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What is the equation for the auto-ionization of water? 2 H2O (l) H3O+1 (aq) + OH-1 (aq)
What is the equation for Kw and what is its value? Kw = [H3O+][OH-1] = 1x10-14
Because the pH scale is a logarithmic scale, every change in 1 is really a change in how much? 10
Using the pH square and the equations learned in class, fill in the blank spots in the chart below:
pH
[H3O+1]
[OH-1]
pOH
-4
-11
3.5
3.16x10
3.16x10
10.5
8.04
9.2x10-9
1.10x10-6
5.96
3.67
2.14x10-4
4.7x10-11
10.33
5.8
1.58x10-6
6.31x10-9
8.2
I
C
E
5.
I
C
E
How are weak acids and bases different from strong ones? Weak acids dissociate <5%
What is the general equation for Ka? HA (aq) + H2O (l) H3O+1 (aq) + A-1 (aq)
What is the general equation for Kb? B (aq) + H2O (l) OH-1 (aq) + HB+1 (aq)
For a 0.25 M solution of HC2H3O2 (Ka = 1.8x10-5) calculate:
a. pH
HA (aq) +
H2O (l) H3O+1 (aq) + A-1 (aq)
0.25
0
0
-x
+x
+x
0.25
x
x
1.8x10-5 = x2/0.25
x = 2.12x10-3 pH = -log (2.12x10-3) = 2.67
b. % dissociation
2.12x10-3 x 100% = 0.85%
0.25
For a 0.75 M solution of C2H5NH2 (Kb = 5.6x10-4) calculate:
a. pH
B (aq) +
H2O (l) OH-1 (aq) +
HB+1 (aq)
0.75
0
0
-x
+x
+x
0.75
x
x
5.6x10-4 = x2/0.75
x = 2.05x10-2 pOH = -log (2.05x10-2) = 1.69 pH = 12.31
b. % dissociation
2.05x10-2 x 100% = 2.73%
0.75
Acid-Base Interactions
Strong-Strong
1. What is the pH when 50 mL of 0.1 M HCl is mixed with 50 mL of 0.1 M NaOH?
Acid = (50/100)(0.1 M) = 0.05 M
Base = (50/100)(0.1 M) = 0.05 M
Equal amounts of strong acid/base so should be neutral
H3O+1 (aq) + OH-1 (l) 2 H2O
I
0.05
0.05
C
-0.05
-0.05
E
0
0
pH = 7
2. What is the pH when 250 mL of 0.2 M HNO3 is mixed with 500 mL of 0.1 M KOH?
Acid = (250/750)(0.2 M) = 0.0667 M
Base = (500/750)(0.1 M) = 0.0667 M
Equal amounts of strong acid/base so should be neutral
I
C
E
H3O+1 (aq) +
0.0667
-0.0667
0
pH = 7
3. What is the pH when 100 mL of 0.001 M HBr is mixed with 50 mL of 0.001 M NaOH?
Acid = (100/150)(0.001 M) = 6.67x10-4 M
Base = (50/150)(0.001 M) = 3.33x10-4 M
More acid than base so should be acidic
I
C
E
I
C
E
I
C
E
I
C
E
Strong-Weak
7. What is the pH when 25 mL of 0.25 M HCl is mixed with 25 mL of 0.25 M NH3? (Kb = 1.8x10-5)?
Acid = (25/50)(0.25 M) = 0.125 M
Base = (25/50)(0.25 M) = 0.125 M
Equal amounts of strong acid/weak base so should be acidic
Shortcut hint- Equivalence point of a strong acid weak base gives a normal Ka problem
(you can skip the actual rxn and go straight to Ka of conj. acid of weak base)
ACTUAL RXN- GOES ALMOST ALL THE WAY (water is a product; math is bad)
H3O+1 (aq) + NH3 (aq) H2O (l) +
NH4+1 (aq)
I
0.125
0.125
0
C
-0.125
-0.125
+0.125
E
0
0
0.125
NOW FLIP RXN AND DO Ka (Ka = 1x10-14/1.8x10-5) = 5.56x10-10
NH4+1 (aq)+
H2O (l) H3O+1 (aq) + NH3 (aq)
I
0.125
0
0
C
-x
+x
+x
E
0.125
x
x
5.56x10-10 = x2/0.125 x = 8.33x10-6 pH = -log (8.33x10-6) = 5.08
8. What is the pH when 20 mL of 0.020 M HNO3 is mixed with 20 mL of 0.030 M C6H5NH2 (Kb = 4x10-10)?
Acid = (20/40)(0.02 M) = 0.01 M
Base = (20/40)(0.030 M) = 0.015 M
Not at equivalence point. Not at midpoint.
