Part 1
Topic 4.3 ACIDS AND BASES
The Arrhenius Theory of acids and bases
Acids are substances which produce hydrogen ions in solution. Bases are substances which produce hydroxide ions in solution.
Neutralisation happens because hydrogen ions and hydroxide ions react to produce water.
Limitations of the theory Hydrochloric acid is neutralised by both sodium hydroxide solution and ammonia solution. In both cases, you get a colourless solution which you can crystallise to get a white salt - either sodium chloride or ammonium chloride.
In the sodium hydroxide case, hydrogen ions from the acid are reacting with hydroxide ions from the sodium hydroxide - in line with the Arrhenius theory. However, in the ammonia case, there don't appear to be any hydroxide ions! You can say that the ammonia reacts with the water it is dissolved in to produce ammonium ions and hydroxide ions:
This is a reversible reaction, and in a typical dilute ammonia solution, about 99% of the ammonia remains as ammonia molecules. Nevertheless, there are hydroxide ions there, and we can squeeze this into the Arrhenius theory. However, this same reaction also happens between ammonia gas and hydrogen chloride gas.
In this case, there aren't any hydrogen ions or hydroxide ions in solution - because there isn't any solution. The Arrhenius theory wouldn't count this as an acid-base reaction, despite the
fact that it is producing the same product as when the two substances were in solution.
The Bronsted-Lowry Theory of acids and bases
An acid is a proton (hydrogen ion) donor. A base is a proton (hydrogen ion) acceptor.
The relationship between the Bronsted-Lowry theory and the Arrhenius theory The Bronsted-Lowry theory doesn't go against the Arrhenius theory in any way - it just adds to it. Hydroxide ions are still bases because they accept hydrogen ions from acids and form water. An acid produces hydrogen ions in solution because it reacts with the water molecules by giving a proton to them. When hydrogen chloride gas dissolves in water to produce hydrochloric acid, the hydrogen chloride molecule gives a proton (a hydrogen ion) to a water molecule. A co-ordinate (dative covalent) bond is formed between one of the lone pairs on the oxygen and the hydrogen from the HCl. Hydroxonium ions, H3O+, are produced.
When an acid in solution reacts with a base, what is actually functioning as the acid is the hydroxonium ion. For example, a proton is transferred from a hydroxonium ion to a hydroxide ion to make water.
It is important to realise that whenever you talk about hydrogen ions in solution, H +(aq), what you are actually talking about are hydroxonium ions. The hydrogen chloride / ammonia problem This is no longer a problem using the Bronsted-Lowry theory. Whether you are talking about the reaction in solution or in the gas state, ammonia is a base because it accepts a proton (a hydrogen ion). The hydrogen becomes attached to the lone pair on the nitrogen of the ammonia via a co-ordinate bond.
If it is in solution, the ammonia accepts a proton from a hydroxonium ion:
If the reaction is happening in the gas state, the ammonia accepts a proton directly from the hydrogen chloride:
Either way, the ammonia acts as a base by accepting a hydrogen ion from an acid. Conjugate pairs When hydrogen chloride dissolves in water, almost 100% of it reacts with the water to produce hydroxonium ions and chloride ions. Hydrogen chloride is a strong acid, and we tend to write this as a one-way reaction:
In fact, the reaction between HCl and water is reversible, but only to a very minor extent. In order to generalise, consider an acid HA, and think of the reaction as being reversible.
Thinking about the forward reaction:
The HA is an acid because it is donating a proton (hydrogen ion) to the water. The water is a base because it is accepting a proton from the HA.
But there is also a back reaction between the hydroxonium ion and the A- ion:
The H3O+ is an acid because it is donating a proton (hydrogen ion) to the A- ion. The A- ion is a base because it is accepting a proton from the H3O+.
The reversible reaction contains two acids and two bases. We think of them in pairs, called conjugate pairs.
When the acid, HA, loses a proton it forms a base, A-. When the base, A-, accepts a proton back again, it obviously refoms the acid, HA. These two are a conjugate pair. Members of a conjugate pair differ from each other by the presence or absence of the transferable hydrogen ion. If you are thinking about HA as the acid, then A- is its conjugate base. If you are thinking about A- as the base, then HA is its conjugate acid. The water and the hydroxonium ion are also a conjugate pair. Thinking of the water as a base, the hydroxonium ion is its conjugate acid because it has the extra hydrogen ion which it can give away again. Thinking about the hydroxonium ion as an acid, then water is its conjugate base. The water can accept a hydrogen ion back again to reform the hydroxonium ion.
