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◆ In the 2nd half of the chapter, our focus will shift to Steps for solving weak acid equilibrium problems:
understanding solutions in which there is some 1. Identify all major species in solution.
combination of acidic and basic species:
2. Identify all potential H+ transfer reactions that
buffer solutions could contribute to the [H3O+]total in the sol’n.
titration experiments
3. By considering K values, determine the dominant
◆ We will need to consider that neutralization source of H3O+ in the solution.
reactions can/will occur, as well as the equilibria that
exist. 4. Set up the equilibrium calculation based on
equilibrium identified in step 3.
◆ use multiple steps:
determine the pH of solutions after 5. Solve!
◆ x = [H3O ]
+
neutralization reactions are complete
◆ solve for pH, % ionization, or Ka
construct and interpret titration curves
example: example:
Determine the pH of 0.10 M HCN (aq). For HCN, Ka = 4.9 x 10–10.
Determine the pH of 0.10 M HCN (aq). For HCN,
Ka = 4.9 x 10–10. 3. By considering K values, determine the dominant source
of H3O+ in the solution.
1. Identify all major species in solution.
◆ there are 2 possible sources of H3O+ in this sol’n:
◆ this is an aqueous solution of a weak acid, so the
HCN (aq) + H2O (aq) ⇄ CN– (aq) + H3O+ (aq); Ka = 4.9 x 10–10
major species are: HCN & H2O
2 H2O (l) ⇄ H3O+ (aq) + OH– (aq); KW = 1 x 10–14
2. Identify all potential H+ transfer reactions that could ◆ Ka > KW, so the acid ionization of HCN will be the
contribute to the [H3O+]total in the sol’n. dominant source of H3O+ in his solution.
◆ there are 2 possible sources of H3O+ in this sol’n: OR
HCN (aq) + H2O (aq) ⇄ CN– (aq) + H3O+ (aq); Ka = 4.9 x 10–10 [H3O+]total = [H3O+]HCN-ionization + [H3O+]H2O-ionization
but we will assume that [H3O+]H2O-ionization is negligibly small
2 H2O (l) ⇄ H3O+ (aq) + OH– (aq); KW = 1 x 10–14
so [H3O+]total ≈ [H3O+]HCN-ionization
example: example:
Determine the pH of 0.10 M HCN (aq). For HCN, Ka = 4.9 x 10–10. Determine the pH of 0.10 M HCN (aq). For HCN, Ka = 4.9 x 10–10.
5. Solve! x = [H3O+]
4. Set up the equilibrium calculation based on
equilibrium identified in step 3. [H3O+][CN–] x2
Ka = ––––––––––– ; 4.9 x 10–10 = –––––––––
[HCN] 0.10 – x
HCN (aq) + H2O (l) ⇄ CN– (aq) + H3O+ (aq)
◆ use a simplifying approximation
initial [ ] 0.10 M --- 0 0 Because Ka is very small, the reaction does not
proceed very far forward (toward products) before
∆[] –x --- +x +x reaching equilibrium.
equil [ ] (0.10–x)M --- xM xM We will assume that “x” in the denominator will be
negligibly small relative to [HCN]0.
[H3O+][CN–] x2 OR
Ka = ––––––––––– ; 4.9 x 10–10 = –––––––––
[HCN] 0.10 – x 0.10 – x ≈ 0.10
example: example:
Determine the pH of 0.10 M HCN (aq). For HCN, Ka = 4.9 x 10–10. Determine the pH of 0.10 M HCN (aq). For HCN, Ka = 4.9 x 10–10.
new equilibrium [H3O+] and [A–] are higher [H3O+], M 4.2 x 10–4 6.7 x 10–4 3.5 x 10–6 7.0 x 10–6
relative to new [HA]0
pH 3.38 3.17 5.46 5.15
∴ % ionization is greater
%
4.2% 2.7% 0.014% 0.0070%
ionization
◆ Be careful when comparing solutions and making qualitative Determination of Ka from Experimental Data:
statements about them. Given [HA]0 and pH
◆ You can compare 2 different acids at the same concentration: example:
acid with larger Ka is the stronger acid The pH of 0.250 M HF (aq) is 2.036. Determine the
∴ acid solution with larger Ka will have: Ka for HF.
