Documente Academic
Documente Profesional
Documente Cultură
H3O+(aq) + F(aq)
Arrhenius
Acid increases H + concentration
Base increases OH- concentration
Brnsted-Lowry (1923)
Acid donates a H +
Base combines with or accepts H +
Lewis
Acid electron acceptor
Base electron donor
Shorthand:
H2O(l)
H+(aq) + OH(aq)
H2O(l)
H+(aq) + OH(aq)
[H + ] [OH ]
Keq =
[H2O]
But H2O is a pure liquid and its concentration is
constant ([H2O] = 55.6 M, activity = 1), so it is not
included in the equilibrium expression:
K w = [H+ ][OH]
K w = 1.0 10 14 @ 20 DC
[H+] [OH] = 1 1014
[H+] = [OH] = 1 107 M
So the [H+] and [OH] concentration in pure water
is 1 107 M
We use Kw to indicate the water self- or autoionization. This is still a Keq or Kc. Chemists use
many subscripts on the equilibrium constant K to
indicate specific types of equilibria:
Kb = base equilibria
Ka = acid equilibria
Ksp = slightly soluble (solubility product) equilibria
Because of the often very small nature of H+
concentrations, chemists (and others) have devised
pH < 7.0
pH = 7.0
pH > 7.0
Acidic
Neutral
Basic (Alkaline)
Substance
pH
10 M HCl
1.0
1 M HCl
0.0
1.4
Lemon Juice
2.1
Orange Juice
2.8
Wine
3.5
Black Coffee
5.0
Urine
6.0
Pure Water
7.0
Blood
7.4
8.5
Ammonia Solution
11.9
1 M NaOH
14.0
10 M NaOH
15.0
pOH = log
[OH ]
pKw = log Kw = 14
So, for a given water solution:
pOH + pH = pKw = 14
or:
pOH = 14 pH
pH = 14 pOH
10
K
w
11
=
3.1
10
[OH ] = + =
[H ] 3.16 10 4
Keq =
[HA]
pKa = log Ka
The smaller (and more negative) the pKa the
stronger the acid!!!! This can be confusing, but is
very important: pKas are commonly used in
biology & chemistry!
HA
A-
Ka
pKa
hydroiodic
HI
1010
10
hydrobromic
HBr
Br
1010
10
perchoric
HClO4
ClO4
108
hydrochoric
HCl
Cl
108
sulfuric
H2SO4
HSO4
108
nitric
HNO3
NO3
108
trichloroacetic
Cl3COOH
Cl3COO
2 102
0.7
oxalic
HOOCCOOH
HOOCCOO
5.9 102
1.2
sulfurous
SO32
1.5 102
1.8
SO42
1.2 102
1.9
phosphoric
H2SO3
HSO4H3PO4
H2PO4
7.5 103
2.1
nitrous
HNO2
4.6 104
3.3
hydrofluoric
HF
NO2
F
3.5 104
3.5
formic
HCOOH
HCOO
1.8 104
3.8
benzoic
C6H5COOH
C6H5COO
6.5 105
4.2
HOOCCH2COO OOCCH2COO
6.4 105
4.2
acetic
CH3COOH
carbonic
hydrogen sulfide
1.7 105
4.7
H2CO3
CH3COO
HCO3
4.3 107
6.4
H2S
HS-
9.1 108
7.1
HPO42
6.2 108
7.2
ammonium ion
H2PO4
NH4+
5.6 1010
9.2
hydrocyanic
HCN
NH3
CN-
4.9 1010
9.3
phosphoric (2nd)
Strong Acids
These are acids that are essentially completely
dissociated in solution (usually water).
