11-Lecture 11 (2015-07-21) (Student Version)

Housekeeping for Tue.
7/21/15
- Exam 3 graded; scores posted to Blackboard; will return at end of class
- Exam 2 corrections due tomorrow (Wed. 7/22)
- HW 13 (and solutions) posted to Blackboard and Google Drive
- Ka of acetic acid work-up due today!
- Exam 3 corrections in play; due in class next Monday (7/27)!
Titration
in an acid-base titration, a solution of known concentration
(titrant) is slowly added to a solution of unknown concentration
(analyte) from a burette until the reaction is complete
when the reaction is complete we have reached the endpoint of
the titration
an indicator may be added to determine the endpoint
an indicator is a chemical that changes color when the pH
changes
when the moles of H3O+ = moles of OH, the titration has reached
its equivalence point
Equivalence point not the same as end point!
Equivalence point is the theoretical point when moles acid = moles base.
End point is experimental point that approximates equivalence point.
Titration
Indicators
many dyes change color depending on the pH of the solution
these dyes are weak acids, establishing an equilibrium with the H2O
and H3O+ in the solution
H-Ind(aq) + H2O(l) Ind(aq) + H3O+(aq)
Ka = [Ind-][H3O+] / [H-Ind]
pKa of indicator is pH where indicator changes color
When using an indicator to monitor a titration, we want to match the
pKa of the indicator with the pH of the equivalence point as closely
as possible.
Phenolphthalein
Methyl Red
H
C
(CH3)2N
H
C
H
C
C
C
H
(CH3)2N
OH-
CH
C
C
H
H
C
H
C
NaOOC
H
C
C
C
H
N
H
C
H
H3O+
H
C
H
C
C
H
CH
C
C
H
NaOOC
Matching indicators with titrations
The equivalence point for the titration of HCl with NaOH occurs at pH 7.
Which indicators would be suitable for this titration?
7
Types of titrations
Four general types of titrations:
- strong acid / strong base (base added to acid; base = titrant)
- strong base / strong acid (acid added to base; acid = titrant)
- weak acid / strong base
- weak base / strong acid
All titrations share common traits
- pH before titrant is added
- pH before equivalence point is reached
- pH at equivalence point (acid or base is entirely neutralized!)
- pH after equivalence point (excess titrant)
Strong acid / strong base titration (NaOH added to HCl)

14
12
pH after equivalence point
equivalence
point
10
pH
8
6
initial pH
4
2
pH before equivalence point
0
0
100
200
Vol. NaOH (mL)
300
400

Case study: 0.5 M NaOH is added to 200.0 mL of 0.5 M HCl
Phase 1: What is the initial pH?

Phase 2: What is the pH when 100 mL of NaOH have been added?
14
12
10
pH
8
6
4
2
0
0
100
200
Vol. NaOH (mL)
300
400

Quick detour Looking at the titration curve, we can see that we
havent reached the equivalence point. But we usually dont have a
titration curve to refer to. In fact, we dont really need the titration
curve to gauge where we are in the titration curve.
What we need to know is
- the total moles of acid before we start to titrate
- the volume of base we need to add to reach the equivalence point
(in other words, the volume of base to react completely with all the
acid)

Phase 3: What is the pH at the equivalence point?
14
12
10
pH
8
6
4
2
0
0
100
200
Vol. NaOH (mL)
300
400

Phase 4: What is the pH when 300.0 mL (total) of NaOH have been
added?
14
12
10
pH
8
6
4
2
0
0
100
200
Vol. NaOH (mL)
300
400

Vol. NaOH (mL)
pH
0
100
200
300
0.3
0.78
7
13
350
13.4
Things to keep in mind when working a titration problem

- total # of moles of acid (or base)
- # of moles of acid (or base) left after addn of titrant; helps you
decide if youve reached the equivalence point yet
- at equivalence point, no moles of acid (or base) left!
- after equivalence point, pH is due to excess titrant
Weak acid / strong base titration (NaOH added to HC2H3O2)

14
pH after equivalence point
12
10
8
equivalence
point
pH
initial pH
6
4
2
pH before equivalence point; *buffering region!*
0
0
100
200
Vol. NaOH (mL)
300
400
16

