4.3 Exercise 3 - Buffer solutions 1. a) What is meant by the term "buffer solution"?

b) Calculate the pH of a buffer solution which contains the weak monoprotic acid, propanoic acid (CH CH!C""H), in concentration #.1 moldm $ and sodium propanoate in concentration #.#% moldm$ . &a of propanoic acid is 1.!' ( 1#$% moldm$ . c) )i*e e+uations to show how the abo*e solution fulfills its buffer function. d) Calculate the pH of the solution after #.#1 moles of ,a"H are added to %## cm of the solution. e) Calculate the pH of the solution after #.#1 moles of HCl are added to %## cm of the solution. f) Calculate the pH after #.#1 moles of ,a"H is added to %## cm of water. -) Comment on your answers to (d) and (f). !. a) Calculate the pH of #.1! moldm$ ethanoic acid (&a . 1./ ( 1#$% moldm$ ). b) Calculate the mass of sodium ethanoate (CH C"",a) which must be added to %## cm this solution to -i*e a buffer solution of pH . 0.'#. c) Calculate the pH of this solution after #.#1 moles of HCl are added. d) Calculate the pH of this solution after #.#1 moles of ,a"H are added. . Calculate the pH of a buffer which is #.! moldm $ with respect to ammonium sulphate and #.1 moldm$ with respect to ammonia. (&a of ,H01 . %.' ( 1#$1# moldm$ ) 0. 2ethanoic acid, HC""H, has a &a *alue of 1.%3 ( 1#$0 moldm$ . What ratio of methanoic acid and sodium methanoate would -i*e a buffer of pH . 0? %. a) Calculate the pH of a buffer solution which is #.1 moldm $ with respect to HC, (&a . 0.4 ( 1#$1# moldm$ ) and #.3 moldm$ with respect to sodium cyanide. b) Calculate the pH after #.#% moles of HCl are added to 1 dm of this buffer. c) Calculate the pH after #.#% moles of ,a"H are added to 1 dm of this buffer. d) Calculate the pH after #.! moles of ,a"H are added to 1 dm of this buffer. e) Comment on your answer to (d).

'.

What amount of sodium ethanoate must be added to 1.# dm of ethanoic acid of concentration #.1# mol dm and &a . !( 1#$% mol dm$ to produce a buffer solution of pH 0./? #.#% mol #.1 mol #.! mol #.% mol
a

a. b. c. d.

/. Citric acid beha*es as a weak monoprotic acid of & Calculate the pH of5

. /.!0( 1#$0 mol dm$ .

a. a solution of #.1## mol dm$ citric acid 1 #.1## mol dm$ sodium citrate. b. a solution of #.1## mol dm$ citric acid 1 #.#%# mol dm$ sodium citrate. 3. 6he pH of a #.#%# mol dm$ solution of propanoic acid is .1#. a. Calculate the *alue of & a for the acid. b. Calculate the pH of a solution which is #.#%# mol dm$ with respect to propanoic acid and also to sodium propanoate. 4. Calculate the pH of a solution formed when 0# cm of 1.## mol dm$ nitrous acid (p& a . . 0) is added to !#.# cm of 1.## mol dm$ sodium hydro(ide solution. 1#. What amount of sodium ethanoate must be added to 1.## dm of ethanoic acid of p& a . 0./ , concentration #.1## mol dm$ , to produce a buffer of pH .%./ ? 11. Calculate the pH of a buffer solution which contained #.%## mol dm $ propanoic acid, C!H%C""H, and 1.## mol dm$ sodium propanoate, C!H%C"",a, &a for propanoic acid . 1. %(1#$% mol dm$ . 1!. Calculate the pH of a buffer solution which contained 1! - ethanoic acid, CH C""H, and 0.1# - sodium ethanoate, CH C"",a dissol*ed in 1## cm of solution. &a for ethanoic acid . 1./0(1#$% mol dm$ . H.17 C.1!7 ".1'7 ,a.! . 1 . Calculate the pH of a solution made by mi(in- !#.# cm of #.1## mol dm$ methanoic acid, HC""H, with 3#.# cm of #.#%## mol dm$ sodium methanoic, HC"",a. &a for methanoic acid . 1./3(1#$0 mol dm$ . 10. 8 buffer solution contained #.%## mol dm $ of a weak acid H8 and #. ## moldm $ of its sodium salt, ,a8. a. Calculate its pH if p&a for H8 . 0.3!. b. Calculate the pH after addin- !.## cm of %.## moldm$ HCl to 1###cm of the buffer solution. c. Calculate the pH after addin- !.## cm of %.## moldm$ ,a"H to 1###cm of the buffer solution.