H+(aq) + Cl(aq)
HCl(aq)
[H+ ][Cl ]
10 8
K =
[HCl]
S can hav e
mor e than 8 ve-
O
O
N
O
Cl can hav e
mor e than 8 v e-
O
O
Cl
nitrate anion
sulfate dianion
perchlorate anion
N
O
O
O
O H
Cl
O H
O
O H
nitric acid
sulfuric acid
O
perchloric acid
Polyprotic Acids
Sulfuric Acid:
H2SO4(aq)
HSO4 (aq)
Ka1 108
Ka2 10-2
Phosphoric Acid:
H3PO4(aq)
H2PO4 (aq)
HPO42 (aq)
Carbonic Acid:
H2CO3(aq)
HCO3 (aq)
Ka1 10-7
Ka2 10-11
Strong Bases
These are usually (and most commonly) alkali
metal hydroxides that dissociate completely in
solution:
NaOH(aq)
Kb =
Na+(aq) + OH(aq)
[Na + ][OH ]
10 8
[NaOH]
10
w
[H+ ] =
=
[OH ]
[OH ]
pH = 14 pOH
NH4+(aq) + OH(aq)
NaOH(aq)
Na+(aq) + OH(aq)
Weak Acids
These are acids that only dissociate to produce a
small amount of H+ in solution:
HF(aq)
H+(aq) + F(aq)
[H+ ][F ]
Ka =
= 3.5 10 4
[HF]
Acetic Acid
Carbonic Acid
Phosphoric Acid
H3C
OH
HO
active ingredient
in vinegar
HO
OH
OH
OH
used in soda
(Coke, Pepsi)
Acetylsalicylic Acid
Ascorbic Acid
O
HO
H3C
O
C
O
C
C
C
HO
CH2
OH
HO
OH
H
Aspirin
Vitamin C
0.1 - x
0M
0M
H+(aq) + OAc(aq)
x
[HOAc]
( x )( x )
= 1 10 5
(0.1 x )
( x )( x )
= 1 10 5
(0.1 x )
assume that x << 0.1 and drop from deonominator
( x )( x )
= 1 10 5
(0.1)
Important Approximation!!
H+(aq) + HS(aq)
H+(aq) + A(aq)
Oxyacids
Oxyacids are those acids in which the central atom
(most commonly N, Cl, S or P) is bonded to at least
one, and usually more, oxygen atoms. The
resulting negative charge on this unit is balanced
by the proper # of H+ that associate with the
oxygen atoms (one per oxygen atom).
A list of common oxyacids and their names:
HNO2
HNO3
Nitrous
Nitric
HClO
HClO2
HClO3
HClO4
Hypochlorous
Chlorous
Chloric
Percloric
H2SO3
H2SO4
Sulfurous
Sulfuric
H3PO2
H3PO3
H3PO4
Hypophosphorous
Phosphorus
Phosphoric
2) for the same # of oxygens, the more electronegative the central atom, the stronger the acid
Reasoning: the more electronegative the central atom, the
more the negative charge on the anion will be pulled
towards the central atom and away from the outlying
oxygens. Thus, there will be a lower electrostatic
attraction to H+ cations, allowing easier dissociation.
Example:
HClO
HClO2
HClO3
HClO4
Hypochlorous
Chlorous
Chloric
Percloric
Ka = 3 x 108
Ka = 1 x 102
Ka = 5 x 102
Ka 1 x 1010
HClO4
Note that the blue area around the H atom indicating positive
charge is increasing as O atoms are added.