ACTUAL RXN- GOES ALMOST ALL THE WAY (water is a product; math is bad)
+1
H3O+1 (aq) + C6H5NH2 (aq)
H2O (l) +
C6H5NH3 (aq)
I
0.01
0.015
0
C
-0.01
-0.01
+0.01
E
0
0.005
0.01
NOW FLIP RXN AND DO Ka (Ka = 1x10-14/4x10-10) = 2.5x10-5
+1
C6H5NH3 (aq) + H2O (l)
H3O+1 (aq) + C6H5NH2 (aq)
I
0.01
0
0.005
C
-x
+x
+x
E
0.01
x
0.005
2.5x10-5 = x(0.005/0.01)
x = 5x10-5
pH = -log (5x10-5) = 4.30
Shortcut hint- Simple buffer problem. Write Ka equation and plug in amounts after strong acid is
neutralized (you can skip the actual rxn)
Strong acid: 0.01 M neutralized is turned into a weak acid
Weak base: 0.015 M -0.01 M neutralized by acid so 0.005 left
Now plug straight into 2nd ICE table above and solve
9. What is the pH when 50 mL of 0.040 M NaOH is mixed with 50 mL of 0.040 M HN3 (Ka = 1.9x10-5)?
Base = (50/100)(0.04 M) = 0.02 M
Acid = (50/100)(0.04 M) = 0.02 M
Equal amounts of strong base/weak acid so should be basic
ACTUAL RXN- GOES ALMOST ALL THE WAY (water is a product; math is bad)
-1
OH-1 (aq) + HN3 (aq) H2O (l) +
N3 (aq)
I
0.02
0.02
0
C
-0.02
-0.02
+0.02
E
0
0
0.02
NOW FLIP RXN AND DO Kb (Kb = 1x10-14/1.9x10-5) = 5.26x10-10
-1
N3 (aq)+
H2O (l) OH-1 (aq) +
HN3 (aq)
I
0.02
0
0
C
-x
+x
+x
E
0.02
x
x
5.26x10-10 = x2/0.02
x = 3.24x10-6
pOH = -log (3.242x10-6) = 5.49
pH = 8.51
Shortcut hint- Equivalence point of a strong base weak acid gives a normal Kb problem
(you can skip the actual rxn and go straight to Kb of conj. base of weak acid)
10. What is the pH when 120 mL of 0.0075 M KOH is mixed with 200 mL of 0.0050 M HOCl (Ka = 3.5x10-8)?
Base = (120/320)(0.0075 M) = 0.00281 M
Acid = (200/320)(0.005 M) = 0.00312 M
Not at equivalence point. Not at midpoint.
ACTUAL RXN- GOES ALMOST ALL THE WAY (water is a product; math is bad)
-1
OH-1 (aq) + HOCl (aq)
H2O (l) +
OCl (aq)
I
0.00281
0.00312
0
C
-0.00281
-0.00281
+0.00281
E
0
0.00031
0.00281
NOW FLIP RXN AND DO Kb (Kb = 1x10-14/3.5x10-8) = 2.89x10-7
-1
OCl (aq) + H2O (l)
OH-1 (aq) +
HOCl (aq)
I
0.00281
0
0.00031
C
-x
+x
+x
E
0.00281
x
0.00031
2.89x10-7= x(0.00031/0.00281)
pOH = -log (2.59x10-6) = 5.59
x = 2.59x10-6
pH = 8.41
Shortcut hint- Simple buffer problem. Write Ka equation and plug in amounts after strong base is
neutralized (you can skip the actual rxn)
Strong base = 0.00281 turns into weak base
Weak acid = 0.00312 neutralized and left with 0.00312-0.00281 = 0.00031
So:
HOCl (aq) + H2O (l) H3O+ (aq) + OCl-1 (aq)
I
0.00031
0
0.00281
C
-x
+x
+x
E
0.00031
x
0.00281
3.5x10-8 = x(0.00281/0.00031)
