DR. MIOY T.
HUYNH | 2020
ACIDS & BASES
ACID-BASE TITRATIONS (PROBLEMS)
CHEMISTRY 165 // SPRING 2020
T itration cu rves
Titrating a weak acid (HCN) with a strong base (NaOH ➝ Na+ + OH–).
Most titration curves will have this general shape. RECAP
At point (1): We haven’t added any NaOH, so the
Mostly OH– , CN–, and H2O
pH comes from the weak acid equilibrium.
At point (2): This is called the midpoint because we
have added exactly half of what we need to get to
the equivalence point.
Here [HCN] = [CN–] and pH = pKa.
Mostly CN– and H2O
some OH–
Near point (2): This region is the buffer region,
where we have HCN and CN– in solution, so you
can apply the Henderson-Hasselbalch equation to
get pH.
Mostly HCN ≈ CN– and H2O
very little H+ At point (3): You add exactly nHCN = nOH and make
the salt NaCN. Here you only have the conjugate-
Mostly HCN and H2O base (CN–) reacting with water, which will
a little H+ and CN– determine the pH.
After point (3): You are adding excess OH, which
will completely determine the pH.
PRACTICE PROBLEM 1
You have a 1.0 L solution of 0.50 M HNO2 (𝐾" = 4.0 × 10)* ) being titrated with 0.50 M NaOH.
Calculate the pH of this solution initially, before any NaOH is added.
— answer —
PRACTICE PROBLEM 1
You have a 1.0 L solution of 0.50 M HNO2 (𝐾" = 4.0 × 10)* ) being titrated with 0.50 M NaOH.
Calculate the pH of this solution initially, before any NaOH is added.
— answer —
At this point, we have only the weak acid dissociating in water since no NaOH has been added.
Thus, we can set up the weak acid dissociation equilibrium in water.
We can construct an ICE chart for this equilibrium, set up a Ka expression, solve for x, and determine the pH.
H - NO)0
HNO2 ⇌ H+ + NO2– 𝐾" = = 4.0×10)*
HNO0
I 0.50 M 0M 0M
C –x +x +x )*
x x
4.0×10 =
E 0.50 – x x x 0.50 − x
Because the value of Ka is very small, we know that the system will x0
4.0×10)* ≈
undergo very little change (x value) toward the right in order to 0.50
achieve equilibrium. In other words, we can take “x” to be very
small/negligible and invoke the approximation that: x = 0.00145 M = H -
0.50 – x ≈ 0.50 pH = − log 0.0013< = 1.85
PRACTICE PROBLEM 2
You have a 1.0 L solution of 0.50 M HNO2 (𝐾" = 4.0 × 10)* ) being titrated with 0.50 M NaOH.
Calculate the pH of this solution after 250. mL of 0.50 M NaOH are added.
— answer —
PRACTICE PROBLEM 2
You have a 1.0 L solution of 0.50 M HNO2 (𝐾" = 4.0 × 10)* ) being titrated with 0.50 M NaOH.
Calculate the pH of this solution after 250. mL of 0.50 M NaOH are added.
— answer —
At this point, we have added some NaOH, which is a strong base, so remember: NaOH ➝ Na+ + OH–
First, determine how much OH– we have added:
0.50 mol HNO0 0.50 mol OH )
𝑛?@AB = 1.0 L × = 0.50 mol HNO0 𝑛A?E = 0.250 L × = 0.12G mol OH )
1L 1L
So we are not at the equivalence point and can use the Henderson-Hasselbach equation to find the pH.
Second, we need to consider the reaction between HNO2 and OH– using an ICF chart:
HNO2 + OH– ➝ NO2– + H2O
I 0.50 mol 0.125 mol 0 mol n/a
C – 0.125 – 0.125 + 0.125 n/a
F 0.375 0 0.125 n/a Use the Henderson-Hasselbalch equation to find pH.
Convert to M
by dividing by NO)
0
Vtot = 1.25 L 0.300 M 0M 0.100 M n/a pH = p𝐾" + log
HNO0
)*
0.10I
= − log 4.0×10 + log
0.30I
= 3.39K − 0.47M
pH = 2.92
PRACTICE PROBLEM 3
You have a 1.0 L solution of 0.50 M HNO2 (𝐾" = 4.0 × 10)* ) being titrated with 0.50 M NaOH.
Calculate the pH of this solution after 500. mL of 0.50 M NaOH are added.
— answer —
PRACTICE PROBLEM 3
You have a 1.0 L solution of 0.50 M HNO2 (𝐾" = 4.0 × 10)* ) being titrated with 0.50 M NaOH.
Calculate the pH of this solution after 500. mL of 0.50 M NaOH are added.
