value for the acid. Show this

NB the point at which the buffer forms and the pH = pKa for the acid will either occur at the half-equivalence point (previous example) or at twice the equivalence point (this example). NB to help you work out which side of the graph the buffer will be on, if a weak acid is involved, then the buffer formed will have an acidic pH. So, if you are starting with a base in the conical flask for example, then the buffer will have to occur on the other side of the graph, because the pH values on the left hand side will be alkaline rather than acidic.

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Acids and bases

Weak-acid strong-base curve strong base in conical flask.

Sketch the curve for 0.100 mol dm-3 sodium hydroxide vs. ethanoic acid (described above). pH

Start pH

Equivalence point pH

Buffer / End pH

25

Volume of CH3CO2H added / cm3 50

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Acids and Bases

Titrations involving weak bases

As weak bases are no longer on the Edexcel syllabus you could choose to ignore this, but they could be asked about by analogy with weak acids in synoptic questions. Weak bases do not fully dissociate, even at high dilution. NH3 + H2O Kb = NH4+ + OH[NH4+ ][OH-] [NH3]

Using ammonia, the dissociation equation is The base dissociation equation is How this equation is used depends on the situation:

If you are working out the pH of a weak base, then the concentration of [NH4+ ] = [OH], and the starting concentration of the ammonia can be used in place of the actual equilibrium concentration (see the weak acids section for a full explanation of these approximations). Therefore, the equation to use is Kb = [OH-]2 [NH3]

Calculate the pH of a 0.100 mol dm-3 solution of ammonia, given that Kb for ammonia is 2.00 x 10-5 mol dm-3.

Answer = 11.1 If you are working out a buffer formed from a mixture of salt (e.g. NH4Cl) and weak base (e.g. NH3), then the equation must stay in its original form.

Calculate the pH of a buffer solution in which the concentrations of ammonia and ammonium chloride are 0.100 mol dm-3 and 0.100 mol dm-3 respectively, given that Kb for ammonia is 2.00 x 10-5 mol dm-3.

Answer = 9.30 NB when the concentration of the salt and base molecules is the same, the buffer is most effective and the pH is equal to 14-pKb. Give the equations that occur when a basic buffer has acid and base added to it.

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Acids and bases

Weak base versus strong acid

A 25.0 cm3 sample of 0.100 mol dm-3 ammonia solution is titrated against 50.0 cm3 of 0.100 mol dm-3 hydrochloric acid solution. Sketch a curve of pH versus volume of hydrochloric acid added. Kb for ammonia solution is 2.00 x 10-5 mol dm-3. NB the reaction occurring is NH3 + HCl NH4Cl

At the start: There is only aqueous ammonia solution in the flask, so we can work out its pH using the method for a weak base. Show this

Answer = 11.1 After 12.5 cm3 of hydrochloric acid has been added: there is a mixture of ammonium chloride formed and un-reacted ammonia solution. This is a buffer, so we can work out the pH using the buffer equation. In fact, there is an exactly equal amount of ammonia molecules as ammonium ions, so the pH is equal to 14-pKb Show this

After 25 cm3 of hydrochloric acid has been added: the equivalence point has been reached and the salt in the conical flask is ammonium chloride. As ammonia is a weak base, the ammonium ion is a weak acid and the solution in the conical flask has the following reaction occurring inside it. NH4+ + H2O NH3 + H3O+

The creation of H3O+ ions in the solution makes the pH at the equivalence point below seven. There is a way of calculating exactly what the pH would be, but for a sketch it is good enough simply to use a pH of 5 for the equivalence point in a strong acid-weak base titration. After 50 cm3 of hydrochloric acid has been added: the ammonia solution has been swamped with hydrochloric acid so for a sketch the pH is taken to be the same as the pH of the hydrochloric acid in the burette, i.e. log[0.1] = 1.

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Acids and Bases

Weak-base vs. strong-acid curve Weak base in conical flask.

