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16 Practice:
What is the pH of a 0.085 M solution of aniline, C6H5NH2 (pKb = 9.37)?
Ch. 16 Practice:
What is the pH of a 0.085 M solution of aniline, C6H5NH2 (pKb = 9.37)?
[OH ] Kb [BOH]
Kb = 10-pKb = 10-9.37 = 4.2710-10
10
6
[OH ] (4.27 10 ) (0.085) 6.02 10
6.02 106
% ionization 0.085 100% 0.007%
pOH = -log(6.0210-6) = 5.22
pH = 14 pOH = 8.78
What is the Ka of benzoic acid if a 0.15 M solution has a pH of 2.51?
[H ][A- ]
K a [HA]
[H+] = 10-2.51 = 3.0910-3 M
[HA] = 0.15 3.0910-3 = 0.1469 M
Ka = (3.0910-3)2 / 0.1469 = 6.510-5
Chapter 17
Additional Aspects of
Aqueous Equilibria
As he that taketh away a garment in cold
weather, and as vinegar upon nitre, so is
he that singeth songs to an heavy heart.
Proverbs 25:20 (KJV)
17.1.1
17.1.2
17.1.3
Example 1
What is the pH of a solution of 0.30 mol acetic acid and 0.30 mol
sodium acetate in 1.0 L solution
What is the significant reaction?
HCH3CO2(aq) + H2O(l) H3O+(aq) + CH3CO2-(aq)
What species are involved in the equilibrium
HCH3CO2(aq), H3O+(aq), CH3CO2-(aq)
What are the equilibrium concentrations of these species?
Init.
[HCH3CO2], M
0.30
Change
Equil.
-x
0.30 - x
[H3O+], M
0
+x
x
[CH3CO2-], M
0.30
+x
0.30 + x
17.1.4
Example 1
Init.
[HCH3CO2], M
0.30
[H3O+], M
0
[CH3CO2-], M
0.30
Change
Equil.
-x
0.30 - x
+x
x
+x
0.30 + x
[H 3O ][CH 3CO-2]
Ka
[HCH 3CO2 ]
(x)(0.30 x)
1.8 10
(0.30 x)
5
5
x
1.8
10
M
[H
]
1.8 10
(0.30)
pH log(1.8 105 ) 4.74
Example 1
17.1.5
2
[H
O
][CH
CO
]
(
x
)
5
3
2
1.8 10 3
[HCH 3CO 2 ]
0.30
x = 2.310-3
pH = -log(2.310-3) = 2.64
The addition of a common ion (CH3CO2-) to a solution of a
weak electrolyte (HCH3CO2) reduced the ionization of the
HCH3CO2
(from 2.310-3 to 1.810-5 moles ionized per liter)
17.1.6
Example 2
[HF], M
0.20
[H3O+], M
0.10
Change
Equil.
-x
0.20 - x
+x
0.10 + x
[F-], M
0
+x
x
17.1.7
Example 2
Init.
[HF], M
0.20
[H3O+], M
0.10
[F-], M
0
Change
Equil.
-x
0.20 - x
+x
0.10 + x
+x
x
[H 3O ][F - ]
Ka
[HF]
(0.10 x)(x)
6.8 10
(0.20 x)
4
(0.10)(x)
6.8 10
(0.20)
4
x 1.4 103 M [F
[F]]
Example 2
17.1.8
2
[H
O
][F
]
(
x
)
2
4
3
x
1.2
10
M
[F
]
6.8 10
[HF]
0.20
We have added an ion (H3O+) common to the ionization of the
weak electrolyte (HF) and reduced the ionization of the HF
(from 1.210-2 to 1.410-3 moles ionized per liter)
17.1.9
Buffered Solutions
17.2.1
[H ][A- ]
Ka
[HA]
Which can be solved for the [H+]:
[HA]
[H ] K a
[A- ]
Buffered Solutions
17.2.2
Buffered Solutions
17.2.3
Buffered Solutions
17.2.4
Buffer Capacity
Buffer capacity is the amount of acid or base neutralized by the
buffer before there is a significant change in pH.
The pH of the solution depends on the Ka of the acid, and the
relative concentrations of the weak acid and its conjugate base.
Buffer capacity depends on the amount of the weak acid and its
conjugate base.
The greater the amounts of conjugate acid-base pair, the greater
the buffer capacity.
Buffered Solutions
17.2.5
[H ] K a
[A- ]
But the buffering capacity of the 1.0 M solution will be greater,
because it contains more of the acid and conjugate base.