higher [H3O+]
lower pH
higher % dissociation
◆ You can compare the same acid at 2 different concentrations:
Ka is the same, so acid strength is the same
solution with higher concentration will have:
higher [H3O+]
lower pH
lower % dissocation
Determination of Ka from Experimental Data: Polyprotic Acids
Given [HA]0 and % Ionization
◆ acid with more than one acidic proton
example:
A 0.340 M solution of HNO2 (aq) is 3.65% dissociated ◆ polyprotic acids dissociate in a step-wise manner
at equilibrium. Determine Ka for nitrous acid, and the each step corresponds to the dissociation
pH of the solution. of one H+
each step has a unique Ka value
◆ Ka1 > Ka2 this is always true for polyprotic acids 1st ionization equation:
◆ the acids become weaker with each successive H2CO3 (aq) + H2O (l) ⇄ HCO3– (aq) + H3O+ (aq)
dissociation step
H2C2O4 is a stronger acid than HC2O4– 2nd ionization equation:
Why? HCO3– (aq) + H2O (l) ⇄ CO32– (aq) + H3O+ (aq)
solution: solution:
◆ because Ka1 > Ka2 & Ka1 >> Kw, the primary source ◆ to determine [CO3 ] we will have to consider the
2–
of H3O+ in the solution will be the 1st ionization 2nd ionization step:
step for H2CO3:
HCO3– (aq) + H2O (l) ⇄ CO32– (aq) + H3O+ (aq)
H2CO3 (aq) + H2O (l) ⇄ HCO3– (aq) + H3O+ (aq)
initial [ ] 1.3 x 10–4 M --- 0 1.3 x 10–4 M
initial [ ] 0.040 M --- 0 0
∆[] –x --- +x +x
∆[] –x --- +x +x
equil [ ] (1.3 x 10–4 –x)M --- xM (1.3 x 10–4 + x)M
equil [ ] (0.040–x)M --- xM xM
◆ use Ka1; solve for x: x = 1.3 x 10–4 ◆ use Ka2; solve for x: x = 5.6 x 10–11
so: [H2CO3] ≈ 0.040 M so: [CO32–] = 5.6 x 10–11 M
[HCO3–] = [H3O+] = 1.3 x 10–4 M
◆ [OH–]? [OH–] = KW/[H3O+] = 7.7 x 10–11 M
pH = 3.89
example:
Steps for solving weak base equilibrium problems:
Calculate pH and % dissociation of 0.40 M NH3 (aq).
1. Identify all major species in solution. For NH3, Kb = 1.8 x 10–5.
2. Identify all potential H+ transfer reactions that
could contribute to the [OH-]total in the sol’n. NH3 (aq) + H2O (l) ⇄ NH4+ (aq) + OH– (aq)
◆ compare 2 solutions of different concentration of pyridine ◆ You can compare 2 different bases at the same concentration:
(C5H5N, Kb = 1.4 x 10–9) base with larger Kb is the stronger base
∴ base solution with larger Kb will have:
◆ compare ammonia and pyridine solutions of the same higher [OH–]
concentration higher pH
0.40 M 0.80 M higher % dissociation
0.15 M NH3 0.40 M NH3
C5H5N C5H5N
◆ You can compare the same base at 2 different concentrations:
[OH–], M 0.0016 0.0027 2.4 x 10–5 3.3 x 10–5 Kb is the same, so base strength is the same
solution with higher concentration will have:
pH 11.20 11.43 9.38 9.52 higher [OH–]
% higher pH
1.1% 0.68% 0.0060% 0.0041%
ionization lower % dissocation
a closer look at a weak acid/conjugate base pair: HA & A- a closer look at a weak base/conjugate acid pair: B & BH+
HA (aq) + H2O (l) ! A– (aq) + H3O+ (aq) B (aq) + H2O (l) ! BH+ (aq) + OH- (aq)
the stronger the acid (HA), the weaker its conjugate base (A-): the stronger the base (B), the weaker its cation:
strong monoprotic acids produce conjugate bases that are not strong bases produce cations that are not effective acids in
effective bases in solution - they are neutral anions solution - they are neutral cations
neutral anions are: Cl–, Br–, I–, NO3– , ClO4– neutral cations are: Li+, Na+, K+, Rb+, Cs+, Ca2+, Sr2+, Ba2+
the weaker the acid (HA), the stronger its conjugate base (A-): the weaker the base (B), the stronger its conjugate acid (BH+):
weak acids produce conjugate bases that can function as bases weak bases produce conjugate acids that can function as acids
in solution - they are basic anions in solution - they are acidic cations
base ionization equilibrium for A-: acid ionization equilibrium for BH+:
A- (aq) + H2O (l) ! HA (aq) + OH- (aq); Kb BH+ (aq) + H2O (l) ! B (aq) + H3O+ (aq); Ka
examples of basic anions include: examples of acidic cations include:
F-, CO32-, ClO2-, SO32-, PO43-, NO2-, BrO4- NH4+, CH3NH3+, C2H5NH3+, C5H5NH+, C6H5NH3+
salts that produce neutral solutions:
recall the relationship between Ka and Kb for a
conjugate acid/base pair: ◆ pH = 7.00 at 25oC
Ka x Kb = Kw
◆ neutral cation with a neutral anion
OR
pKa + pKb = pKw examples: KNO3, NaCl, Ca(ClO4)2, SrBr2, CsI
salts that produce acidic solutions: ◆ type 3: hydrated metal cation of high positive charge-
◆ pH < 7.00 at 25oC density with neutral anion
example:
for comparison:
0.10 mol HC2H3O2 and 0.10 mol NaC2H3O2 are
combined in a solution with a total volume of 1.0 L. 0.10 M HC2H3O2 (aq)
0.10 M HC2H3O2 (aq) +
Determine the [H3O+], pH, and % ionization in this 0.10 M NaC2H3O2 (aq)
solution. For HC2H3O2, Ka = 1.8 x 10–5.
[H3O+] 1.3 x 10 -3 M 1.8 x 10-5 M
the equilibrium that controls the pH of this sol’n:
How does the pH change after the addition of 0.010 mol HCl to
Consider, again, 0.10 M HC2H3O2 & 0.10 M NaC2H3O2 1.00 L of a solution composed of 0.10 M HC2H3O2 & 0.10 M
common ion solution; starting pH = 4.74. NaC2H3O2 (initial pH = 4.74).
◆ How does the pH change after the addition of 0.010 mol
HCl to 1.00 L of this solution? 1st: addition of strong acid (H+) results in a neutralization
reaction (note: Cl- is a spectator ion; this is the net
◆ 1st: addition of strong acid (H+) results in a neutralization ionic equation):
reaction (note: Cl- is a spectator ion; this is the net ◆ the added strong acid (H+) will react with the base
ionic equation): (C2H3O2-) in the buffer solution
C2H3O2- (aq) + H+ (aq) " HC2H3O2 (aq)
C2H3O2– (aq) + H+ (aq) → HC2H3O2 (aq)
◆ 2nd: after the strong acid is consumed, equilibrium is
established that determines the pH of the solution: before rxn 0.10 mol 0.010 mol 0.10 mol
HC2H3O2 (aq) ! C2H3O2- (aq) + H+ (aq) ∆ –0.010 mol –0.010 mol +0.010 mol
◆ resulting solution pH = 4.66; ∆pH = -.08 after rxn 0.090 mol 0 0.11 mol
How does the pH change after the addition of 0.010 mol HCl
to 1.00 L of a solution composed of 0.10 M HC2H3O2 & 0.10 M the result of the neutralization reaction:
NaC2H3O2 (initial pH = 4.74).
