1 FFER SOLUTIONS LESSON 21 This lesson deals with: Writing equations for the buffering action that occurs when a strong acid or base is added to a buffer solution. Calculating the pH value of a buffer solution. Calculating the resulting pH value after a strong base is added to a weak acid buffer solution Calculating the resulting pH value after a strong acid is added to a weak acid buffer solution. Calculating the resulting pH when a strong acid or base is added to a weak base buffer solution. Concepts in Buffer Solutions ( eauilibrium (Hy base] [acid] ‘resists change inpH K, ‘contains bolh Weak weak acid ‘weak acid weak base base a reacts with added H * to form reacts with added OH - to form weak rion of eis fA eat ae en, fare (weak base BUFFER SOLUTIONS A buffer solution is a solution that resists changes its pH when an acid or a base is added to itLESSON 21: BUFFER SOLUTIONS 245 ‘Two types of mixtures form buffer solutions: weak acid and a salt of the weak acid weak base and a salt of the weak base BUFFERING ACTION For a buffer containing a weak acid and a salt of the weak acid. weak acid: HA. salt of weak acid: NaA (A7) This buffer solution contains a reaction at equilibrium. HA == HY + A This buffer solution contains significant amounts of both HA and A~. What happens if H* is added (e.g., from HCI)? AC reacts with the added H™. HT + A” —— HA This is buffering action. Most of the added H’' is consumed, so the pH changes only slightly. What happens if OH is added (e.g,, from NaOH)? HA reacts with the added OF. OH” + HA —— H,0 + A” This is buffering action, Most of the added OH is consumed, so the pH changes only slightly. For a buffer containing a weak base and a salt of the weak base. weak base: M salt of weak base: (MH)CI (MH) This buffer solution contains a reaction at equilibrium. M + H,0 == MH" + OH This buffer solution contains significant amounts of both M and MH". ‘What happens if His added (e.g., from HCI)? M reacts with the added H” HY + M—— MH ‘This is buffering action, Most of the added His consumed, so the pH changes only slightly. What happens if OH” is added (e.g, from NaOH)? MH reacts with the added OF". OH + MH* —— H,0 + M This is buffering action. Most of the added OH is consumed, so the pH changes only slightly.246 ._ A buffer solution contains HC)H30, and NaCyH;0,. WORKBOOK FOR GENERAL CHEMISTRY. —_————————————————————— Exercise Ons Write the equation for the buffering action that occurs when HCI is added to this buffer solution, Write the equation for the buffering action that occurs when NaOH is added to this buffer solution Another buffer solution contains NH and NH,Cl. Write the equation for the buffering action that occurs when HCI is added to this, buffer solution. Write the equation for the buffering action that occurs when NaOH is added to this buffer solution. CALCULATING THE pH OF A BUFFER SOLUTION Example 4 Calculate the pH of a buffer solution prepared by dissolving 0.10 mole of cyanic acid, HCNO, and 0.50 mole of sodium cyanate, NaCNO, in enough water to make 0.500 liter of solution. For HCNO, K, = 2.0 10 at 25°C. Write the equation for the equilibrium reaction and its K expression. HCNO(aq) = H((aq) + CNO“ad) (H"][CNO7] 2.0« 104 * [HCNO]LESSON 21: BUFFER SOLUTIONS 247 2. Summarize the information in a table based on the chemical equation. HCNO === Ht + CNO- initial moles 0.10. * 0 0.50 initial conc 0.20 0 10 cone change te +x equil cone 0.20-x x 1.0+e 3. Test to see if the calculation can be simplified: 400 « K, = 400 = (2.0 10) = 0.08 0.08 is less than both 0.20 and 1.0 ‘Therefore, assume 0.20 -x = 0.20 and 1.0 += 1.0. 4. Find the value of x by substituting equilibrium concentrations into K expression. LH'V[CNO™] _ (+) (1.0) _ [HCNO] (0.20) 2.0 x 104 10 4 2 «(2.010 Seeoce : 4.0 « 105 .0 «105M log(4.0 x 10°5) = Exercise Two A. Calculate the pH ofa buffer solution prepared by dissolving 0,400 mole of formic acid, HCHO,, and 0.100 mole of sodium formate, NaCHO;, in 0.250 liter of solution, For formic acid, K, = 1.77 x 10 at 25°C.248 WORKBOOK FOR GENERAL CHEMISTRY B. Calculate the pH of a buffer solution containing 0.20 mole of NH; and 0.15 mole of NH,CI in 0.500 liter of solution. For NH, Ki = 1.8» 10° at 25°C. CALCULATIONS INVOLVING BUFFERING ACTION ‘Adding a Base to a Weak Acid Buffer Solution Example 2 Calculate the pH of the buffer solution in Example | after 0.020 mole of NaOH has been added to it, 1, Write the equation for the equilibrium reaction and its K expression. HCNO(aq) == H’(aq) + CNO“(aq) _ BETICNO}) ~ 59 57 Okeno} 2.0% 104 2, Summarize the information in a table based on the chemical equation HCNO == HY + CNO initial conc 0.20 0 1.0 ‘Now take into account the buffering action that results when 0.020 mole of NaOH is added.LESSON 21: BUFFER SOLUTIONS 249 oH + = HENO ~~ CNO + «0 0.020 mol 0.020 mol 0.020 mol added ‘eonsumed* formed ‘Therefore, as a result of buffering action, 0. the concentration of HCNO decreases by Oe 040 mol/L. and 0.020 mol the concentration of CNO increases by “5 Z5q z= 0.040 moVL. Put these results of buffering action into the table. HCNO == HY + CNO™ initial cone 0.20 o Lo buffaction 0.040 ° +0.040 conc change — +x te equil cone 0.16-x x Lode 3. Simplifications can still be made, Assume 0.16 —x= 0.16 and 1.04 += 1.04. 