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What is the pH of an ethanoic acid (CH3CO2H) / sodium ethanoate (CH3CO2–) buffer
containing 0.700 mol dm–3 of CH3CO2H and 0.600 mol dm–3 of CH3CO2–?
(Ka of ethanoic acid = 1.80 × 10–5 mol dm–3)




http://www.wewwchemistry.com                                               Page 1
Method 1: Constructing the ICE table

 Let x be the concentration of CH3CO2H that has dissociated.
 This means x mol dm–3 of H+ and x mol dm–3 of CH3CO2– are formed from the
  dissociation of x mol dm–3 of CH3CO2H.

                                                CH3CO2H ∏ H+ + CH3CO2–
                  (I)nitial conc / mol dm–3       0.700   0      0.600
                  (C)hange in conc / mol dm–3      –x     +x      +x
                  (E)qm conc / mol dm–3         0.700 – x  x   0.600 + x
                                                 ≈ 0.700        ≈ 0.600

Assumption:
 CH3CO2H is a weak acid dissociating in the presence of its conjugate base,
  CH3CO2–, of similar concentration.
 The presence of CH3CO2– suppresses the dissociation of CH3CO2H due to the
  Common Ion Effect.
 It is thus assumed that x is insignificant, such that 0.700 – x ≈ 0.700 and 0.600 + x ≈
  0.600.



http://www.wewwchemistry.com                                                        Page 2
[CH3CO2–][ H+]
                                       Ka =
                                              [CH3CO2H]

                                               (0.600 + x)(x)
                               1.80 × 10–5 =
                                                (0.700 – x)

                                               0.600 x
                               1.80 × 10–5 ≈
                                               0.700

                                        x = 2.10 × 10–5

∴ pH of buffer = –lg(2.10 × 10–5) = 4.68




http://www.wewwchemistry.com                                    Page 3
Method 2:
Substituting given data into the Henderson-Hasselbalch equation (H Eqn) directly

                                              [CH3CO2–]
                               pH = pKa + lg
                                             [CH3CO2H]

 The H Eqn is derived from the Ka expression.
 Like the Ka expression, all concentration terms in the H Eqn are equilibrium
  concentrations.
 If we substitute the equilibrium concentrations from the ICE table in Method 1 into the
  H Eqn, we have the expression shaded in yellow (page 5). Normally, this step is
  skipped, and many students simply substitute the initial concentrations of CH3CO2H
  and CH3CO2– given in the question without fully understanding why.
 Note that initial concentrations of CH3CO2H and CH3CO2– are substituted directly into
  the H Eqn as x is assumed to be insignificant compared to the initial concentrations
  of CH3CO2H and CH3CO2–.




http://www.wewwchemistry.com                                                        Page 4
[CH3CO2–]
                                    pH = pKa + lg
                                                  [CH3CO2H]

                                                 –5        (0.600 + x)
                               pH = –lg(1.80 × 10 ) + lg
                                                           (0.700 – x)

                                                   –5        0.600
                                 pH ≈ –lg(1.80 × 10 ) + lg
                                                             0.700
                                     = 4.68




http://www.wewwchemistry.com                                             Page 5

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To Calculate the pH of a Buffer

  • 1. Question What is the pH of an ethanoic acid (CH3CO2H) / sodium ethanoate (CH3CO2–) buffer containing 0.700 mol dm–3 of CH3CO2H and 0.600 mol dm–3 of CH3CO2–? (Ka of ethanoic acid = 1.80 × 10–5 mol dm–3) http://www.wewwchemistry.com Page 1
  • 2. Method 1: Constructing the ICE table  Let x be the concentration of CH3CO2H that has dissociated.  This means x mol dm–3 of H+ and x mol dm–3 of CH3CO2– are formed from the dissociation of x mol dm–3 of CH3CO2H. CH3CO2H ∏ H+ + CH3CO2– (I)nitial conc / mol dm–3 0.700 0 0.600 (C)hange in conc / mol dm–3 –x +x +x (E)qm conc / mol dm–3 0.700 – x x 0.600 + x ≈ 0.700 ≈ 0.600 Assumption:  CH3CO2H is a weak acid dissociating in the presence of its conjugate base, CH3CO2–, of similar concentration.  The presence of CH3CO2– suppresses the dissociation of CH3CO2H due to the Common Ion Effect.  It is thus assumed that x is insignificant, such that 0.700 – x ≈ 0.700 and 0.600 + x ≈ 0.600. http://www.wewwchemistry.com Page 2
  • 3. [CH3CO2–][ H+] Ka = [CH3CO2H] (0.600 + x)(x) 1.80 × 10–5 = (0.700 – x) 0.600 x 1.80 × 10–5 ≈ 0.700 x = 2.10 × 10–5 ∴ pH of buffer = –lg(2.10 × 10–5) = 4.68 http://www.wewwchemistry.com Page 3
  • 4. Method 2: Substituting given data into the Henderson-Hasselbalch equation (H Eqn) directly [CH3CO2–] pH = pKa + lg [CH3CO2H]  The H Eqn is derived from the Ka expression.  Like the Ka expression, all concentration terms in the H Eqn are equilibrium concentrations.  If we substitute the equilibrium concentrations from the ICE table in Method 1 into the H Eqn, we have the expression shaded in yellow (page 5). Normally, this step is skipped, and many students simply substitute the initial concentrations of CH3CO2H and CH3CO2– given in the question without fully understanding why.  Note that initial concentrations of CH3CO2H and CH3CO2– are substituted directly into the H Eqn as x is assumed to be insignificant compared to the initial concentrations of CH3CO2H and CH3CO2–. http://www.wewwchemistry.com Page 4
  • 5. [CH3CO2–] pH = pKa + lg [CH3CO2H] –5 (0.600 + x) pH = –lg(1.80 × 10 ) + lg (0.700 – x) –5 0.600 pH ≈ –lg(1.80 × 10 ) + lg 0.700 = 4.68 http://www.wewwchemistry.com Page 5