C2H3O2– (aq) + H+ (aq) → HC2H3O2 (aq)
2nd: after the strong acid is consumed, equilibrium is
established that determines the pH of the solution:
◆ C2H3O2– is consumed ◆ HC2H3O2 is formed
HC2H3O2 (aq) + H2O (l) ! C2H3O2- (aq) + H3O+ (aq) [C2H3O2–] decreases [HC2H3O2] increases
◆ initial [HC2H3O2] and [C2H3O2–] in equilibrium problem
determined by consideration of what is in solution after ◆ strong acid, H+, is the limiting reactant
the neutralization reaction is complete H+ is completely consumed
HC2H3O2 (aq) + H2O (l) ⇄ C2H3O2– (aq) + H3O+ (aq)
◆ pH of solution decreases slightly
initial [ ] 0.11 M --- 0.090 M 0 solution becomes slightly more acidic
∆[] –x --- +x +x
equil [ ] (0.11–x)M --- (0.090+x)M xM
How does the pH change after the addition of 0.010 mol NaOH
Consider, again, 0.10 M HC2H3O2 & 0.10 M NaC2H3O2 to 1.00 L of a solution composed of 0.10 M HC2H3O2 & 0.10 M
common ion solution; pH = 4.74. NaC2H3O2 (initial pH = 4.74).
How does the pH change after the addition of 0.010 mol
NaOH to 1.00 L of this solution? 1st: addition of strong base (OH–) results in a neutralization
reaction (note: Na+ is a spectator ion; this is the net
1st: addition of strong base (OH-) results in a neutralization ionic equation):
reaction (note: Na+ is a spectator ion; this is the net ◆ the added strong base (OH–) will react with the acid
ionic equation): (HC2H3O2) in the buffer solution
HC2H3O2 (aq) + OH- (aq) " C2H3O2- (aq) + H2O (l)
HC2H3O2 (aq) + OH– (aq) → C2H3O2– (aq) + H2O (l)
2nd: after the strong base is consumed, equilibrium is
established that determines the pH of the solution: before rxn 0.10 mol 0.010 mol 0.10 mol ---
HC2H3O2 (aq) ! C2H3O2- (aq) + H+ (aq) ∆ –0.010 mol –0.010 mol +0.010 mol ---
resulting solution pH = 4.82; ∆pH = +.08 after rxn 0.090 mol 0 0.11 mol ---
How does the pH change after the addition of 0.010 mol NaOH
to 1.00 L of a solution composed of 0.10 M HC2H3O2 & 0.10 M the result of the neutralization reaction:
NaC2H3O2 (initial pH = 4.74).
HC2H3O2 (aq) + OH– (aq) → C2H3O2– (aq) + H2O (l)
2nd: after the strong base is consumed, equilibrium is
established that determines the pH of the solution:
◆ HC2H3O2 is consumed ◆ C2H3O2– is formed
HC2H3O2 (aq) + H2O (l) ! C2H3O2- (aq) + H3 O+ (aq) [HC2H3O2] decreases [C2H3O2–] increases
◆ initial [HC2H3O2] and [C2H3O2–] in equilibrium problem
determined by consideration of what is in solution after ◆ strong base, OH–, is the limiting reactant
the neutralization reaction is complete OH– is completely consumed
HC2H3O2 (aq) + H2O (l) ⇄ C2H3O2– (aq) + H3O+ (aq)
◆ pH of solution increases slightly
initial [ ] 0.090 M --- 0.11 M 0 solution becomes slightly more basic
∆[] –x --- +x +x
equil [ ] (0.090–x)M --- (0.11+x)M xM
Change of pH of a Buffer Solution With H+ or OH– Added How Does a Buffer Work?
◆ pH is controlled by [H+]
◆ in an HA/A– buffer solution:
HA (aq) ⇄ H+ (aq) + A– (aq)
[H+][A–] [HA]
Ka = –––––––– OR [H+] = Ka –––––
[HA] [A–]
example:
example:
40.0 mL of 0.110 M HCl (aq) is titrated with 0.095 M 40.0 mL of 0.110 M HCl (aq) is titrated with 0.095 M NaOH (aq).
NaOH (aq).
◆ neutralization reaction (Na+ and Cl– spectator ions):
H+ (aq) + OH– (aq) → H2O (l) ◆ Determine the initial pH; pH of the solution before
adding any NaOH (aq).
◆ calculate mol H+ (aq):
another way to say this . . .
mol H+ = (0.0400 L)(0.110 mol/L)
What is the pH of 0.110 M HCl (aq)?