x = 3.86x10-9
pH = 8.41
Midpoint
11. What is the pH when 25 mL of 0.050 M HCl is mixed with 50 mL of 0.050 C5H5N (Kb = 1.5x10-9)?
acid = (25/75)(0.050 M) = 0.0166 M
base = (50/75)(0.050 M) = 0.0333 M
At midpoint! (Half as much strong acid as base)
pH = pKa
so
12. What is the pH when 40 mL of 0.80 M NaOH is mixed with 80 mL of 0.8 M HNO2 (Ka = 4.5x10-4)?
base = (40/120)(0.80 M) = 0.266 M
acid = (80/120)(0.80 M) = 0.5333 M
At midpoint! (Half as much strong base as acid)
pH = pKa
so
13. What is the pH when 30 mL of 0.006 M HNO3 is mixed with 30 mL of 0.012 M (CH3)3N (Kb = 7.4x10-5)?
so
14. What is the pH when 100 mL of 0.0078 M KOH is mixed with 100 mL of 0.0156 M C6H5CO2H (Ka = 6.3x10-5)
so
Ksp and pH
Titration Curves
1. Draw a titration curve of a strong base being titrated by a strong acid. Be sure to label a pH of 7 in the
appropriate spot.
pH
mL acid added
2. Draw a titration curve of a strong acid being titrated by a strong base. Be sure to label a pH of 7 in the
appropriate spot.
pH
mL acid added
3. Draw a titration curve of a weak base being titrated by a strong acid. Be sure to label a pH of 7 in the
appropriate spot.
pH
mL acid added
4. Draw a titration curve of a weak acid being titrated by a strong base. Be sure to label a pH of 7 in the
appropriate spot.
pH
mL acid added
Mid Pt @15 mL pH = 5
Mid Pt @ 30 mL pH = 8
Eq. Pt @60 mL pH = 4
HCl
Buffers
1. What is the definition of a buffer? A solution that resists changes in pH.
2. What kind of an acid and base are present in a buffer? Weak acid and conj base or weak base
and conj acid
3. The Ka of carbonic acid is 4.3x10-7.
a. What is the pH of a solution that is 0.25 M H2CO3 and 0.25 M NaHCO3?
-log (4.3x10-7) = 6.4
b. What would the ratio of acid to base be if you wanted to buffer at exactly a pH of 6?
4.3x10-7 = 1x10-6 (B/A)
B:A = 0.43:1 or
A:B = 2.32:1
4. The Ka of hydrozoic acid is 1.9x10-5.
a. What is the pH of a solution that is 0.25 M HN3 and 0.75 M N3-1?
Ka = 1.9x10-5 = [H3O+1](0.25/0.75) = 5.7x10-5
pH = -log(5.7x10-5) = 4.24
b. What would the ratio of acid to base be if you want to buffer exactly at a pH of 5?
1.9x10-5 = 1x10-5 (B/A)
B:A = 1.9:1 or
A:B = 0.53:1
-10
5. The Kb of aniline is 4x10 .
a. What is the pH of a solution that is 0.050 M C6H5NH2 and 0.050 M C6H5NH3+1?
pOH = -log (4x10-10) = 9.4 so
pH = 4.6
or
pH = -log (2.5x10-5) = 4.6
b. What would the ratio of acid to base be if you want to buffer exactly at a pH of 5?
2.5x10-5 = 1x10-5 (B/A)
B:A = 2.5:1 or
A:B = 0.4:1
-4
6. The Kb of ethyleamine is 4.4x10 .
a. What is the pH of a solution that is 0.25 M C5H5N and 1.25 M C5H5NH+1?
Ka = 1x10-14/4.4x10-4 = 2.27x10-11
2.27x10-11 = [H3O+1] (0.25/1.25) = 1.14x10-10
pH = -log(1.14x10-10) = 9.95
b. What would the ratio of acid to base be if you want to buffer exactly at a pH of 10?
2.5x10-11 = 1x10-10 (B/A)
B:A = 0.25:1 or
A:B = 4:1
7. Which of the following buffer systems would you choose if you want to buffer at a pH of 2?
a. HC3H5O2 / C3H5O2-1
Ka = 1.35x10-5
-1
b. HNO2 / NO2
Ka = 7.2x10-4
c. HIO / IO-1
Ka = 2.3x10-11
-1
d. H3PO4 / H2PO4
Ka = 7.6x10-3
You would pick system d. The Ka value is closest to the pH you want to buffer at.
Describe how to make the buffer so it is exactly at a pH of 2.
7.6x10-3 = 1x10-2 (B/A)
so:
B:A = 0.76:1 or
A:B = 1.316
8. Lactic acid has a Ka of 8.3x10-4. A buffer is made so that it is 0.50 M in HC3H5O3 and 0.50
M in C3H5O3-1.
a. What is the pH of the buffer? pH = -log(8.3x10-4) = 3.1
b. What will the pH of the buffer be if 0.15 M of HCl are added?