Buffered Solutions
17.2.6
[HA]
[H ] K a
[A- ]
If the negative log of this equation is taken, we get the
Henderson-Hasselbach equation:
[HA]
[A - ]
p H pK a log
[HA]
Buffered Solutions
17.2.7
Buffered Solutions
17.2.8
17.2.9
Buffered Solutions
Buffer
Acid
Initial
Base
Water
Buffered Solutions
17.2.10
Buffer:
mol(HCH3CO2) = (0.100 M)(0.0500 L) = 0.00500 mol
mol(CH3CO2-) = (0.100 M)(0.0500 L) = 0.00500 mol
Aliquots:
mol(H+) = (0.100 M)(0.00500 L) = 5.0010-4 mol
mol(OH-) = (0.100 M)(0.00500 L) = 5.0010-4 mol
Buffered Solutions
Calculate the pH of the buffer alone:
[HCH3CO3] = 0.00500 mol / 0.0500 L = 0.100 M
[CH3CO3-] = 0.100 M
[CH 3CO-2]
p H pK a log
[CH CO H]
3
0.100 M
p H log(1.80 10 ) log
0.100 M
5
p H 4.745 log(1)
p H 4.745
17.2.11
Buffered Solutions
17.2.12
[CH 3CO-2]
p H pK a log
[HCH CO ]
3
0.0818M
p H 4.745 log
0.100M
p H 4.745 0.0872 4.658
Buffered Solutions
17.2.13
[CH 3CO-2]
p H pK a log
[HCH CO ]
3
0.100M
p H 4.745 log
0.0818M
p H 4.745 0.0872 4.832
Buffered Solutions
Calculate the pH of the water with the added HCl:
M = mol/L
M = 5.0010-4 mol/0.0550 L = 9.0910-3 M
pH = -log(9.0910-3) = 2.041
17.2.14
Buffered Solutions
Calculate the pH of the water with the added NaOH:
M = mol/L
M = 5.0010-4 mol/0.055 L = 9.0910-3 M
pOH = -log(9.0910-3) = 2.041
pH = 14 2.041 = 11.959
17.2.15
17.2.16
Buffered Solutions
Buffer
Water
Acid
4.658
2.041
Initial
4.745
7.000
Base
4.832
11.959
17.3.1
Acid-Base Titrations
Titration
pH
8.00
6.00
4.00
2.00
0.00
0.00
5.00
10.00
15.00
20.00
25.00
Acid-Base Titrations
17.3.2
Titration
As the base is added, it consumes a stoichiometric quantity of
the acid.
HA(aq) + BOH(aq) A-(aq) + B+(aq) + H2O(l)
The equivalence point in a titration is the point at which the acid
and base are present in stoichiometric quantities
The end point in a titration is the point at which the color
change of the indicator occurs
The difference between equivalence point and end point is
called the titration error
Acid-Base Titrations
17.3.3
Acid-Base Titrations
17.3.4
Example
17.3.5
Example
17.3.6
Acid-Base Titrations
Strong Base-Strong Acid Titrations
The shape of a strong basestrong acid titration curve is
very similar to a strong acidstrong base titration curve,
except that the pH starts
high, then decreases as the
titration progresses.
Either phenolphthalein or
methyl red would work as
an indicator.
17.3.7
Example
17.3.8
Example
17.3.9
Acid-Base Titrations
17.3.10
Acid-Base Titrations
17.3.11
Example
17.3.12
Example
17.3.13
Example
17.3.14
3
(5.3
10
)
5
[H ] 1.8 10
(4.7 102 )
[H+] = 2.010-6
pH= -log(2.010-6) = 5.70
Acid-Base Titrations
17.3.15
Acid-Base Titrations
17.3.16
Acid-Base Titrations
17.3.17
Acid-Base Titrations
17.3.18
12
10
pKa
8
pH
0
2
6
4
6
8
0
0.00
0.25
0.50
0.75
1.00
Fraction of Equivalence Point
1.25
Example
17.3.19
Example
17.3.20
5 (1.7 10 )
4
[H ] 6.3 10
1.9
10
M
3
(5.6 10 )
Example
17.3.21
Example
17.3.22
5 (4.5 10 )
5
[H ] 6.3 10
2.1
10
M
2
(1.4 10 )
pH log(2.1105 ) 4.68
Example
17.3.23
Example
17.3.24
Example
17.3.25
Example
What is the final [OH-] and pH?
[OH-] = (2.510-4 mol) / (0.0650 L) = 3.810-3 M
pOH = 2.41, pH = 11.59
17.3.26
Acid-Base Titrations
17.3.27
Acid-Base Titrations
17.3.28
Practice
17.3.29
Practice
17.3.29a
Practice
17.3.29b
2
[OH
](3.2
10
)
5
1.8 10
(3.50 102 )
[OH ] 2.0 105 M
Practice
When 21.05 mL HCl has been added?
How many moles of NH3 were in the original solution?
(0.100 mol/L) (0.0200 L) = 2.0010-3 mol NH3
How many moles of H+ were added?
(0.095 mol/L) (0.02105 L) = 2.0010-3 mol H+
How many moles NH3 remain?
2.0010-3 mol - 2.0010-3 mol = 0.00 mol
How many moles NH4+ are formed?
2.0010-3 mol NH4+
What is the total volume of solution?
0.0200 L + 0.02105 L = 0.0410 L
17.3.29c
Practice
17.3.29d
pH 5.28
Practice
When 30.0 mL HCl has been added?
How many moles of NH3 were in the original solution?
(0.100 mol/L) (0.0200 L) = 2.0010-3 mol NH3
How many moles of H+ were added?