A second example of conjugate pairs This is the reaction between ammonia and water that we looked at earlier:
Think first about the forward reaction. Ammonia is a base because it is accepting hydrogen ions from the water. The ammonium ion is its conjugate acid - it can release that hydrogen ion again to reform the ammonia. The water is acting as an acid, and its conjugate base is the hydroxide ion. The hydroxide ion can accept a hydrogen ion to reform the water. Looking at it from the other side, the ammonium ion is an acid, and ammonia is its conjugate base. The hydroxide ion is a base and water is its conjugate acid. Amphoteric substances You may possibly have noticed that in one of the last two examples, water was acting as a base, whereas in the other one it was acting as an acid. A substance which can act as either an acid or a base is described as being amphoteric.
An acid is a substance which can behave as a proton donor. A proton can be represented as a hydrogen ion, H+. Any substance which contains hydrogen bonded to a more electronegative element can thus behave as an acid: HCl == H+ + ClH2SO4 == H+ + HSO4CH3COOH == H+ + CH3COOA base is a substance which can behave as a proton acceptor. Any species which has a lone pair of electrons can thus behave as a base: NH3 + H+ == NH4+
OH- + H+ == H2O CO32- + H+ == HCO32. Conjugate acid-base pairs Eg Cl- is the conjugate base of HCl; HCl is the conjugate acid of ClEg NH3 is the conjugate base of NH4+; NH4+ is the conjugate acid of NH3 Not all acids are equally good proton donors; in fact some give up their protons very reluctantly; conversely, some bases accept protons readily whereas others accept protons very reluctantly. The better an acid is at losing protons, the worse its conjugate base will be at accepting them. The better a base is at accepting protons, the worse its conjugate acid will be at losing them. Thus a strong acid will have a weak conjugate base, and a weak acid will have a strong conjugate base. Acids and bases can be ranked in order of decreasing strength; a list of common acids and their conjugate bases ranked in such a way is shown below: ACID H2NO3+ (NO2+ + H2O) H2SO4 HNO3 HCl H3O+ H2SO3 (SO2 + H2O) HSO4H3PO4 HF HNO2 CH3COOH H2PO4H2CO3 (CO2 + H2O) HSO3NH4+ HCN HCO3HPO42H2O OH== == == == == == == == == == == == == == == == == == == == BASE HNO3 HSO4NO3ClH2O HSO3SO42H2PO4FNO2CH3COOHPO42HCO3SO32NH3 CNCO32PO43OHO2+ H+ + H+ + H+ + H+ + H+ + H+ + H+ + H+ + H+ + H+ + H+ + H+ + H+ + H+ + H+ + H+ + H+ + H+ + H+ + H+
The strongest acids are at the top; these have the weakest conjugate bases. The strongest bases are at the bottom; these have the weakest conjugate acids.
Note that some species (eg H2O, HSO3-, HCO3- amongst others) appear in both columns. Such species can behave as either acids or bases and are said to be amphoteric. 3. Acid-base reactions Protons are not given up by acids unless there is a base which can accept them; and bases can only accept protons if there is an acid present to provide them. Reactions between acids and bases thus involve proton transfer from acid to base. A general acid-base reaction can thus be represented as follows: Acid 1 + Base 2 == Base 1 + Acid 2 Eg HCl + H2O == H3 O+ + ClAcid 1 Base 2 Acid 2 Base 1 Eg NH3 + H2O == NH4+ + OHBase 1 + Acid 2 Acid 1 Base 2 Eg O2- + H2O == OH- + OHBase 1 + Acid 2 Acid 1 + Base 2 Eg H3O+ + OH- == H2O + Acid 1 Base 2 Base 1 H2 O Acid 2
Amphoteric substances can undergo acid-base reactions with themselves: Eg H2O + H2O == H3O+ + OHAcid 1 + Base 2 Base 1 Acid 2 Eg HCO3- + HCO3- == CO32- + CO2 + H2O Acid 1 Base 2 Base 1 Acid 2 Any acid-base reaction which takes place in aqueous solution will reveal which of two acids is the stronger: Eg HCl(aq) + H2O(l) H3O+(aq) +Cl-(aq) goes 95% So HCl is a stronger acid than H3O+ CH3COOH(aq) + H2O(l) CH3COO-(aq) + H3O+(aq) only goes 1% So H3O+ is a stronger acid than CH2COOH CO32-(aq) + SO2(aq) [+ H2O(l)] CO2(aq) [+ H2O(l)] + SO32-(aq) goes 90% So SO2 is a stronger acid than CO2
THE IONIC PRODUCT FOR WATER, Kw
Kw and pKw
The important equilibrium in water Water molecules can function as both acids and bases. One water molecule (acting as a base) can accept a hydrogen ion from a second one (acting as an acid). This will be happening anywhere there is even a trace of water - it doesn't have to be pure. A hydroxonium ion and a hydroxide ion are formed.