H2SO3 or H2SO4
g)
O
H
H
C
C
OH
or
F
F
C
C
OH
Weak Bases
These are bases that only react to a relatively small
extent with H+ in solution:
:NH3(aq) + H+(aq)
NH4+(aq)
The convention, however, for writing equilibria for
weak bases is to react the base with water, which
generates a small quantity of OH-:
NH4+(aq) + OH(aq)
:NH3(aq) + H2O
This is the equilibrium we use to define our base
equilibrium constant, Kb:
[NH4 + ][ OH ]
= 1.8 10 5
K =
[NH3]
Formula
Structure
Kb
methylamine
NH2CH3
H N CH 3
4.4 x 10-4
carbonate ion
CO32-
2-
1.8 x 10-4
C
O
ammonia
NH3
H N H
1.8 x 10-5
hydrosulfide ion
nicotine
HS-
1.8 x 10-7
H S
C10H14N2
N
CH 3
N
hydroxylamine
NH2OH
H N OH
7 x 10-7
1.4 x 10-11
1.1 x 10-8
pyridine
C5H5N
1.9 x 10-9
ammonia? Kb 1 105
Init:
0.1 M
0M
:NH3(aq) + H2O
0M
NH4+(aq) + OH(aq)
@ Eq: 0.1 - x
[NH3]
( x )( x )
= 1 10 5
(0.1 x )
But, this will be a quadratic expression and the
quadratic formula is needed to exactly solve for x
(ugh!).
But lets use the very good approximation from
weak acid equilibria problem solving that will
dramatically simplify the algebra.
( x )( x )
= 1 10 5
(0.1 x )
assume that x << 0.1 and drop from deonominator
Important Approximation!
( x )( x )
= 1 10 5
(0.1)
x 2 = 1 10 6 } take square root of each side
pH = 14 pOH = 11
DANGER!!
VERY
Common
mistake!!
HCO3(aq) + OH(aq)
Cl
Os
O
H
PhO
H3C
Cl
H2
N
R3P
Pd
PR3
N
PR3
Cl
O H2
Problem: Identify the Lewis Base and Acid parts of
each compound shown above. Extra: What is the
oxidation state of the metal in each compound?
Al
F
F
Cl
Cl
BCl3 will form a moderately strong bond to :NH3:
Cl
B
Cl
Cl
Cl
B
N
H
Cl
Cl
N
H
[NH4+ ][ OH ]
Kb =
[NH3]
Kw
but remember that : [OH ] =
[H+ ]
substituting this in for [OH ] we now have :
[NH4+ ] Kw
Kb =
[NH3] [H+]
:NH3(aq) +
H+(aq)
NH4+(aq)
:NH3(aq) +
H+(aq)
[NH3][H+ ]
Ka =
[ NH+4 ]
But note that the reciprocal of this expression is
already in the Kb relationship:
[NH3][H+ ]
Ka =
[ NH+4 ]
[NH4+ ] Kw
Kb =
[NH3] [H+]
Kw
Kb =
Ka
-or-
Kw
Ka =
Kb
Kw = Ka Kb
H+(aq)
H+(aq)
H+(aq)
H+(aq)
+
+
+
+
Cl(aq)
Br(aq)
I(aq)
NO3(aq)
2H+(aq) + SO4(aq) *
H+(aq) + ClO4(aq)
These are
extremely
weak
conjugate
bases -Neutral
Anions!
Strong Bases:
LiOH(aq)
NaOH(aq)
KOH(aq)
RbOH(aq)
CsOH(aq)
Li+(aq)
Na+(aq)
K+(aq)
Rb+(aq)
Cs+(aq)
+
+
+
+
+
OH(aq)
OH(aq)
OH(aq)
OH(aq)
OH(aq)
These are
extremely
weak
conjugate
acids -Neutral
Cations!
Neutral
Cation
Li+
Na+
K+
Rb+
Cs+
Neutral
Anion
Cl
Br
I
NO3
SO42
ClO4
Neutral Salts
LiCl, LiBr, LiI, LiNO3, Li2SO4,
NaCl, NaBr, NaI, NaNO3, Na2SO4,
KCl, KBr, KI, KNO3, K2SO4,
RbCl, RbBr, RbI, RbNO3, Rb2SO4,
CsCl, CsBr, CsI, CsNO3, Cs2SO4,
Perchlorate salts are explosive !!!