Case study: 0.5 M NaOH is added to 200.0 mL of 0.5 M HC2H3O2
17

Phase 2: What is the pH when 100 mL of NaOH are added?
14
12
10
pH
8
6
4
2
0
0
100
200
Vol. NaOH (mL)
300
400
18

Quick detour Looking at the titration curve, we can see that we
havent reached the equivalence point. Again, we usually dont have
a titration curve to refer to. And again, we dont really need the
titration curve to gauge where we are in the titration curve.
What we need to know is
- the total moles of acid before we start to titrate
- the volume of base we need to add to reach the equivalence point
(in other words, the volume of base to react completely with all the
acid)
- this is exactly the same as what we did with the strong acid /
strong base titration
19

14
12
Half-equivalence
point!
10
pH = pKa!
Buffering region is pKa +/- 1.
pH
At half-equivalance point, [acid] =

[conjugate base].
Buffering region
2
0
0
100
200
Vol. NaOH (mL)
300
400
20

14
Equivalence point
12
10
pH
8
6
4
2
0
0
100
200
Vol. NaOH (mL)
300
400
21

14
Equivalence point
12
10
pH
Notice that the pH is not 7! This

is because of the equilibrium of
acetate as a weak base at the
equivalence point.
6
4
2
0
0
100
200
Vol. NaOH (mL)
300
400
22

added?
14
12
10
pH
8
6
4
2
0
0
100
200
Vol. NaOH (mL)
300
400
23

Vol. NaOH (mL)
0
100
200
300
350
pH
2.52
4.74
9.1
13
13.4
Things to keep in mind for a weak acid/strong base titration

- total # of moles of acid (or base)
- what equilibrium is taking place in the buffer region? Weak acid
or weak base?
- what equilibrium is taking place at the equivalence point? Weak
base or weak acid?
- beyond equivalence point, calculations are same as strong acid/
strong base titration
24
Matching indicators with titrations
The equivalence point for the titration of HC2H3O2 with NaOH occurs at ~
pH 9. Which indicators would be suitable for this titration?
25
Solutions to exercises

Whats going on?
The initial pH is the pH of the solution before we add any titrant.
Since HCl is a strong acid, the pH is just the hydronium
concentration.
[H3O+] = [HCl] = 0.5 M
pH = -log (0.5 M)
= 0.3

Whats going on?
Before we start our calculations, lets just do a quick detour to
determine the total number of moles of acid that youre starting
with. This will tell us two things:
- what volume of base we need to reach the equivalence point;
- how much acid is left over after weve added our 100 mL of base
Initial moles of HCl = [HCl] x Vol. HCl
= (0.5 moles / L) x (0.200 L)
= 0.1 moles = 100 mmoles

Whats going on?
All right, so how much base do we need to add to react
completely with 100 mmoles of our acid? The neutralization
reaction shows that NaOH reacts 1:1 with HCl
HCl + NaOH NaCl + H2O
So we need 100 mmoles of base. Well use the molarity of NaOH to
determine the volume
0.100 moles NaOH x (1 L / 0.5 moles) = 0.2 L = 200 mL

Whats going on?
All right! Now were ready to calculate the pH
From the previous calculation, we determined that we need to add
200 mL of our base to reach the equivalence point. In phase 2,
weve only added 100 mL of base. So, we havent reached the
equivalence point. Well still have HCl left over.
So, pH will be due to the hydronium from the remaining HCl.
How much acid will be left over?

Calculations
Moles of NaOH added = [NaOH] x Vol. NaOH
= (0.5 moles / L) x (0.100 L)
Since HCl reacts with NaOH in a 1:1 manner, 50 mmoles of HCl
are neutralized.
Moles HCl remaining = 100 mmoles - 50 mmoles = 50 mmoles

Calculations
OK, almost there. Now we just need to calculate the pH based on
the amount of remaining hydronium.
[H3O+] = moles remaining acid / new volume!
We need to keep track of our volume:
initial volume = 200 mL
100 mL of NaOH added
New volume = (200 + 100) mL = 300 mL

Calculations
OK, almost there. Now we just need to calculate the pH based on
the amount of remaining hydronium.
[H3O+] = moles remaining acid / new volume!
= 50 mmoles / 300 mL
= 0.17 M
pH = -log (0.17 M)
= 0.78