= 0.00440 mol H+
[H+] = 0.110 M
◆ calculate volume NaOH (aq) required to reach the
pH = – log (0.110) = 0.96
stoichiometric point:
0.00440 mol H+ x 1––––––––––
mol OH– x –––––––––––
1 L sol’n = 0.0463 L
1 mol H + .095 mol OH–
or 46.3 mL
example: example:
40.0 mL of 0.110 M HCl (aq) is titrated with 0.095 M NaOH (aq). 40.0 mL of 0.110 M HCl (aq) is titrated with 0.095 M NaOH (aq).
◆ Determine the pH after the addition of 30.0 mL ◆ Determine [excess reactant] after neutralization
NaOH (aq). reaction is complete:
mol OH– added = (0.0300 L)(0.095 mol/L) mol H+ after rxn
[H+] = ––––––––––––––––
= 0.0029 mol OH– total sol’n volume
◆ set up a reaction table to identify limiting and excess reactant:
0.0015 mol H+
[H+] = –––––––––––––––––
(0.0400 + 0.0300) L
H+ (aq) + OH– (aq) → H2O (l)
before rxn: 0.00440 mol 0.0029 mol ---
change: –0 .0029 mol – 0.0029 mol --- [H+] = 0.021 M
after rxn: 0.0015 mol 0 --- pH = 1.68
example: example:
40.0 mL of 0.110 M HCl (aq) is titrated with 0.095 M NaOH (aq). 40.0 mL of 0.110 M HCl (aq) is titrated with 0.095 M NaOH (aq).
◆ Determine the pH at the stoichiometric point.
◆ Determine the pH after the addition of 60.0 mL
46.3 mL NaOH (aq) added to reach stoichiometric pt NaOH (aq).
at stoichiometric point: mol OH– added = (0.0600 L)(0.095 mol/L)
mol OH– added = mol H+ present = 0.00440 mol = 0.0057 mol OH–
◆ set up reaction table: ◆ set up a reaction table to identify limiting and excess reactant:
H+ (aq) + OH– (aq) → H2O (l)
H+ (aq) + OH– (aq) → H2O (l)
before rxn: 0.00440 mol 0.0044 mol ---
before rxn: 0.00440 mol 0.0057 mol ---
change: –0 .0044 mol – 0.0044 mol ---
change: –0 .0044 mol – 0.0044 mol ---
after rxn: 0 0 ---
after rxn: 0 0.0013 mol ---
◆ after reaction the solution is neutral; pH = 7.00
example:
40.0 mL of 0.110 M HCl (aq) is titrated with 0.095 M NaOH (aq).
Some Titration Data/Titration Curves
◆ Determine [excess reactant] after neutralization Strong Acid/Strong Base Titrations:
• Consider the titration of 40.0 mL of 0.110 M HCl (aq) with 0.095 M NaOH (aq).
reaction is complete: mL NaOH added total sol’n vol. [H3O+] after rxn pH
before 0 40 0.110 M 0.96
stoichiometric 5 45 0.087 M 1.07
mol OH–
[OH–] = –––––––––––––––– point: 10 50 0.070 M 1.15
0.0013 mol
[OH–] = ––––––––––––––––– beyond 47 87
[OH–] after rxn
0.00115 M 11.06
(0.0400 + 0.0600) L
Some Titration Data/Titration Curves
stoichiometric
point:
50
60
90
100
0.0044 M
0.013 M
11.64
12.11
Strong Acid/Strong Base Titrations:
• Consider the titration of 40.0 mL of 0.110 M HCl (aq) with 0.095 M NaOH (aq). 70 110 0.020 M 12.31
mL NaOH added total sol’n vol. [H3O+] after rxn pH 80 120 0.027 M 12.43
before 0 40 0.110 M 0.96
stoichiometric 5 45 0.087 M 1.07
point:
[OH–] = 0.013 M
10
30
50
70
0.070 M
0.021 M
1.15
1.68
45 85 0.012 M 1.92
12
Titration Curve for Strong Acid + Strong Base Weak Acid + Strong Base Titrations
Titration of 40.0 mL of 0.110 M HCl (aq) with 0.095 M NaOH (aq)
14
strategy: 10
pH
12
8
10
reaction that will occur
◆ strong base is completely ionized
6
pH
0
3. set up a reaction table; identify the limiting and
0
0 20 40 60 80
notes: 0 20 40 60 80
excess reactant
volume NaOH added, mL volume NaOH added, mL
example: example:
30.0 mL of 0.125 M HC2H3O2 (aq) is titrated with 0.100 M NaOH. 30.0 mL of 0.125 M HC2H3O2 (aq) is titrated with 0.100 M NaOH.