0.15 M HCl will react away 0.15 M of the weak base and add 0.15 M of the weak acid
8.3x10-4 = [H3O+1](0.35/0.65) = 1.54x10-3
pH = -log(1.54x10-3) = 2.8
pH = 4.55
b. How many grams of NaAsO2 must be added so the solution is a buffer at a pH of 10?
Assume no change in volume.
6.6x10-10 = 1x10-10 ([base]/1.2 M acid) so [base] = 7.92 M
[base] = 7.92 M so 7.92 moles/L * 0.05 L = 0.396 moles NaAsO2
0.396 moles NaAsO2 * 129.9 g/mole = 51.4 g NaAsO2
10. Methylamine has a Kb of 4.2x10-4. A buffer is made so that it is 0.75 M in CH3NH2 and
0.75 M in CH3NH3+1.
a. What is the pH of the buffer?
pOH = -log(4.2x10-4) = 3.4 so
pH = 10.6
or
pH = -log(2.4x10-11) = 10.6
b. What will the pH of the buffer be if 0.25 M of HNO3 are added?
0. 25 M HNO3 will react away 0.25 M of the weak base and add 0.25 M of the weak acid
2.4x10-11 = [H3O+1](0.50/1.0) = 4.8x10-11
pH = -log(4.8x10-11) = 10.3
11. Quinoline has a Kb of 6.3x10-10. A solution is made so that it is 250 mL of 1.75 M C9H7N.
a. What is the pH of the solution?
6.3x10-10 = x2/1.75 x = 3.32x10-5 pOH = 4.48 pH = 9.52
b. How many grams of C9H7NHCl must be added so that the solution is a buffer exactly
at a pH of 5? Assume no change in volume.
Ka = 1x10-14/6.3x10-10 = 1.59x10-5
1.59x10-5 = 1x10-5(1.75 M/[acid]) so [acid] = 1.1 M
[acid] = 1.1 M so 1.1 moles/L * 0.25 L = 0.275 moles acid
0.275 moles acid * 165.5 g/mole = 45.5 grams C9H7NHCl
b.
c.
H+ +
LA
OH-1 H2O
LB
Combination Problems
1.
Vb = 12.5 mL
ii) Less NaOH will be needed so the concentration will be higher resulting in a more
concentrated base and so a higher equivalence point
2.
pH = 8.82
[]o
[]eq
pOH = 5.18
C6H5NH2 +
0.10
-6.61 x10-6
0.1
H2O
C6H5NH3+ +
0
+6.61 x10-6
6.61 x10-6
OH0
+6.61 x10-6
6.61 x10-6
c) The solution prepared in part (b) is titrated with 0.10 M HCl. Calclulate the pH of the
solution when 5.0 mL of the acid has been added.
c)
C6H5NH3+ +
0
+0.0167
0.0167
H2O
[]o
[]eq
C6H5NH2 +
0.0833
-0.0167
0.0666
H2O
[]o
[]eq
C6H5NH2 +
0.0666
-x
0.0666
C6H5NH3+ +
0.0167
+x
0.0167
OH0
+x
x
C6H5NH3+ +
0
+0.05
0.05
H2O
[]o
[]eq
C6H5NH2 +
0.05
-0.05
0
H2O
[]o
[]eq
C6H5NH3+ +
0.05
-x
0.05
C6H5NH2 +
0
+x
x
H3O+
0
+x
x
d)
e) The pKa values for several indicators are given below. Which is most suitable for this
titration? Justify.
Erythrosine
pKa = 3
Litmus
pKa = 7
Thymolphthalein
pKa = 10
e)
As the pH changes at about 3, erythrosine is the best as it changes at the same pH value.
x = 7.48 x10-5
c) Write the net ionic equation for the reaction between HOCl and NaOH
c) HOCl (aq) + OH-1 (aq) H2O (l) + OCl-1 (aq)
ii) Calculate the [H3O+1] in the flask after the NaOH has been added
dii)
[]o
[]eq
[]o
[]eq
3.2x10-8 = x(0.107/0.025)
0
+0.107
0.107
x = 7.48x10-9 pH = 8.13
ii) Calculate the [OH-1] in the flask after the NaOH has been added
1x10-14/7.48x10-9 = 1.34x10-6 M OH-1