Whats going on?
At the equivalence point, the amount of base is equal to the amount
of acid. That is, moles base = moles acid.
All the acid has been neutralized!
The only source of acidity is from the autoionization of water.
Kw = [H3O+][OH-] = 1.0 x 10-14
Since [H3O+] = [OH-] for pure water, [H3O+] = 1.0 x 10-7
pH = -log (1.0 x 10-7) = 7

For the titration of a strong acid with a strong base (or vice versa),
the pH at the equivalence point will always be 7.
This is not the case for weak acids and weak bases, as well see
shortly.

added?
Whats going on?
At this point, were adding excess base. The pH will be due to the
excess hydroxide.
How much excess hydroxide do we have?
There are two ways we can figure this out:
- calculate the total moles of base that have been added; subtract
the amount of base needed to neutralize the acid
- or calculate the volume of base required to neutralize the acid;
the excess base will come from the volume of base thats left over

added?
Calculations:
-Determining amount of excess base
We started with 100 mmoles of acid. So we need 100 mmoles of
base to neutralize the acid.
moles of base in 300 mL 0.5 M NaOH = ?
moles NaOH = [NaOH] x Vol. NaOH
= (0.5 moles / L) x (0.300 L)
= 0.150 moles or 150 mmoles

added?
Calculations:
Excess moles base = 150 mmoles 100 mmoles = 50 mmoles
[OH-] = moles excess base / new volume
We started with 200 mL of acid; weve added 300 mL of base
new volume = (200 + 300) mL = 500 mL
[OH-] = 50 mmoles / 500 mL = 0.1 M
pOH = -log (0.1 M) = 1
pH = 14 - pOH = 14 - 1 = 13

Whats going on?
The initial pH is the pH of the solution before we add any titrant.
Since acetic acid is a weak acid, it exists in equilibrium between its
acid form and its conjugate base form:
HC2H3O2 + H2O <===> C2H3O2- + H3O+
The pH is determined by the equilibrium concentration of
hydronium.
39

Calculations
Set up an ICE table with 0.5 M as the initial concentration of acetic
acid and 0 M as the initial concentration of acetate and hydronium
[HC2H3O2]
[C2H3O2-]
[H3O+]
Initial
0.5
Change
-x
+x
+x
0.5 - x
+x
+x
Equilibrium
40

Calculations
Set up equilibrium expression:
Ka = [C2H3O2-][H3O+] / [HC2H3O2]
1.8 x 10-5 = x(x) / (0.5 x); invoke x is small approximation
x2 = 0.5 x (1.8 x 10-5)
x = 3 x 10-3
[H3O+] = 3 x 10-3 M
pH = -log [H3O+] = -log (3 x 10-3 M) = 2.52
41

Whats going on?
Before we start our calculations, lets just do a quick detour to
determine the total number of moles of acid that youre starting
with. This will tell us two things:
- what volume of base we need to reach the equivalence point;
- how much acid is left over after weve added our 100 mL of base
Initial moles of HC2H3O2 = [HC2H3O2] x Vol. HC2H3O2
= (0.5 moles / L) x (0.200 L)

Whats going on?
All right, so how much base do we need to add to react
completely with 100 mmoles of our acid? The neutralization
reaction shows that NaOH reacts 1:1 with HC2H3O2
HC2H3O2 + NaOH NaC2H3O2 + H2O
So we need 100 mmoles of base. Well use the molarity of NaOH to
determine the volume
0.100 moles NaOH x (1 L / 0.5 moles) = 0.2 L = 200 mL

Whats going on?
All right! Now were ready to calculate the pH
From the previous calculation, we determined that we need to add
200 mL of our base to reach the equivalence point. In phase 2,
weve only added 100 mL of base. So, we havent reached the
equivalence point. Well still have HC2H3O2 left over.
So, pH will be due to the hydronium from the remaining
HC2H3O2

Whats going on?
HC2H3O2 is being neutralized by NaOH:
We still have HC2H3O2 left over - because we havent reached the
equivalence point.
Neutralization of acetic acid creates its conjugate base, acetate.
Weve created a buffer!
*So, we can use the Henderson-Hasselbach equation to
determine the pH!*
45

