Module 24-26 Notes
Module 24-26 Notes
Practice Questions:
16.15, 16.31, 16.85, 16.87, 16.89, 16.93, 16.107, 16.109, 16.119, 16.121,
16.135, 16.143.
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– TITRATIONS CURVES –
REACTIONS BETWEEN ACIDS AND
BASES
MODULE 24
1. General Remarks
Recall the 3 types of Acid-Base reactions that we will consider:
(i) Strong Acid + Strong Base: H3O+(aq) + OH–(aq) → 2 H2O(l) Keq =
(ii) Weak Acid + Strong Base: HA(aq) + OH–(aq) → H2O(l) + A–(aq) Keq =
(iii) Strong Acid + Weak Base: H3O+(aq) + B(aq) → H2O(l) + BH+(aq) Keq =
When will the reaction (titration) be complete when we are adding Acid to a solution of Base?
At that time we will observe a sudden ________ of the pH as the solution becomes ______
When will the reaction (titration) be complete when we are adding Base to a solution of Acid?
At that time we will observe a sudden ________ of the pH as the solution becomes ______
2
(i) Strong Acid + Strong Base: H3O+(aq) + OH–(aq) → 2 H2O(l)
pH at Equivalence Point =
2. Colored Indicators
We will use colored indicators when we do not have a pH meter to determine the equivalence point.
To be accurate, these indicators must change color as close as possible to the time we reach the
equivalence point. In other words we need these to change color at the pH value expected at the
equivalence point.
Thus, we will need to choose the right indicator! Since this pH will vary depending on the species
titrated (see above what we just discussed).
Colored Indicators are organic dyes which are _________________ and thus can be converted to
their organic conjugate base following the equation:
In(aq) + H2O(l) ⇌ H3O+(aq) + In–(aq)
For successful use, HIn & In–must be brightly and differently coloured.
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2.1 When do indicators change color: i.e. how do they work?
Reaction Equation:
HIn(aq) + H2O(l) ⇌ H3O+(aq) + In–(aq)
At any time we have a mixture of both HIn and In– but depending on the ratio of the two we see the
[In–] 1
= = 0.1 We see HIn (in that case red)
[HIn] 10
If
[In–] 10
= = 10 We see In– (in that case blue)
[HIn] 1
From this equation you can understand that the color that we see depends both on the [H 3O+] (or pH) and
Ka(HIn) (or pKa) of the colored indicator.
For example: Let’s assume that we have a colored indicator with Ka(HIn) = 10–7
At [H3O+] = 10–6 M (i.e. pH = 6):
[In–] Ka(HIn) 10–7 1
= = = 10–1 = 0.1 = we SEE HIn
[HIn] [H3O+] 10–6 10
Remember that the pH of the solution at the equivalence point depends on the species that is being titrated
(go back to section 1.2), thus in order to successfully determine the equivalence point
Pay Attention!!! The equivalence point and end point have nothing to do with each other, unless we
intentionally choose the proper indicator! We must choose the indicator carefully so that the pK a of the
indicator is close to the pH anticipated at the equivalence point.
The end point pH & equivalence point pH should be as close as possible.
b. When we react a Weak acid (e.g. HAc) with a Strong Base what do you think the pH will be at
Equivalence?
Question 1: Consider the titration below and answer the questions a-c (next page)
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a. What type of titration are we looking at?
CALCULATE pH FOR POINT 3-6 BY YOURSELVES go page 8 (see results in table below)
[H3O+] = pH = 1.95
etc., etc.,
7
Point 5: Add 24.00 mL of 0.100 M NaOH to 25.00 mL of a 0.100 M HCl (pH = 2.69)
Point 6: Add 24.50 mL of 0.100 M NaOH to 25.00 mL of a 0.100 M HCl (pH = 3.00)
pH
6.0
5 24.00 0.00204 2.69
4.0
6 24.50 1.0×10–3 3.00
2.0
7 25.00 1.0×10–7 7.00
0.0
8 25.10 5.0×10–11 10.30
0 5 10 15 20 25 30 35
Volume of NaOH added (mL)
pH at the equivalence point will be equal to 7.00: we have a neutral solution (spectator cations &
anions). Refer to Figure 16.12 (pg. 693) in your text for the titration curve of a strong base titrating
a strong acid.
Pick an indicator whose pKa 7 or Ka 10–7, so that the End Point of the indicator is at the
same pH as the Equivalence Point for the Titration.