Sketch the curve for 0.100 mol dm-3 ammonia solution vs. hydrochloric acid (described on previous page). pH Start pH

Buffer pH

Equivalence point pH

Finish pH

25

Volume of HCl added / cm3 50

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Acids and bases Weak base versus strong acid continued A 25.0 cm3 sample of 0.100 mol dm-3 hydrochloric acid is titrated against 50.0 cm3 of 0.100 mol dm-3 ammonia solution. Sketch a curve of pH versus volume of ammonia solution added. Kb for ammonia solution is 2.00 x 10-5 mol dm-3. This is very similar to the previous example but the opposite way round. NB the reaction occurring is still NH3 + HCl NH4Cl

At the start: There is only hydrochloric acid in the flask so we can use the method for a strong acid to work out the pH. Show this

Answer = 1.00 As ammonia solution is added to the conical flask, mixture of ammonium chloride formed and un-reacted hydrochloric acid is created, and this mixture is not a buffer! When 25 cm3 of ammonia solution has been added: the equivalence point has been reached and the conical flask contains the salt ammonium chloride. As this is the salt of a weak base with a strong acid, it makes the solution acidic, due to the following reaction: NH4+ + H2O NH3 + H3O+

When 50 cm3 of ammonia solution has been added: there is a mixture of additional ammonia in the conical flask and ammonium chloride formed at the equivalence point. This is a buffer, so we can find out its pH using the buffer equation. In fact, the amount of ammonia and ammonium chloride is exactly the same at this point, so the pH is equal to the 14-pKb. Show this

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Acids and Bases

Weak-base vs. strong-acid curve strong acid in conical flask.

Sketch the curve for 0.100 mol dm-3 hydrochloric acid vs. ammonia (described on previous page). pH Finish and buffer pH

Equivalence point pH

Start pH

25

Volume of NH3 added / cm3 50

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Acids and bases

Indicators
Indicators are weak acids or bases where the protonated and deprotonated forms of the molecule are different colours. For example, imagine is a weak acid where the acid molecule (HA) is red, whereas the conjugate base (A-) is blue, and the acid dissociation constant is 1.0 x 10-7 mol dm-3. The dissociation equation is HA red A- + H+ blue

To understand how such an acid can act as an indicator, imagine how the equilibrium would respond if it were occurring in an acidic solution or an alkaline solution. In an acidic solution: The increased concentration of H+ ions shifts the position of equilibrium to the left hand side, so the solution appears red. In an alkaline solution: The increased concentration of OH- ions react with the H+ ions the equilibrium position shifts to the right hand side, so the solution appears blue.

To find out the pH about which an indicator changes colour we can use the acid dissociation equation for the indicator. The acid dissociation equation is Ka = [A- ][H+] [HA]

The indicator changes colour when the concentration of [A- ] and [HA] are equal, because at this point an excess of either colour molecule would be obtained if a drop of acid or base were added to the solution. At this point, you can see from the equation that the values of [A- ] and [HA] cancel, leaving Ka = [H+], so the pH about which an indicator changes colour is given by pH = pKa. For the indicator we are using as an example, the Ka is 1 x 10-7 mol dm-3 so the pH about which it changes colour is pKa = -log[1 x 10-7] = 7. In order for the solution to be identifiably one colour or the other, there must be a 10:1 excess of whichever species. So, the pH at which the solution is blue can be found by making [A- ] = 10 and [HA] = 1. Show this

the pH at which the solution is red can be found by making [A- ] = 1 and [HA] = 10. Show this

Consequently an indicator changes colour over a pH range of about two units.

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Acids and Bases Indicators continued An indicator is chosen so that it changes colour at a pH about which the pH of the solution in the conical flask is changing rapidly. As you have seen from titration curves, the steep section (rapid change of pH) occurs at the equivalence point, so an indicators end-point must also occur at the same volume, thereby indicating the volume at which the acid or base has in the conical flask has been neutralised.

For a given concentration of solutions involved in the titration, the strong acidstrong base curve has the longest steep section, so the largest number of indicators can be used. As long as the solutions of acid and base are not very dilute, any indicator will work.

The weak acid-strong base curve has a shorter steep section that is above seven, so an indicator must be chosen that changes colour at a pH above seven, such as phenolphthalein. When adding alkali from the burette the colour change is colourless to pink.

The weak base strong acid curve also has a shorter steep section that is below seven, so an indicator must be chosen that changes colour at a pH below seven, such as methyl orange. When adding acid from the burette the colour change is orange to red.

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Acids and bases The remaining factor to be considered is that the acid and salt molecules of an indicator are of significantly different colours and that the colours are intense, to make it easier to detect the end point. NB A titration involving a weak acid and a weak base does not have a steep section, so any indicator would change colour gradually and be no use in indicating the equivalent point of the reaction. For this reason, we never titrate weak acids with weak bases in volumetric analysis.

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