1%. 9n what proportions should you mi( 1.## mol dm$ solutions of methanoic acid, HC""H, and sodium methanoate, HC"",a, to -i*e a buffer solution of pH .%#? &a for methanoic acid. 1./3(1#$0 mol dm$ . 1'. %## cm of a 1.## mol dm $ solution of a weak base : was mi(ed with %## cm of a 1.## mol dm$ solution of one of its salts, :H1Cl$ . p&a for :H1 ion .1#.'0. a. Calculate the pH of the buffer solution formed on mi(in- the two solution. b. Calculate the effect of addin- (i) 0.## cm of %.## mol dm$ HCl, and (ii) 0.## cm of %.## mol dm$ ,a"H solution to 1### cm of the buffer solution. c. 9n what proportions would you ha*e to mi( the ori-inal solution to -i*e a buffer solution of pH 1#.%? 1/. ;ou ha*e a*ailable 1.## mol dm$ solutions of amomium, ammonium chloride, ethanoic acid and sodium ethanoate. Which solutions would you mi(, and in what proportions, to obtain a buffer solution of (a) pH 0.%# (b) 4.!% p&a for the ammonium ion . 4.!% p&a for ethanoic acid . 0./' 13. 8 buffer solution contained a mi(ture of '#.#- of ethanoic acid, CH C""H, and 3!.# - of sodium ethanoate, CH C"",a, in 1### cm of solution. &a for ethanoic acid . 1./0(1#$% mol dm$ . a. Calculate the pH of the buffer solution. b. Calculate the pH after addin- 1.## cm of %.## mol dm$ HCl to %## cm of the buffer solution. c. Calculate the pH after addin- 1.## cm of %.## mol dm$ ,a"H to %## cm of the buffer solution. 14. <how details of all calculation in answerin- this +uestion. <olution < is #.1' 2 hydrochloric acid, HCl a stron- acid. <olution W is #.1' 2H=, a weak monoprotic acid ( & a . !.#/(1#$% mol dm$ , pH .!./0) <olution > is #.1! 2 barium hydro(ide, :a("H)!, a stron- base. 8t a temperature of !%#C, 13 cm of solution < are titrated with solution >. 6he titration is repeated usin- 13 cm of solution W. a. ?etermine the e+ui*alence *olume (end$ point) for these titration and enter your result into the appropriate space in a copy of the incomplete table -i*en below. @nter also the half e+ui*alence *olume and the double$ e+ui*alence *olume in the appropriate space. b. Calculate the missin- pH *alues for each of the two titration solution and enter these into a copy of the table. ( ;ou should assume that , at half Ae+ui*alence, BH=C. B= $C for the weak acid H=, and that, for both acids at double Ae+ui*alence, only the alkali that is in e(cess contributes to the pH of the resultin- solution).

c. Dlot these results on a -raph of pH a-ainst *olume of :a("H)! (a+) and use the points you ha*e plotted to sketch the complete titration cur*es for solution < and solution W titrated with solution >. <tart Eolume Fcm :a("H)! #.# solution added pH for titration of < #.3# pH for titration of W !./0 Half e+ui*alence 1.!! @+ui*alence ?ouble e+ui*alence

/ 3.%

1.

a) resists lar-e pH chan-e on addition of small amounts of acid or alkali

!. . 0. %. '. /. 3. 4. 1#. 11. 1!. 1 . 10. 1%. 1'. 1/. 13. 14.

b) 0.'# c) CH CH!C""H 1 "H$ CH CH!C""$ 1 H!" CH CH!C""$ 1 H1 CH CH!C""H d) 0.30 e) 0. # f) 1!. # -) the buffer solution restricts the pH chan-e to #.!0 units, but the water chan-es its pH by %. # units (from / to 1!. ). a) !.3% b) . c) 0.01 d) 0.// 3.'% salt5 acid ratio 1.%351 a) 1#.!1 b) 1#.#1 c) 1#.%0 d) 1 .## e) :ufferin- capacity has been e(ceeded, so cannot resist chan-e in pH. B (a) .10 (b) !.30 (a) 1.!'( 1#$% mol dm$ (b) 0.4# . 0 1.# mol %.1/ 0.1' 0.#% a. 0.'# b. 0.%3 c.0.'! BHC""$CFBHC""HC . #.%' F1 a. 1#.' b.(i) 1#.' b (ii)1#./ c. B:CFB:H$C .#./!%F1 (a) 2i( sodium ethanoate and ethanoic acid solutions in the ratio #.%%# 5 1. (b) 2i( amomonium chloride and ammonia solutions in the ratio #.%'!5 1. (a) 0./' (b) 0./% (c) 0.//

Equivalence volume of Ba(OH)2 : 2ole number of < (HCl)5 ( #.1'( 13(1#$ ).!.33(1#$ moles 2ole number of > :a( "H)! 5 (!.33(1#$ )F!.1.00(1#$ moles <o *olume of :a("H)!5 (1.00(1#$ )F#.1!.#.#1! dm . 1! cm

<o half e+ui*alence5 1!F! . ' cm <o half e+ui*alence5 1!(! . !0 cm pH for titration of S at ou!le equivalence: @(tra base added (!0$1!) .1! cm 2ole number of e(cess :a("H)! . #.1!(1!(1#$ .1.00(1#$ moles <o mole number of "H .1.00(1#$ (! . !.33(1#$ moles 6otal *olume5 (!0113) .0! cm

Concentration of "H . (!.33(1#$ ) F#.#0! .#.#'3% 2 p"H . $lo-( #.#'3%) .1.1' <o pH .10$1.1'.1!.30 pH for titration of S at "alf equivalence: 6otal *olume .( 131').!0 cm 2ole number of W (2H=)5 (#.1'( 13(1#$ ) .!.33(1#$ moles 2ole number of > :a( "H)! 5 (1.00(1#$ ) F! ./.!(1#$0 moles 2ole number of W neutraliGed 5 (/.!(1#$0)(!.1.00(1#$ moles 2ole number of W left 5 (!.33(1#$ )$ (1.00(1#$ ) moles .1.00(1#$ moles Concentration of left o*er acid (W) . (1.00(1#$ ) F(!0(1#$ ).#.#' 2 <o &a.BH1C.!.#/(1#$% pH.0.'3