Question 2:
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2. What is the original concentration of acid? (Ans C)
A. 10 M C. 0.10 M
B. 1.0 M D. 0.010 M
3. If the concentration of NaOH is 0.10 M, what was the starting volume of acid? (Ans D)
A. 1.0 mL C. 10 mL
B. 1.5 mL D.15 mL
END OF MODULE 24
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– TITRATIONS CURVES –
REACTIONS BETWEEN ACIDS AND
BASES
MODULE 25
4. Weak Acid (WA) + Strong Base (SB)
Consider 50.00 mL 1.0 M of Cyanic Acid NCOH [Ka(NCOH) = 3.5 × 10–4, pKa(NCOH) = 3.46] and titrate
this with 1.0 M NaOH.
Calculate the pH as titration proceeds.
As long as there is some strong base it will react with the weak acid. Then once all the OH – has been reacted
we will have in solution NCO– and NCOH: ie. a conjugate acid/base pair in equilibrium with one another
[H3O+] × [NCO–]
Ka(NCOH) =
[NCOH]
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CNCOH 1.0 M
= =
Ka(NCOH 3.5×10–4
x= ⇨ [H3O+] =
⇨ pH = = 1.73
x
× 100 > 5 % ⇒ × 100 = %
CNCOH
What we end up with: we now have is a solution with both NCOH & NCO – present in non-trivial amounts.
Buffer equilibrium:
nNCO–
pH = pKa(NCOH) + log
nNCOH
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Point 3. After 25.00 mL of 1.0 M base added to 50.00 mL of 1.0 M NCOH:
n(NCOH) = 1.0 mmoles/mL 50.00 mL = mmol
n(OH–) = 1.0 mmoles/mL 25.00 mL = mmol
new volume = 75 mL
What point in the titration have we reached?
Rxn: OH–(aq) + NCOH(aq) NCO–(aq) + H2O(l)
I 25 50 0 (mmol)
C
E
This is a
nNCO–
pH = pKa(NCOH) + log
nNCOH
DYI Point 4. After 40.00 mL of 1.0 M base added to 50.00 mL of 1.0 M NCOH (Ans: pH = 4.06)
n(NCOH) = 1.0 mmoles/mL 50.00 mL = mmol
n(OH–) = 1.0 mmoles/mL 40.00 mL = mmol
new volume = 90 mL
This is a
nNCO–
pH = pKa(NCOH) + log
nNCOH
Point 5. After 49.00 mL of base added to 50.00 mL of 1.0 M NCOH (Ans: pH = 5.15)
n(NCOH) = 1.0 mmoles/mL 50.00 mL = mmol
n(OH–) = 1.0 mmoles/mL 49.00 mL = mmol
new volume = 99 mL
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Rxn: OH–(aq) + NCOH(aq) NCO–(aq) + H2O(l)
I 49 50 0 (mmol)
C
E
Not an effective buffer at all, but we can still use the H-H equation, because we still have both conjugates
present in the solution.
Remember the H-H equation was derived from the K a expression for the equilibrium:
NCOH(aq) + H2O(l) ⇌ H3O+(aq) + NCO–(aq)
Equilibrium 1 –x x 49+ x
x <<< 1 and 49: x is still much smaller than 1 mmol and 49 mmol- we can therefore still use the H-H
equation to calculate the pH, even though this is no longer a buffer!
nNCO–
pH = pKa(NCOH) + log
nNCOH
Point 6. After 50.00 mL base added to 50.00 mL of 1.0 M NCOH
n(NCOH) = 1.0 mmoles/mL 50.00 mL = mmol
n(OH–) = 1.0 mmoles/mL 50.00 mL = mmol
new volume = 100 mL
What point in the titration have we reached?
Kw 10–14
Kb(NCO-) = = = 2.86 × 10–11
Ka(NCOH) 3.5×10–4
14
CNCONa 0.5 M
= =
Kb(NCO–) 2.86 × 10–11
[OH–] = y = Kb×Cb =
pOH = –log [OH–] =
pH = 14.00 – pOH =
To verify the approximation (5% rule) calculate %Prot =
Point 7. After 51.00 mL strong base added to 50.00 mL of 1.0 M NCOH
n(NCOH) = 1.0 mmoles/mL 50.00 mL = mmol
n(OH–) = 1.0 mmoles/mL 51.00 mL = mmol
new volume = 101 mL
NCOH(aq) + OH–(aq) NCO–(aq) + H2O(l)
I 50 51 0 (mmol)
C
End
⇨ The amount of OH– produced from the reaction of NCO– with H2O is INSIGNIFICANT. So when we
have SB + WB, we can IGNORE the WB contribution because the y value is so small in comparison.