example: example:
30.0 mL of 0.125 M HC2H3O2 (aq) is titrated with 0.100 M NaOH. 30.0 mL of 0.125 M HC2H3O2 (aq) is titrated with 0.100 M NaOH.
◆ using an equilibrium table (Ka = 1.8 x 10–5): ◆ Determine the pH at the stoichiometric point.
HC2H3O2 ⇄ C2H3O2 – + H+
37.5 mL NaOH (aq) added to reach stoichiometric pt
initial [ ]: .0350 M .0400 M 0
at stoichiometric point:
change [ ]: –x +x +x
mol OH– added = mol HC2H3O2 present = 0.00375 mol
equil [ ]: (.0350 – x) M (.0400 + x) M xM
◆ set up reaction table:
x= [H+] = 1.6 x 10–5 M; pH = 4.80
HC2H3O2 + OH– → C2H3O2– + H2O
◆ using Henderson-Hasselbalch (pKa = 4.74): before rxn: .00375 mol .00375 mol 0 ---
change: –.00375 mol –.00375 mol +.00375 mol ---
.0400
pH = 4.74 + log ––––––
.0350 after rxn: 0 0 .00375 mol ---
pH = 4.80
example:
example:
30.0 mL of 0.125 M HC2H3O2 (aq) is titrated with 0.100 M NaOH.
30.0 mL of 0.125 M HC2H3O2 (aq) is titrated with 0.100 M NaOH.
◆ the equilibrium table and calculation:
◆ after the neutralization reaction, HC2H3O2 and OH– C2H3O2– + H2O ⇄ HC2H3O2 + OH–
are completely consumed initial [ ]: .0556 M --- 0 0
◆ base ionization of C2H3O2 controls the pH of sol’n:
–
∆ [ ]: –x --- +x +x
C2H3O2– (aq) + H2O (l) ⇄ HC2H3O2 (aq) + OH– (aq) equil [ ]: (.0556 –x)M --- xM xM
Kb = KW÷(Ka for HC2H3O2) = 5.6 x 10–10 x2
Kb = 5.6 x 10–10 = ––––––––––
.0556 – x
◆ determine [C2H3O2–] after neutralization reaction:
◆ solve for x: x = [OH–] = 5.6 x 10–6 M
.00375 mol pOH = 5.25
[C2H3O2–] = ––––––––––– = 0.0556 M
.0675 L pH = 8.75
◆ for a weak acid titrated with a strong base, the pH > 7 at
the stoichiometric point
example: example:
30.0 mL of 0.125 M HC2H3O2 (aq) is titrated with 0.100 M NaOH. 30.0 mL of 0.125 M HC2H3O2 (aq) is titrated with 0.100 M NaOH.
◆ determine [excess reactant] after neutralization
◆ Determine the pH after the addition of 50.0 mL reaction is complete:
NaOH (aq).
mol OH–
mol OH– added = (0.0500 L)(0.100 mol/L) [OH–] = ––––––––––––––––
total sol’n volume
= 0.00500 mol OH–
◆ set up a reaction table to identify limiting and excess reactant: 0.00125 mol
[OH–] = –––––––––––––––––
(0.0300 + 0.0500) L
HC2H3O2 + OH– → C2H3O2– + H2O
before rxn: .00375 mol .00500 mol 0 --- [OH–] = 0.0156 M
change: –.00375 mol –.00375 mol +.00375 mol --- pOH = 1.81; pH = 12.19
after rxn: 0 .00125 mol .00375 mol ---
point: 60 90 0.025 M 12.40
75 105 0.0357 M 12.55
pH
point: 10 40 5.0 x 10 5 M
! 4.30
20 50 1.6 x 10 5 M
! 4.80 8
30 60 4.6 x 10 5 M
! 5.34
35 65 1.3 x 10 6 M
! 5.89
37 67 2.5 x 10 7 M
! 6.61 6
example:
example:
12
half-way to the stoichiometric point mol OH– added = (0.01875 L)(0.100 mol/L)
vol required = !(vol to reach stoich.pt.)