(0.095 mol/L) (0.0300 L) = 2.8510-3 mol H+
How many moles H+ are excess?
2.8510-3 mol - 2.0010-3 mol = 8.510-4 mol
What is the total volume of solution?
0.0200 L + 0.0300 L = 0.0500 L
What is the final [H+] and pH?
[H+] = (8.510-4 mol) / (0.0500 L) = 1.710-2 M
pH = 1.77
17.3.29e
Acid-Base Titrations
17.3.30
Acid-Base Titrations
17.3.31
Acid-Base Titrations
17.3.32
Solubility Equilibria
17.4.1
Solubility Equilibria
17.4.2
Solubility Equilibria
17.4.3
Solubility Equilibria
17.4.4
Solubility Equilibria
17.4.5
Example
17.4.6
Ksp = [Pb2+][Br-]2
[Pb2+] = 1.010-2 M
[Br-] = 2(1.010-2 M) = 2.010-2 M
Ksp = (1.010-2)(2.010-2)2
Ksp = 4.010-6
17.4.7
Example
2.1103g 1000 mL
100 mL
1L
mol
331.73 g
6.3 105 M
Ksp = [Ag+]2[CrO42-]
[CrO42-] = 6.310-5 M
[Ag+] = 2(6.310-5) = 1.310-4 M
Ksp = (1.310-4)2 (6.310-5)
Ksp = 1.010-12
Solubility Equilibria
17.4.8
Example
17.4.9
mol
1.7 10 2 g/L
Example
17.4.10
Ksp = [Mg2+][OH-]2
[H+] = 10-10.52 = 3.0210-11
[OH-] = 10-14 / 3.0210-11 = 3.3110-4 M
[Mg2+] = [OH-] = 1.6610-4 M
Ksp = (1.6610-4)(3.3110-4)2
Ksp = 1.810-11
17.5.1
Example
17.5.2
17.5.3
Solubility and pH
Lets look at another aspect of Le Chteliers principle:
CaF2(s) Ca2+(aq) + 2 F-(aq)
If Ca2+ is added, then the equilibrium shifts away from the
increase and CaF2 precipitates
The equilibrium can also be shifted the other direction
F- can be removed by adding a strong acid:
F-(aq) + H+(aq) HF(aq)
As pH decreases, [H+] increases and solubility increases, and
the effect can be dramatic
Example
17.5.4
Ksp = [Mg2+][OH-]2
[H+] = 10-9.52 = 3.0210-10 M
[OH-] = 10-14 / 3.0210-10 = 3.3110-5 M
Let x = moles of Mg(OH)2 that dissolves in 1 liter
[Mg2+] = x M
[OH-] = 3.3110-5 M
1.810-11 = (x)(3.3110-5)2
x = 0.017 moles of Mg(OH)2 would dissolve per liter
17.5.5
Solubility and pH
When Mg(OH)2 dissolves in water, the solubility was 1.710-4
M, and the resulting solution has a pH of 10.52 (slide 17.4.10)
A decrease of one pH unit, to pH = 9.52, increased the
solubility by a factor of 100, to 0.017 M
Mg(OH)2 works as an over-the-counter antacid, even though it
is insoluble
Due to the lower concentration of OH- at a lower pH, more
Mg(OH)2 dissolves, releasing more OH- to neutralize the
acid
Cleopatras Needle
Originally erected in the
Egyptian city of Heliopolis,
around 1450 BC
(Cleopatra lived over a
thousand years later)
224 tons of red granite
Moved to New York,
erected in Central Park
on February 22, 1881
Has been deteriorating
because of the acidic rain in
New York
17.5.6
17.5.7
17.5.8
17.5.9
17.5.10
Precipitation and
Separation of Ions
17.6.1
Precipitation and
Separation of Ions
17.6.2
Precipitation and
Separation of Ions
17.6.3
Example
Will a precipitate form when 0.10 L of 8.010-3 M Pb(NO3)2 is
added to 0.40 L of 5.010-3 M Na2SO4?
Which salts are possible precipitates?
Metathesis products:
Pb(NO3)2(aq) + Na2SO4(aq) PbSO4(?) + 2 NaNO3(?)
NaNO3 is soluble, so only PbSO4
Calculate concentration of these ions (0.5 L total volume):
Pb2+: (8.010-3 M)(0.10 L)/(0.50L) = 1.610-3 M Pb2+
SO42-: (5.010-3 M)(0.40 L)/(0.50L) = 4.010-3 M SO42-
Precipitation and
Separation of Ions
Example
Now solve for Q, and compare it to the Ksp:
Q = [Pb2+][SO42-]
= (1.610-3 M)(4.010-3 M)
= 6.410-6
The Ksp of PbSO4 is 6.310-7
Since Q > Ksp, the salt will precipitate
17.6.4
Precipitation and
Separation of Ions
17.6.5
Example
17.6.6
Precipitation and
Separation of Ions
17.6.7
17.7.1
17.7.2
17.7.3
17.7.4
17.7.5
Read Chapter 17
Chapter 17 Homework
Due: Friday, February 28