4, Find the value of x by substituting equilibrium concentrations into K expression, k= FUUCENO] © 0.04) 299, 9 [HCNO] (0.16) 2 O16 (99x 104 xa Ty 20x10) x= 31x 105 [1] == 3.1 «105M =z " ~log(3.1 x 10°) = 4.51250 _WORKBOOK FOR GENERAL CHEMISTRY = Exercise Three A buffer solution contains 0.400 mole of formic acid, HCHO,, and 0.100 mole of sodium formate, NaCHO,, in 1.00 liter of solution. Calculate the pH of this buffer solution after 0.100 mole of NaOH is added. For HCHO}, K,= 1.77 10 at 25°C.LESSON 21: BUFFER SOLUTIONS 254 CALCULATIONS INVOLVING BUFFERING ACTION ‘Adding an Acid to a Weak Acid Buffer Solution Example 3 Calculate the pH of the buffer solution from Example 1 after 0.030 mole of HCI is added. Take into account the buffering action that results when 0.030 mole of HCI is added, HY + CNO —-+ — HCNO 0.030 mol 0.030 mol 0.030 mol added consumed formed Therefore, as a result of buffering action, es 0.030 mot _ the concentration of CNO™ decreases by —5 gq 1 ~ 0.060 mol/L. and 0.030 mol the concentration of HCNO increases by soae net = 0.060 molL. Put these results of buffering action into the table. HCNO === Hi + CNO™ initial conc 0.20 ° 10 buffaction _+0.060 0 0.060 concchange_— te te equil cone 0.26- x 0.94+x Make simplifications: Assume 0.26 ~ x = 0.26 and 0.94 + x= 0.94 Pind the value of x by substituting equilibrium concentrations into K expression. THIEN]. ()(094) <9 10-4 THCNO] (0.26) 0.26 4 = 926 x (20x10 = p54 * 6 y x= 55 x 10% pH = —log(5.5 « 10%) = 426252 WORKBOOK FOR GENERAL CHEMISTRY. Exercise Four A butfer solution contains 0.400 mole of formic acid, HCHO,, and 0.100 mole of sodium formate, NaCHO,, in 1.00 liter of solution. Calculate the pH of this solution after 0.050 mole of HCI is added. For HCHO), K, = 1.77 10° at 25°C.LESSON 21: BUFFER SOLUTIONS 253 CALCULATIONS INVOLVING BUFFERING ACTION Buffering Action in a Weak Base Buffer Solution Example 4 ‘A buffer solution is prepared by dissolving 0.100 mole of methylamine, CH,NH, and 0.0600 mole of methylammonium chloride, CH.NH,ClI in 0.250 liter of solution. Calculate the pH of this solution after 0.0200 mole of HCI has been added. For CHsNH, Ki = 4.38 * 10 1, Write the equation for the equilibrium reaction and its K expression. CH,NH,(aq) + H,0(1) == CH;NH;"(aq) + OH"(aq) _ (CH,NH,'] [OH7] [CH,NH,] 2. Summarize the information in a table based on the chemical equation. The volume of the solution is 0.250 L. CH,NH, + H,0 === CHNH,' + OH initial moles 0.100 0.0600 initial cone 0.400 0.240 = 438104 ‘Take into account the buffering action. The added H” is consumed by CH;NHy. w + CHNH, —— CHNH;* 0.020 mot 0.020 mol 0.020 mol added consumed formed Therefore, as a result of buffering action, the concentration of CH;NH3 decreases by sae mel = 0.0800 mol/L. and 0.0200 mol the concentration of CH NH," increases by 5-545 1 ~ 0.0800 mol/L. CH.NH, + H,0 = CH.NH,” + OFF initial cone 0.400 0.240 ° buff action 0.0800 +0.0800 cone change — + a at equil 0.320-x 0.32042 x254 WORKBOOK FOR GENERAL CHEMISTRY 3. Simplifications: 4. Solve for x and find pH. (CH,NH,"}[0H] _ ( [CH,NH,] (0.32) 032 = OSS x (4.38% 104 7a 7 C - 438 « 104 = [OH] 358 = 438 x 104 x POH = —log(4.38 = 104) pH = 14.000 — pO# = 14.000 ~ 3.358 = 10.642 Exercise Five A buffer solution contains 0.20 mole NH, and 0.60 mole NH,CI in 750 mL of solution, Calculate the pH of this buffer solution after 0.10 mole of NaOH is added to it. For NH3, Kj, = 1.8 * 10° at 25°C.LESSON 21: BUFFER SOLUTIONS 255 B. One liter of a buffer solution is prepared so that it contains 0.10 mole of NH and 0.10 mole of NH,CI. When one mole of NaOH is added to this solution, the pH changes drastically. Why did the buffer solution fail to maintain its pH? PROBLEMS 1. a. Calculate the pH of a solution made by adding 0.50 mole of nitrous acid, HNO,, and 0.10 mole of potassium nitrite, KNO,, to enough water to make 1.0 liter of solution ‘The K, for HNO, is 4.5 * 10 at 25°C. b. Calculate the pH of this solution after 0.010 mole of HCI is added to it 2. Ethyl amine, CoHsNH,, ionizes in aqueous solution according to the equation C)H.NH, + HO === C,H.NH,” + OH ‘The value of K;, for this reaction is 5.6 10 at 25°C. a. Calculate the pH of a solution made by adding 0.20 mole of CHsNH, and 0.10 mole of ethylammonium chloride, (C,HsNH,)Cl, to enough water to make 0,50 liter of solution. b, Calculate the pH of this solution after 0.010 mole of HCI has been added to it.