Unit 4.

4 Acid-base equilibria Define pH pH = -log10[H+] Define Ka with units For acid HA

no units [H+][A-]
-3

Acid dissociation constant Ka = [HA] moldm Temperature dependent, Ka varies with different bases Define Kw with units Temperature dependent, Define pKa Ionic product of water

Kw = [H3O+] [OH]

mol dm

-6

pKa = log10 Ka

Define pKw pKw = log10 Kw Understand the terms strong and weak as applied to acids and bases Difference between acid and acidic solution: HCl acts as an acid when it dissolves in water and donates its proton to the water molecule Solution is acidic because concentration of H3O+ ions is greater than conc of OH- ions Strong/weak acid fully/partially ionised Strong/weak base fully/partially dissociate Conc No of moles of acid dissolved in a given vol of water The greater the value of Ka the stronger the acid HA Strength of acid, measured by equil constant (which determines the POE) HCl(aq) + H2O(l) H3O+(aq) + Cl-(aq) Equil lies so far to RHS that acid is considered to be completely ionised(strong acid) Recall the Brnsted-Lowry theory and use it to identify acids-bases Identify acid-base conjugate pairs and relate them by means of suitable equations Students are not expected to recall the Lewis theory of acids and bases Monoprotic/monobasic acid Diprotic/dibasic acid Acid Proton donor Acid 1 Base 2 H2SO4 + H 2O Acid 3 Base 2 HSO4+ H 2O Acids that have a single proton to donate/accept Acids that have a two protons to donate/accept Base Proton acceptor Acid 2 Base 1 Ionisation of H2SO4 in water occurs in 2 stages + HSO4- is conjugate base of H2SO4 but conjugate acid of SO42H3O + HSO4 Acid 2 Base 3 H3O+ + SO42-

Calculate the pH of solutions of strong acids and strong bases and of weak acids given Ka Explain the action of a buffer solution and calculate its pH from suitable data based on the equations for the equilibria involved Buffer solution - Solution that maintains almost constant pH for small addition of acid or alkali A buffer solution has to contain things which will remove any hydrogen ions or hydroxide ions that you might add to it otherwise the pH will change. An acidic buffer solution is simply one which has a pH less than 7. Acidic buffer solutions are commonly made from a weak acid and one of its salts - often a sodium salt, eg a mixture of ethanoic acid and sodium ethanoate in solution. Ka[acid] [A-] + [H ] = [salt] pH = pKa + log [HA] Why is a mixture of nitrous acid and sodium nitrite act as a buffer solution whereas sodium nitrite solution on its own doesnt In a buffer both [acid] & [salt] must be large compared to the added H + or OH- ions Acidic Neutral Alkaline 01 2 3 4 5 6 7 8 9 10 11 12 13 14 1 10-1 10-2 10-3 10-4 10-5 10-6 10-7 10-8 10-9 10-10 10-11 10-12 10-13 10-14 [OH-] =0.3moldm-3

pH [H3O+]/moldm-3

x (if pH is a whole number) 10-x moldm-3 (hydrogen ion conc)

NaOH(aq) Na+(aq) + OH-(aq)

Kw = 10-14mol2dm-6

[H3O+] x 0.3moldm-3 = 10-14 mol 2 dm-6 [H3O+] =3.33x10-14moldm-3 pH = -log10(3.33x10-14) = 13.5 + HCl(aq) pH of 3, hydrogen ion conc? Molarity of acid? pH =3 [H3O ] = 10-3 = 1 x10moldm-3 Assuming the acid to be 100% ionised, acid being monoprotic, molarity of acid also 1 x10 -3moldm-3 HNO2 is a weak acid Ka = 4.7 x10-4moldm-3 HNO2(aq) + H2O(l) H3O+(aq) + NO2-(aq) K a? [H3O+]x[NO2-] Ka = [HNO2] Calculate pH of 0.12moldm-3 nitrous acid solution [H+] = [NO2-] so [H+]2 = Ka x[HNO2] Ka x0.12 = 0.00751moldm-3 pH =-log10[H+] =2.12 3 Calculate pH of buffer solution made by adding 1.38g of sodium nitrite NaNO2 to 100cm of 0.12moldm-3 nitrous acid solution,

Ka = 4.7 x10-4moldm-3 Moles NaNO2 =1.38/69 =0.02, [NO2-] =0.02/0.1 =0.2moldm-3 Ka[acid] 4.7 x10-4x0.12 [H ] = [salt] = 0.2 =2.82x10-4, pH =-log10 2.82x10-4 =3.55 A buffer solution contains HA(aq) at a concentration of 0.300 mol dm3, and its sodium salt, NaA, at a concentration of 0.600 mol dm3. Calculate the pH of this buffer solution.
+

pH = pKa + log

[A ] [HA]

= log10 (5.62 105) + log10

[0.600 ] = 4.55 [0.300 ]

Understand the principles involved in acid-base titrations Recall the sketch curves for the variation in pH during the following titrations strong acid strong base weak acid strong base strong acid weak base

Strong acid and strong base, running acid into alkali Strong acid and strong base, running alkali into acid Large change in pH for a very small addition of acid and around the end point of the titration

Strong acid and weak base, running acid into alkali At equivalence point all acid and base react to make a salt An aq solution of ethanoic acid of conc 1.0moldm-3 has a pH of 2.8 Sketch how the pH changes during the titration of 25cm3 of 1moldm-3 aq ethanoic acid with aq NaOH of the same conc

Weak acid and strong base, running acid into alkali

25cm3 of 1moldm-3 HA(aq)(weak acid) was titrated with 1moldm3 NaOH(aq) and the pH measured throughout. Use titration curve to find pH at end point of titration 9.0-9.4 Find range of pH values over which the mixture acts as a buffer 5.2-5.8

Use titration curves to determine Ka for a weak acid Explain the choice of a suitable indicator for an acid-base titration given pKInd Students will not be expected to recall the pH ranges of indicators other than methyl orange and phenolphthalein HIn + H2O H3O+ + In[In-][H3O+] KIn = [HIn] Indicator Methyl orange Phenolphthalein Bromothymol blue pH range(working range) 3.2-4.5 8.2-10.0 6.0-7.0 Acid colour Red Colourless Yellow Alkaline colour Yellow Thus suited for strong acid/weak base titrations Magenta Thus suited for strong base/weak acid titrations Blue

Demonstrate an understanding of how the value of enthalpy of neutralisation is related to the strength of acids and bases Enthalpy of neutralisation HN Enthalpy change when one mole of water is formed from reaction of an acid with a base Enthalpy of neutralisation is H for: HCl(aq) + NaOH(aq) NaCl(aq) + H2O(l) H2SO4(aq) + NaOH(aq) Na2SO4(aq) + H2O(l) CH3CO2H(aq) + NaOH(aq) CH3CO2Na(aq) + H2O(l) -1 HN quite constant at -56kJmol when acid and base are both strong If acid and base are fully ionised, ionic equation for all these reactions is the same: H+(aq) + OH-(aq) H2O(l) If either the acid or base is weak, however, some of the energy is absorbed in order to ionise the weak acid or base(amount of heat liberated less than -57kJmol-1) HN of some acids and bases are sometimes more exothermic than -57kJmol-1 because there is also heat liberated on hydration of ions once formed. Energy released on hydration of ions is sometimes greater than energy required to complete ionisation of the acid or base