Documente Academic
Documente Profesional
Documente Cultură
CHEM10003 2014
INORGANIC CHEMISTRY
Brendan Abrahams
bfa@unimelb.edu.au
Room 267 Chemistry
2
Lecture 1
CHEM10003 (inorganic chemistry)
H
+
(aq)
+Cl
-
(aq)
+Na
+
(aq)
+ OH
-
(aq)
! H
2
O
(l)
+ Cl
-
(aq)
+ Na
+
(aq)
5
Thus Bronsted acids and bases are a special
class of Lewis acids and bases involving
hydrogen ions or protons.
A Bronsted acid is a proton donor.
A Bronsted base is a proton acceptor.
HCl H
+
(aq)
+ Cl
-
(aq)
or H
2
O + HCl H
3
O
+
(aq)
+ Cl
-
(aq)
H
2
O
Such representations are simplications.
Representations of the hydrated proton
Copyright:Houghton Mifin
7
The hydrogen ion does not exist as a "naked proton" in
aqueous solution.
2H
2
O H
3
O
+
+ OH
-
K
w
= [H
+
][OH
-
] = 10
-14
at 25 C
In pure water, [H
+
] = [OH
-
] = 10
-7
M
When [H
+
] = [OH
-
] the solution is said to be neutral.
11
If [H
+
] > 10
-7
M then the solution is acidic.
If [OH
-
] > 10
-7
M then the solution is basic.
The addition of other substances may change [H
+
]
and [OH
-
] but the product of their concentrations is
always constant (for a given temperature).
Thus if [H
+
] = 10
-1
M then the [OH
-
] = 10
-13
M.
12
The pH and pOH Scales
-log([H
+
][OH
-
])= -log(10
-14
)
-log[H
+
] + (-log[OH
-
])= -log(10
-14
)
pH + pOH = 14
14
pH - Important points to keep in mind
pH = -log
10
[H
+
]
The pH scale is logarithmic.
pH 1 ! 2; [H
+
] = 0.1 ! 0.01 M; # = 0.09 M
pH 2 ! 5; [H
+
] = 0.01 ! 0.00001 M; # = 0.00999 M
15
Acids and bases exhibit a variety of strengths.
Copyright:Houghton Mifin, 2003
Copyright:Houghton Mifin, 2003
16
Quantifying acid strength
For acids:
H
2
O + HA H
3
O
+
(aq)
+ A
-
(aq)
K
a
=
[H
3
O
+
][A
-
]
[HA]
pK
a
= -log
10
K
a
For bases:
H
2
O + B HO
-
(aq)
+ BH
+
(aq)
K
b
=
[HO
-
][BH
+
]
[B]
pK
b
= -log
10
K
b
H
2
O + HA H
3
O
+
+ A
-
Copyright:Houghton Mifin
19
Strong Acids
H
2
O + HA H
3
O
+
+ A
-
The H
3
O
+
concentration is thus equal to the acid
concentration.
Ans: pH = 9; pOH = 5
Similarly, for strong bases such as NaOH, we can
assume that the concentration of the base is equal to
the HO
-
concentration.
RCOOH + H
2
O RCOO
-
(aq)
+ H
3
O
+
(aq)
23
A representation of the difference in the degree of
ionization of a strong acid and a weak acid.
Copyright:Houghton Mifin
Strong acid Weak acid
24
Calculation of the pH of solutions of weak acids:
i) Write the chemical equation:
HA + H
2
O H
3
O
+
+ A
-
ii) Write the acidity constant:
K
a
= [H
3
O
+
][A
-
]
/
[HA]
iii) If only an acid has been added then [H
3
O
+
] = [A
-
].
K
a
= [H
3
O
+
]
2
/ [HA]
[H
3
O
+
] = $(K
a
[HA])
25
iv) Take negative logs of both sides:
pH = - log{$(K
a
[HA])}
pH = 1/2 pK
a
- 1/2 log [HA]
26
Example
HCN has K
a
of 4.93 x 10
-10
.
HCN + H
2
O ! H
3
O
+
(aq)
+ CN
-
(aq)
ii) Write the acidity constant:
K
a
= [H
3
O
+
][CN
-
]
/
[HCN]
27
iii) If an acid only has been added then [H
3
O
+
] = [CN
-
].
28
Thus: K
a
= X
2
/
0.00200-X
X
2
+ K
a
X - 0.00200 K
a
= 0
Substituting in our value for K
a
we can solve our
quadratic equation.
pH = -log 9.93 x 10
-7
= 6.00
K
a
tells us that the degree of dissociation is very
small.
[H
3
O
+
] = $(K
a
[HCN])
= $(4.93 x10
-10
x 0.00200)
= 9.93 x10
-7
M
iv) Take negative logs of both sides:
pH = 6.00
The similarity in the answers is a consequence of the very weak
nature of the acid.
When the acid is not quite as weak, the assumption is less valid
and the estimation of pH is cruder.
32
How do we know if the acid is weak enough to use the
approximation???
pH = 2.39, [H
+
] = 10
-2.39
= 4.07 x10
-3
M
% dissociation = 4.07 x10
-3
/0.1000
= 4.1%
% dissociation = 1 x10
-6
/0.00200 = 0.05%
Approximation is valid.
NR
3
+ H
2
O HNR
3
+
+ OH
-
[HO
-
] = $(K
b
[B])
Calculation of the pH for weak bases:
B + H
2
O HO
-
+ BH
+
36
iv) Take negative logs of both sides:
pOH = - log{$(K
b
[B])}
pOH = 1/2 pK
b
- 1/2 log [B]
37
Determine the pOH and pH of a 0.050 M ammonia
solution.
Ammonia has a K
b
of 1.77 x 10
-5
.
K
b
= [NH
4
+
][OH
-
]
/
[NH
3
]
38
iii) If only ammonia has been added then [NH
4
+
] = [OH
-
].
iv)
NH
3
+ H
2
O NH
4
+
+ OH
-
39
K
b
= [OH
-
]
2
/
[NH
3
]
1.77 x 10
-5
= [OH
-
]
2
/
0.0500
[OH-] = $(1.77 x 10
-5
x 0.050)
= 9.41 x 10
-4
pOH = -log 9.41 x 10
-4
= 3.0
pH = 11.0
then K
a
for the conjugate acid (BH
+
) may be dened
as:
K
a
= [B][H
+
]
/
[BH
+
]
If K
a
and K
b
are multiplied together:
K
a
x K
b
= ([B][H
+
]
/
[BH
+
]) x ([HO
-
][BH
+
]
/
[B])
and
pK
a
+ pK
b
= 14
Note K
a
and K
b
must be for an acid and conjugate
base.
42
Read Burrows
Sections 7.1, 7.2
Problems 7.1-7.6.
After today!s lecture