y <<< COH- ⇨ [OH-] COH-
COH– = 1 mmol/101 mL = 0.01 M
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Summary for the Weak Acid + Strong Base Titration:
Base
Pt. added pH Comments
(ml)
1. 0 1.73
2. 10 2.86
3. 25 3.46
4. 40 4.06
5. 49 5.15
6. 50 8.58
7. 51 12.0
12.000
10.000
8.000
pH
6.000
4.000
2.000
0.000
0 5 10 15 20 25 30 35 40 45 50 55
Volume NaOH Added (mL)
END OF MODULE 25
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– TITRATIONS CURVES –
REACTIONS BETWEEN ACIDS AND
BASES
MODULE 26
y2
Kb(NH3) =
1.0 – y
CNH3 1.0 M
= =
Kb 1.8 × 10-5
y= ⇨ [OH–] = ⇨ pOH = pH =
17
Let’s check that indeed:
y
× 100 > 5 % ⇒ × 100 = %
CNH3
What we end up with: we now have is a solution with both NH 3 & NH4+ present in non-trivial amounts.
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What is the ratio of NH3 to NH4+?
What do we call this kind of solution?
n(NH3)
pH = pKa(NH4+) + log
n(NH4+)
DYI: Point 4. Add 40.00 mL of 1.0 M HCl to initial 50.00 mL of 1.0 M NH3 (Ans: pH = 8.65)
n(NH3) = 1.0 mmoles/mL 50.00 mL = mmol
n(H3O+) = 1.0 mmoles/mL 40.00 mL = mmol
new volume = 50.00 + 40.00 = 90.00 mL
H3O+ is the ___________________________
What we end up with: we now have is a solution with both NH 3 & NH4+ present in non-trivial amounts.
What is the ratio of NH3 to NH4+?
What do we call this kind of solution?
n(NH3)
pH = pKa(NH4+) + log
n(NH4+)
DYI Point 5. Add 49.00 mL of 1.0 M HCl to initial 50.00 mL of 1.0 M NH3 (Ans: pH = 7.57, Not an
effective buffer)
n(NH3) = 1.0 mmoles/mL 50.00 mL = mmol
n(H3O+) = 1.0 mmoles/mL 49.00 mL = mmol
new volume = 50.00 + 49.00 = 99.00 mL
H3O+ is the ___________________________
Rxn: H3O+(aq) + NH3(aq) NH4+(aq) + H2O(l)
I 49 mmol 50 mmol 0
C
End
What we end up with: we now have is a solution with both NH 3 & NH4+ present in non-trivial amounts.
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What is the ratio of NH3 to NH4+?
Not an effective buffer at all, but we can still use the H-H equation, because we still have both conjugates
present in the solution.
n(NH3)
pH = pKa(NH4+) + log
n(NH4+)
Ka(NH4+) = 10–9.26
CNH4+ 0.5 M
= =
Ka
[H3O–] = x = Ka×Ca =
pH =
20
Point 7. Add 51.00 mL of 1.0 M HCl to initial 50.00 mL of 1.0 M NH3
n(NH3) = 1.0 mmoles/mL 50.00 mL = mmol
n(H3O+) = 1.0 mmoles/mL 51.00 mL = mmol
new volume = 50.00 + 51.00 = 101.00 mL
What we end up with: we now have is a solution with both H 3O+ (SA) & NH4+ (WA) present in non-trivial
amounts.
Rxn: NH4+(aq) + H2O(l) ⇌ NH3(aq) + H3O+(aq)
CNH4+ – x +x CH3O+ + x
⇨ The amount of H3O+ (x) produced from the reaction of NH4+ with H2O is INSIGNIFICANT. So when
we have SA + WA, we can IGNORE the WA contribution because the x value is so small in comparison.
x <<< CH3O+ ⇨ [H3O+] CH3O+
CH3O+ = 1 mmol/101 mL = 0.01 M = 10–2 M
pH =
1. 0 11.63 10.0
2. 10 9.86 8.0
pH
6.0
3. 25 9.26
4.0
4. 40 8.65
2.0
5. 49 7.57 0.0
0 5 10 15 20 25 30 35 40 45 50 55
6. 50 4.78 Volum e of Acid Added (m L)
7. 51 2.00
8. 55 1.32
(Refer to Figure 16.14, pg. 696)
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Summary: Weak + Strong Titrations
END OF MODULE 26
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