6 = 0.001875 mol OH–
◆ set up a reaction table to identify limiting and excess reactant:
◆ for this titration:
4
Strong Acid + Weak Base Titrations Strong Acid + Weak Base Titrations
4. identify the species present when the neutralization example:
reaction is complete, and determine which of them are 20.0 mL of 1.20 M CH3NH2 (aq) is titrated with
key to determining the pH of the solution 0.750 M HNO3 (aq).
◆ before the stoichiometric point, the neutralization
Determine the following:
reaction results in a B/BH+ buffer solution
◆ initial pH of the solution
◆ at the stoichiometric point, the acid ionization of
BH+ will determine the pH ◆ pH after the addition of 10.0 mL of HNO3
◆ pH at the stoichiometric point
◆ beyond the stoichiometric point excess H+
determines the pH ◆ pH after the addition of 50.0 mL HNO3
5. using post-neutralization concentrations of species, set up
the appropriate calculation and determine pH of solution
example: example:
20.0 mL of 1.20 M CH3NH2 (aq) is titrated with 0.750 M HNO3. 20.0 mL of 1.20 M CH3NH2 (aq) is titrated with 0.750 M HNO3.
◆ neutralization reaction (NO3– spectator ion): ◆ Determine the initial pH; pH of the solution before
CH3NH2 (aq) + H+ (aq) → CH3NH3+ (aq) adding any CH3NH2 (aq).
◆ calculate mol CH3NH2 (aq): another way to say this . . .
mol CH3NH2 = (0.0200 L)(1.20 mol/L) What is the pH of 1.20 M CH3NH2 (aq)?
= 0.0240 mol CH3NH2 weak base calculation; Kb for CH3NH2 = 3.7 x 10–4
◆ calculate volume HNO3 (aq) required to reach the x = [OH–] = 0.021 M
stoichiometric point:
pOH = – log (0.021) = 1.68
1 mol H+ x –––––––––––
0.0240 mol CH3NH2 x –––––––––––– 1 L sol’n = 0.0320 L
1 mol CH3NH2 .750 mol H+
or 32.0 mL pH = 12.32
example: example:
20.0 mL of 1.20 M CH3NH2 (aq) is titrated with 0.750 M HNO3. 20.0 mL of 1.20 M CH3NH2 (aq) is titrated with 0.750 M HNO3.
◆ Determine the pH after the addition of 10.0 mL ◆ determine [CH3NH2] and [CH3NH3+] after
HNO3 (aq). neutralization reaction is complete:
mol H+ added = (0.0100 L)(0.750 mol/L) .0165 mol
[CH3NH2] = –––––––––––––– .00750 mol
[CH3NH3+] = ––––––––––––
= 0.00750 mol H+ (.0200 + .0100)L (.0200 + .0100)L
example: example:
20.0 mL of 1.20 M CH3NH2 (aq) is titrated with 0.750 M HNO3. 20.0 mL of 1.20 M CH3NH2 (aq) is titrated with 0.750 M HNO3.
