Chemistry 09-107: Honors Chemistry Carnegie Mellon University

Lecture Notes L: Acid/base titrations; Environmental effects on pKa

1) A simple titration
A + B  C K=∞
Red

The end point is reached when 50. mL of 1.00 M B is added. What is the
concentration of A?
1.00M B a) 0.5 M b) 1.0 M c) 1.5 M d) 2.0 M

25 mL of A

How will you know the end point has been reached?
Before endpoint At endpoint Past endpoint
A + B  C A + B  C A + B  C
Initial Moles 0.50 0.49 0.50 0.50 0.50 0.51
Final Moles 0.01 0.49 0.50 0.01 0.50

Moles A [A] pA = -log10([A])

2) Strong acid-base titrations

H+ + OH-  H2O K=1014

Before endpoint
Initial [X] 0.500 0.490
K=∞ [X]
K=1014 [X]

After endpoint
Initial [X] 0.500 0.510
K=∞ [X]
K=1014 [X]

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pH

Initial ½ equivalence pt. equivalence pt. past eq. pt.

Volume of 0 12.5 25 37.5
Base
Added (mL)
Dilution  25   0  25   12.5   25   25   25   37.5 
 H  :1 37.5   0.66 OH  :1 37.5   0.33  H  :1 50   0.50 OH  :1 50   0.50
   
 H  :1 25   1 OH  :1 25   0  H  :1 62.5   0.4 OH  :1 62.5   0.6
   

Phase 1 H+ + OH-  H2O H+ + OH-  H2O H+ + OH-  H2O H+ + OH-  H2O

I 1 0 I 0.66 0.33 I 0.50 0.50 I 0.40 0.60
∞ ∞ ∞ ∞

Majority: [H+]= Majority: [H+]= Majority: pure water Majority: [OH-]=0.20

Phase 2 pOH =-log10( ) =
pH =-log10( ) = pH =-log10( )= pH =
pH =

Sketch what you expect when titrating 25 mL of 0.1 M HCl with 0.2 M NaOH

pH pH

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3) Weak acid titrations

Titration of 25ml of 1M acetic acid (HAc) with a solution of 1M NaOH. pKa = 4.75

16
14
12
10
8
6
4
2
0
0 20 40 60

ml of NaOH aded

Initial ½ equivalence pt. equivalence pt. past eq. pt.

Base Added 0 12.5 25 37.5
(mL)
 HA :1
25   0
 HA :1
25   37.5 
 HA :1
25   12.5 
 HA :1
25   25 
Dilution   1 OH  :1   0

  0.66 OH  :1

  0.33   0.50 OH  :1   0.50

  0.4 OH  :1

  0.6
 25   25   37.5   37.5   50   50   62.5   62.5 
Phase 1 HA + OH  A - -
HA + OH-  A- HA + OH-  A- HA + OH  A - -

I 1 0 0 I 0.66 0.33 0 I 0.50 0.50 0 I 0.40 0.60 0

∞ ∞ ∞ ∞

Majority: [HA]= Majority: [HA]= Majority: Majority:

- -
[A ] = [A ] = [A-] =
[OH-]=
Phase 2

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4) Using titrations to determine concentrations and properties of unknown acids

50ml of an unknown acid solution is being titrated with 0.10M NaOH.

0.10 M NaOH
pH

50 mL of HA

Volume of 0.10M NaOH (ml)

What is the concentration of the unknown acid?

What is the pKa of the unknown acid?

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5) What do you expect for the titration of 25 mL of 1M NH3 with 1M HCl

NH3 ⇌ NH4+ + OH- Kb=1.79x10-5 pKb = 4.74

NH4+ ⇌ NH3 + H+ Ka=10-14/1.79x10-5 = 5.59x10-11 pKa = 9.26

Initial ½ equivalence pt. equivalence pt. past eq. pt.