Calculations
Total moles acetic acid = [acetic acid] x Vol. Acetic acid
= (0.5 M) x (0.2 L)
= 100 mmoles
Moles NaOH added = [NaOH] x Vol. NaOH
= (0.5 M) x (0.1 L)
= 50 mmoles
46

Calculations
Moles NaOH = moles acetate formed = moles acetic acid consumed
So, moles acetate = 50 mmoles
Moles acetic acid remaining = 100 mmoles 50 mmoles
= 50 mmoles
47

Calculations
pH = pKa + log ([A-] / [HA])
= -log (1.8 x 10-5) + log (50 mmoles acetate / 50 mmoles
acetic acid)
= 4.74 + log (1)
= 4.74
We can replace the concentration terms with

# of moles because the volumes in each of the
concentrations will cancel each other out!
48

Whats going on?
At the equivalence point, all the acid has been neutralized. That is,
all the acetic acid has been converted to acetate.
Rather than pure water, we have a solution of a weak base (the
acetate anion):
C2H3O2- + H2O <===> HC2H3O2 + OHWell set up an ICE table to determine the equilibrium
concentration of hydroxide.
49

Calculations
C2H3O2- + H2O <===> HC2H3O2 + OHWhats the concentration of acetate?
Moles acetate = 100 mmoles = 0.1 moles
Vol. Solution = ?
Initial vol. = 200 mL
What vol. of NaOH have we added to get to equivalence point?
[NaOH] = moles NaOH / Vol. NaOH
Vol. NaOH = moles NaOH / [NaOH] = 0.1 moles / (0.5 moles/L)
= 0.2 L = 200 mL
50

Calculations
C2H3O2- + H2O <===> HC2H3O2 + OHWhats the concentration of acetate?
Moles acetate = 100 mmoles = 0.1 moles
Vol. Solution = ?
Initial vol. = 200 mL
200 mL of 0.5 M NaOH added to reach equivalence point
New volume = 200 mL + 200 mL = 400 mL
[C2H3O2-] = 0.1 moles / 0.4 L = 0.25 M
51

Calculations
C2H3O2- + H2O <===> HC2H3O2 + OH[C2H3O2-] = 0.1 moles / 0.4 L = 0.25 M
Now we can set up our ICE table
Initial
Change
Equilibrium
[C2H3O2-]
[HC2H3O2]
[OH-]
0.25
-x
+x
+x
0.25 - x
+x
+x
52

Calculations
Before we set up our equilibrium expression, we need to remember
that were dealing with the equilibrium of a weak base in water.
Whats the equilibrium constant?
We need the Kb for acetate as a weak base. But how do we get Kb?
Well use the relationship between Kw, Ka, acid, Kb, conjugate base :
Kw = Ka,acid x Kb, conjugate base
Kb, conjugate base = Kw / Ka, acid
Kb, acetate = Kw / Ka, acetic acid; Ka, acetic acid = 1.8 x 10-5
-14
-5
-10
53

Calculations
Set up equilibrium expression:
Kb = [HC2H3O2][OH-] / [C2H3O2-]
5.6 x 10-10 = x(x) / (0.25 x); invoke x is small approximation
x2 = 0.25 x (5.6 x 10-10)
x = 1.2 x 10-5 M
[OH-] = 1.2 x 10-5 M
pOH = -log [OH-] = -log (1.7 x 10-5 M) = 4.9
pH = 14 - pOH = 14 - 4.8 = 9.1
54

added?
Whats going on?
At this point, were adding excess base. The pH will be due to the
excess hydroxide.
What about the acetate? Why isnt it contributing?
Addition of excess hydroxide will prevent acetate from converting
to its conjugate acid form. We can explain this using Le Chteliers
Principle.
C2H3O2- + H2O <===> HC2H3O2 + OH-
55

added?
Whats going on?
Since the pH is due to the excess hydroxide, we have the exact
same scenario as we did with the titration of HCl with NaOH. The
calculations are exactly the same. For completeness, Ill repeat
them.
How much excess hydroxide do we have?
There are two ways we can figure this out:
- calculate the total moles of base that have been added; subtract
the amount of base needed to neutralize the acid
- or calculate the volume of base required to neutralize the acid;
the excess base will come from the volume of base thats left over 56