SALTS
Cation(+)Anion(-)
Cation comes from the base Anion comes from the acid
Identify the Cation
Is the cation from a strong base (Group 1A or Ca 2+, Sr 2+, Ba 2+)
YES
NO
NO
Anion is from
a weak acid
(anion is a
moderate to
good conjugate
base)
Salt solution
will be basic
(salt of a
weak acid)
NO
Salt of a
weak acid &
a weak base!
Complicated!
Dont worry
c)
N H+ Cl-
Ka (HCl) = 1 108
Ka (pyridineH+) = 5 10-6
Ka (HBr) = 1 1010
f) CH3COOCs
g) Cs2S
h) NH4NO3
i) KCN
j) KNO3
Basic
Anion
Cation
Initial:
@ Eq:
1M
F(aq) + H2O
HF(aq) + OH(aq)
1-x
Kw
1 10
10
Kb =
=
=
1
10
Ka
1 10 4
DANGER!!
VERY
Common
mistake!!
10
[F ]
( x )( x )
= 1 10 10
(1 x )
assume that x << 1 and drop from deonominator
( x )( x )
= 1 10 10
(1)
x 2 = 1 10 10 } take square root of each side
DANGER!!
VERY
Common
mistake!!
5 mmol
= 0.033 M H+
150 mL
p H = 1.5
DANGER!!
VERY Common mistake!!
Kw
1 10 14
9
Kb =
=
=
1
10
Ka
1 10 5
Not realizing this - DANGER!!
Kb =
[HOAc][OH ]
[OAc ]
= 1 10 9
75 mmol
= 0.25M OAc
300 mL
0.25 M
H2O + OAc(aq)
@ Eq:
HOAc(aq) + OH(aq)
0.25 - x
[HOAc][OH ]
9
1
10
=
Kb =
[OAc ]
( x )( x )
= 1 10 9
(0.25 x )
assume that x << 0.25 and drop from deonominator
Approximation
( x )( x )
9
= 1 10
(0.25)
x 2 = 2.5 10 10 } take square root of each side
x = 1.6 10 5 = [OH ]
Titrations
A titration is the careful measured addition of a
known concentration of one substance that will
react with another unknown material in order to
determine the concentration of the unknown
material.
Determining the concentrations of unknown materials is a
routine procedure in chemistry. Titrations are commonly
used to determine the concentrations of acids and bases in
solution, as well as many other chemicals. Titrations are also
often the simplest and least expensive way of determining
concentrations of unknown materials.
Indicators
An indicator is a weak organic acid or base that
has sharply different colors in its associated and
dissociated forms:
HIn(aq)
H+(aq) + In(aq)
red acidic
blue basic
Indicators usually have very intense colors so one
only has to use a very small amount (a few drops)
so it will not affect the titration of the solution.
Remember that the indicator is an acid or base so if
you add a lot it will affect the titration!!
OH
Phenophtalein
OH
H+
HO
HO
acidic form - colorless
Methyl Red
O
O
OH
N N
O
N
N N
H+
pH color change
region
Acid color
Base color
Methyl violet
0-2
yellow
violet
methyl yellow
1.2 - 2.3
red
yellow
methyl orange
2.9 - 4.0
red
yellow
methyl red
4.2 - 6.3
red
yellow
bromthymol blue
6.0 - 7.6
yellow
blue
thymol blue
8.0 - 9.6
yellow
blue
phenolphthalein
8.3 - 10
colorless
pink
Alizarin yellow
10.1 - 12
yellow
red
HIn(aq)
H+(aq) + In(aq)
[H+][In ]
Ka =
[HIn]
At the color change [H+] = [In] = [HIn], so:
Buffer Solutions
Consider an acetic acid solution:
HOAc(aq)
HOAc(aq)
+
H (aq)
OAc(aq)
[OH ]
[Base]
= Kb
[
acidic
salt
]
[Acid]
= Ka
[
basic
sal
t]
[basic salt]
pH = pK a + log
[
acid
]
[acidic salt]
pOH = pKb + log
[
base
]