— answer —
At this point, we have added some NaOH, which is a strong base, so remember: NaOH ➝ Na+ + OH–
First, determine how much OH– we have added:
0.50 mol HNO0 0.50 mol OH )
𝑛?@AB = 1.0 L × = 0.50 mol HNO0 𝑛A?E = 0.500 L × = 0.25 mol OH )
1L 1L
So we are not at the equivalence point and can use the Henderson-Hasselbalch equation to find the pH.
Second, we need to consider the reaction between HNO2 and OH– using an ICF chart:
HNO2 + OH– ➝ NO2– + H2O
I 0.50 mol 0.25 mol 0 mol n/a
C – 0.25 – 0.25 + 0.25 n/a
F 0.25 0 0.25 n/a Use the Henderson-Hasselbalch equation to find pH.
Convert to M
by dividing by NO)
0
Vtot = 1.50 L 0.17 M 0M 0.17 M n/a pH = p𝐾" + log
HNO0
)*
0.17
= − log 4.0×10 + log
This is the midpoint where [HNO2] = [NO2–] and
0.17
1 = 3.39K + 0
𝑛A?E = ×𝑛?@AB
2 pH = 3.40
PRACTICE PROBLEM 4
You have a 1.0 L solution of 0.50 M HNO2 (𝐾" = 4.0 × 10)* ) being titrated with 0.50 M NaOH.
Calculate the pH of this solution after 1000. mL of 0.50 M NaOH are added.
— answer —
PRACTICE PROBLEM 4
You have a 1.0 L solution of 0.50 M HNO2 (𝐾" = 4.0 × 10)* ) being titrated with 0.50 M NaOH.
Calculate the pH of this solution after 1000. mL of 0.50 M NaOH are added.
— answer —
At this point, we have added some NaOH, which is a strong base, so remember: NaOH ➝ Na+ + OH–
First, determine how much OH– we have added:
0.50 mol HNO0 0.50 mol OH )
𝑛?@AB = 1.0 L × = 0.50 mol HNO0 𝑛A?E = 1.000 L × = 0.50 mol OH )
1L 1L
We are at the equivalence point. Second, we need to consider the reaction between HNO2 and OH– using an ICF chart:
𝑛A?E = 𝑛?@AB HNO2 + OH– ➝ NO2– + H2O First, find the Kb from the Ka and Kw:
𝐾O 1.0×10)5*
I 0.50 mol 0.50 mol 0 mol n/a 𝐾N = = = 2.5×10)55
𝐾" 4.0×10)*
C – 0.50 – 0.50 + 0.50 n/a
F 0 0 0.50 n/a Set up a Kb expression and solve for x.
Convert to M HNO0 OH )
𝐾N =
by dividing by NO)0
Vtot = 2.00 L 0M 0M 0.25 M n/a x x
)55
2.5×10 =
Now we consider the weak-base (NO2–) equilibrium: 0.25 − x
0
x
2.5×10)55 ≈
NO2– + H2O ⇌ HNO2 + OH– 0.25
x = 2.5 × 10)P M = OH )
I 0.25 M n/a 0M 0M
C –x n/a +x +x Now find pOH and pH:
E 0.25 – x n/a x x pOH = − log 2.5 × 10)P = 5.600
pH = 14 − 5.600 = 8.40
PRACTICE PROBLEM 5
You have a 1.0 L solution of 0.50 M HNO2 (𝐾" = 4.0 × 10)* ) being titrated with 0.50 M NaOH.
Calculate the pH of this solution after 1500. mL of 0.50 M NaOH are added.
— answer —
PRACTICE PROBLEM 5
You have a 1.0 L solution of 0.50 M HNO2 (𝐾" = 4.0 × 10)* ) being titrated with 0.50 M NaOH.
Calculate the pH of this solution after 1500. mL of 0.50 M NaOH are added.
— answer —
At this point, we have added a lot of NaOH, which is a strong base, so remember: NaOH ➝ Na+ + OH–
First, determine how much OH– we have added:
0.50 mol HNO0 0.50 mol OH )
𝑛?@AB = 1.0 L × = 0.50 mol HNO0 𝑛A?E = 1.500 L × = 0.75 mol OH )
1L 1L
We are past the equivalence point. Second, we need to consider the reaction between HNO2 and OH– using an ICF chart:
HNO2 + OH– ➝ NO2– + H2O
I 0.50 mol 0.75 mol 0 mol n/a
C – 0.50 – 0.50 + 0.50 n/a
F 0 0.25 0.50 n/a
Convert to M
by dividing by
Vtot = 2.50 L 0M 0.10 M 0.20 M n/a
Because OH– is a much stronger base than NO2–, we need only consider its effect on pH.
pOH = − log 0.10 = 1.00
pH = 14 − 1.00 = 13.00