added?
Calculations:
-Determining amount of excess base
We started with 100 mmoles of acid. So we need 100 mmoles of
base to neutralize the acid.
moles of base in 300 mL 0.5 M NaOH = ?
moles NaOH = [NaOH] x Vol. NaOH
= (0.5 moles / L) x (0.300 L)
= 0.150 moles or 150 mmoles
57

added?
Calculations:
Excess moles base = 150 mmoles 100 mmoles = 50 mmoles
[OH-] = moles excess base / new volume
We started with 200 mL of acid; weve added 300 mL of base
new volume = (200 + 300) mL = 500 mL
[OH-] = 50 mmoles / 500 mL = 0.1 M
pOH = -log (0.1 M) = 1
pH = 14 - pOH = 14 - 1 = 13
58

11-Lecture 11 (2015-07-21) (Student Version)

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Housekeeping for Tue.

Matching indicators with titrations

Strong acid / strong base titration (NaOH added to HCl)

pH after equivalence point

pH before equivalence point

Strong acid / strong base titration (NaOH added to HCl)

Strong acid / strong base titration (NaOH added to HCl)

Strong acid / strong base titration (NaOH added to HCl)

Strong acid / strong base titration (NaOH added to HCl)

Strong acid / strong base titration (NaOH added to HCl)

Strong acid / strong base titration (NaOH added to HCl)

Things to keep in mind when working a titration problem

Weak acid / strong base titration (NaOH added to HC2H3O2)

pH after equivalence point

pH before equivalence point; *buffering region!*

Weak acid / strong base titration (NaOH added to HC2H3O2)

Weak acid / strong base titration (NaOH added to HC2H3O2)

Weak acid / strong base titration (NaOH added to HC2H3O2)

Weak acid / strong base titration (NaOH added to HC2H3O2)

Buffering region is pKa +/- 1.

At half-equivalance point, [acid] =

Weak acid / strong base titration (NaOH added to HC2H3O2)

Weak acid / strong base titration (NaOH added to HC2H3O2)

Notice that the pH is not 7! This

Weak acid / strong base titration (NaOH added to HC2H3O2)

Weak acid / strong base titration (NaOH added to HC2H3O2)

Things to keep in mind for a weak acid/strong base titration

Matching indicators with titrations

Strong acid / strong base titration (NaOH added to HCl)

Strong acid / strong base titration (NaOH added to HCl)

Strong acid / strong base titration (NaOH added to HCl)

Strong acid / strong base titration (NaOH added to HCl)

Strong acid / strong base titration (NaOH added to HCl)

Strong acid / strong base titration (NaOH added to HCl)

Strong acid / strong base titration (NaOH added to HCl)

Strong acid / strong base titration (NaOH added to HCl)

Strong acid / strong base titration (NaOH added to HCl)

Strong acid / strong base titration (NaOH added to HCl)

Strong acid / strong base titration (NaOH added to HCl)

Strong acid / strong base titration (NaOH added to HCl)

Weak acid / strong base titration (NaOH added to HC2H3O2)

Weak acid / strong base titration (NaOH added to HC2H3O2)

Weak acid / strong base titration (NaOH added to HC2H3O2)

Weak acid / strong base titration (NaOH added to HC2H3O2)

Weak acid / strong base titration (NaOH added to HC2H3O2)

Strong acid / strong base titration (NaOH added to HCl)

Weak acid / strong base titration (NaOH added to HC2H3O2)

Weak acid / strong base titration (NaOH added to HC2H3O2)

Weak acid / strong base titration (NaOH added to HC2H3O2)

Weak acid / strong base titration (NaOH added to HC2H3O2)

We can replace the concentration terms with

Weak acid / strong base titration (NaOH added to HC2H3O2)

Weak acid / strong base titration (NaOH added to HC2H3O2)

Weak acid / strong base titration (NaOH added to HC2H3O2)

Weak acid / strong base titration (NaOH added to HC2H3O2)

Weak acid / strong base titration (NaOH added to HC2H3O2)

Weak acid / strong base titration (NaOH added to HC2H3O2)

Weak acid / strong base titration (NaOH added to HC2H3O2)

Weak acid / strong base titration (NaOH added to HC2H3O2)

Weak acid / strong base titration (NaOH added to HC2H3O2)

Weak acid / strong base titration (NaOH added to HC2H3O2)

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pH before equivalence point; buffering region!