However, the hydroxonium ion is a very strong acid, and the hydroxide ion is a very strong base. As fast as they are formed, they react to poduce water again. The net effect is that an equilibrium is set up.
At any one time, there are incredibly small numbers of hydroxonium ions and hydroxide ions present. Further down, we shall calculate the concentration of hydroxonium ions present in pure water. It turns out to be 1.00 x 10-7 mol dm-3 at room temperature. You may well find this equilibrium written in a simplified form:
This is OK provided you remember that H+(aq) actually refers to a hydroxonium ion.
Defining the ionic product for water, Kw Kw is essentially just an equilibrium constant for the reactions shown. You may meet it in two forms: Based on the fully written equilibrium . . .
. . . or on the simplified equilibrium:
You may find them written with or without the state symbols. Whatever version you come across, they all mean exactly the same thing! You may wonder why the water isn't written on the bottom of these equilibrium constant expressions. So little of the water is ionised at any one time, that its concentration remains virtually unchanged - a constant. Kw is defined to avoid making the expression unnecessarily complicated by including another constant in it. The value of Kw Like any other equilibrium constant, the value of Kw varies with temperature. Its value is usually taken to be 1.00 x 10-14 mol2 dm-6 at room temperature. pKw The relationship between Kw and pKw is exactly the same as that between Ka and pKa, or [H+] and pH.
The Kw value of 1.00 x 10-14 mol2 dm-6 at room temperature gives you a pKw value of 14. Try it on your calculator! Notice that pKw doesn't have any units.
The pH of pure water
Why does pure water have a pH of 7? That question is actually misleading! In fact, pure water only has a pH of 7 at a particular temperature - the temperature at which the Kw value is 1.00 x 10-14 mol2 dm-6.
This is how it comes about: To find the pH you need first to find the hydrogen ion concentration (or hydroxonium ion concentration - it's the same thing). Then you convert it to pH. In pure water at room temperature the Kw value tells you that: [H+] [OH-] = 1.00 x 10-14 But in pure water, the hydrogen ion (hydroxonium ion) concentration must be equal to the hydroxide ion concentration. For every hydrogen ion formed, there is a hydroxide ion formed as well. That means that you can replace the [OH-] term in the Kw expression by another [H+]. [H+]2 = 1.00 x 10-14 Taking the square root of each side gives: [H+] = 1.00 x 10-7 mol dm-3 Converting that into pH: pH = - log10 [H+] pH = 7 That's where the familiar value of 7 comes from.
The variation of the pH of pure water with temperature The formation of hydrogen ions (hydroxonium ions) and hydroxide ions from water is an endothermic process. Using the simpler version of the equilibrium:
The forward reaction absorbs heat. According to Le Chatelier's Principle, if you make a change to the conditions of a reaction in dynamic equilibrium, the position of equilibrium moves to counter the change you have made. According to Le Chatelier, if you increase the temperature of the water, the equilibrium will move to lower the temperature again. It will do that by absorbing the extra heat.
That means that the forward reaction will be favoured, and more hydrogen ions and hydroxide ions will be formed. The effect of that is to increase the value of Kw as temperature increases. The table below shows the effect of temperature on Kw. For each value of Kw, a new pH has been calculated using the same method as above. It might be useful if you were to check these pH values yourself. T (C) 0 10 20 25 30 40 50 100 Kw (mol2 dm-6) 0.114 x 10-14 0.293 x 10-14 0.681 x 10-14 1.008 x 10-14 1.471 x 10-14 2.916 x 10-14 5.476 x 10-14 51.3 x 10-14 pH 7.47 7.27 7.08 7.00 6.92 6.77 6.63 6.14
You can see that the pH of pure water falls as the temperature increases. A word of warning! If the pH falls as temperature increases, does this mean that water becomes more acidic at higher temperatures? NO! A solution is acidic if there is an excess of hydrogen ions over hydroxide ions. In the case of pure water, there are always the same number of hydrogen ions and hydroxide ions. That means that the water remains neutral - even if its pH changes.
The problem is that we are all so familiar with 7 being the pH of pure water, that anything else feels really strange. Remember that you calculate the neutral value of pH from K w. If that changes, then the neutral value for pH changes as well. At 100C, the pH of pure water is 6.14. That is the neutral point on the pH scale at this higher temperature. A solution with a pH of 7 at this temperature is slightly alkaline because its pH is a bit higher than the neutral value of 6.14. Similarly, you can argue that a solution with a pH of 7 at 0C is slightly acidic, because its pH is a bit lower than the neutral value of 7.47 at this temperature.