Volume of 0 12.5 25 37.5
Base
Added (mL)
 NH 3  :1
25   0
 NH 3  :1
25   37.5 
 NH 3  :1
25   12.5 
 NH3  :1
25   25 
Dilution   1  H  :1   0

  0.66  H  :1

  0.33   0.50  H  :1   0.50

  0.4  H  :1

  0.6
 25   25   37.5   37.5   50   50   62.5   62.5 
Phase 1 NH + H  NH
3
+
4
+
NH3 + H+  NH4+ NH3 + H+  NH4+ NH + H  NH
3
+
4
+

I 1 0 0 I 0.66 0.33 0 I 0.50 0.50 0 I 0.40 0.60 0

∞ ∞ ∞ ∞

Majority: Majority: Majority: Majority:

Phase 2 NH3 ⇌ NH4+ + OH- NH4+ ⇌ NH3 + H+

pH

Volume of 1.0 M HCl (ml)

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H2SO4 Ka1 =1000 pKa1 = -3 Ka2 =l.2 x l0-2 pKa2 = 1.92

H2SO3 Ka1 =l.54 x l0-2 pKa1 = 1.81 Ka2 =l.02 x l0-7 pKa2 = 6.91

H2S Ka1 =9.1 x l0-8 pKa1 = 7.04 Ka2 =1.1 x l0-12 pKa2 = 11.9

H2CO3 Ka1 =4.3 x l0-7 pKa1 = 6.37 Ka2 = 4.8 x l0-11 pKa2 = 10.32

6) H3PO4 Titration of a polyprotic acid

H2SO3 + OH- ⇌ H2O + HSO3-

HSO3- + OH- ⇌ H2O + SO3=

At which volume of added NaOH are HSO3- and SO3-2 the majority species?
a) 0 ml b) 25 ml c) 50 ml d) 75 ml e) 100 ml f) 125 ml g) none

At which volume of added NaOH are H2SO3- and SO3-2 the majority species?
a) 0 ml b) 25 ml c) 50 ml d) 75 ml e) 100 ml f) 125 ml g) none

At what volume of added NaOH is HSO3- the majority species?

a) 0 ml b) 25 ml c) 50 ml d) 75 ml e) 100 ml f) 125 ml g) none

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7) Mixtures of weak acids

Suppose I add 100 mL of 1M NaOH to 100 mL of a solution that is 2M in HX (pKa=5) and 2M in HY (pKa=9).
What are the concentrations of all species at equilibrium?

Additional strong reaction: Weaker acid (HY/Y-) wants protons more:

Y- + H+ HY K=1/Ka=109
HX ⇌ X- + H+ K=10-5 -
X + H +
HX K=1/Ka=105
Y- + H+ ⇌ HY K=109
HX + Y- ⇌ HY + X- K = 104

Approach 1: React OH- with HX

Phase 1:
HX + OH-  X- K >> 1
I 1 0.5
K=∞ 0.5 0.5 Majority species are [HX]=0.5 [X-]=0.5 [HY] = 1

Phase 2:

Approach 2: React OH- with HY

Phase 1:
HY + OH-  Y- K >> 1
I 1 0.5
K=∞ 0.5 0.5

But Y- reacts with HX

Y- + HX  HY + X- K >> 1
I 0.5 1 0.5 0
K=∞ 0 0.5 1 0.5

Majority species are [HX]=0.5 [X-]=0.5 [HY] = 1

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8) Relative strength of acids within structural families

Which is the strongest acid?
a) HOCl b) HOClO c) HOClO2 d) HOClO3

9) Environmental effects on acid strength

In water, acetic acid has a pKa of 4.8. What is the pKa in ethanol?
a) 1.5 b) 4.6 c) 5.0 d) 10.1

What happens to the pKa of each of the following groups when they are buried inside a protein?
-COOH -NH3+
a) increases increases
b) increases decreases
c) decreases increases
d) decreases decreases

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What happens to the pKa of each of the following groups when they are near a positive charge?
-COOH -NH3+
a) increases increases
b) increases decreases
c) decreases increases
d) decreases decreases

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