◆ the equilibrium table and calculation:
◆ after the neutralization reaction, CH3NH2 and H+
CH3NH3+ ⇄ CH3NH2 + H+
are completely consumed
initial [ ]: 0.462 M 0 0
◆ acid ionization of CH3NH3+ controls the pH of sol’n:
∆ [ ]: –x +x +x
CH3NH3+ (aq) ⇄ CH3NH2 (aq) + H+ (aq)
equil [ ]: (0.462 – x) M xM xM
Ka = KW÷(Kb for CH3NH2) = 2.7 x 10–11 x2
Ka = 2.7 x 10–11 = ––––––––––
◆ determine [CH3NH3+] after neutralization reaction: .462 – x
.0240 mol ◆ solve for x: x = [H ] = 3.5 x 10–6 M
+
◆ Determine the pH after the addition of 50.0 mL HNO3 (aq). ◆ determine [excess reactant] after neutralization
reaction is complete:
mol H+ added = (0.0500 L)(0.750 mol/L)
= 0.0375 mol H+ mol H+
[H+] = ––––––––––––––––
total sol’n volume
◆ set up a reaction table to identify limiting and excess reactant:
0.0135 mol
CH3NH2 + H+ → CH3NH3+ [H+] = –––––––––––––––––
(0.0200 + 0.0500) L
before rxn: .0240 mol .0375 mol 0
change: –.0240 mol –.0240 mol +.0240 mol
[H+] = 0.193 M
after rxn: 0 .0135 mol .0240 mol
pH = 0.741
example: example:
20.0 mL of 1.20 M CH3NH2 (aq) is titrated with 0.750 M HNO3. 20.0 mL of 1.20 M CH3NH2 (aq) is titrated with 0.750 M HNO3.
◆ Determine the pH after the add’n of 16.0 mL HNO3 (aq). ◆ determine [CH3NH2] & [CH3NH3+] after neutralization
reaction is complete:
mol H+ added = (0.0160 L)(0.750 mol/L)
.0120 mol .0120 mol
= 0.0120 mol H+ [CH3NH2] = –––––––––––––
.0360 L
[C2H3O2–] = ––––––––––––
.0360 L
◆ set up a reaction table to identify limiting and excess reactant: [HC2H3O2] = 0.330 M [C2H3O2–] = 0.330 M
CH3NH2 + H+ → CH3NH3+
◆ this is a buffer solution with [acid] = [base]
before rxn: .0240 mol .0120 mol 0 ◆ using Henderson-Hasselbalch (pKa = 10.57):
.330
pH = 10.57 + log ––––––
change: –.0120 mol –.0120 mol +.0120 mol
.330
after rxn: .0120 mol 0 .0120 mol pH = pKa = 10.57
◆ at the half-way point in a weak + strong titration, the
pH of the solution equals the pKa of the acid
50 70 0.193 M 0.714
60 80 0.263 M 0.580
pH
20 40 2.2 x 10 4 M
!
10.35
25 45 1.0 x 10 4 M 10.01
stoichiometric pt
!
6
30 50 2.5 x 10 5 M
!
9.40
[H3O+] after rxn
4
at stoich. point: 32 52 3.5 x 10 6 M
!
5.46
beyond 35 55 0.042 M 1.38
stoichiometric 40 60 0.100 M 1.00 2
12
Acid-Base Indicators Acid-Base Indicators
◆ an indicator is used to indicate the stoichiometric
point in a titration - typically by change in color
10 ◆ a few examples of indicators:
Weak Acid + Strong Base Titration: Strong Acid + Weak Base Titration:
pH at stoichiometric point > 7 pH at stoichiometric point < 7
Final Thoughts on Acid-Base Titrations
Final Thoughts on Acid-Base Titrations
◆ if H3O+ or OH– is present after the neutralization reaction,
go straight to pH calculation
◆ neutralization reactions happen 1st
fast at any point in a strong acid + strong base titration
beyond the stoichiometric point in weak + strong titration
go to completion
◆ if HA & A– or B & BH+ are present after the neutralization
◆ set up reaction table (with mol of species) for the reaction:
neutralization reaction buffer solution – use equilibrium calculation or
Henderson-Hasselbalch equation
◆ assess what is in solution when the neutralization before the stoichiometric point in weak + strong titration
reaction is complete
◆ if A– or BH+ are present after the neutralization reaction:
◆ calculate post-neutralization [ ] of important species equilibrium calculation based on ionization:
[ ] = mol ÷ total sol’n volume A– (aq) + H2O (l) ⇄ HA (aq) + OH– (aq)
BH+ (aq) ⇄ B (aq) + H+ (aq)
at the stoichiometric point in weak + strong titration