Académique Documents
Professionnel Documents
Culture Documents
ACID BASE
EQUILIBRIA
Contents
Definition of Acid and Base :
Arrhenius
Brnsted-Lowry , conjugate acid-base pairs
Lewis
Learning Outcomes
Able to differentiate and calculate acid
dissociation constants for weak and strong
acids (applicable to bases)
Calculate pH and pOH
Arrhenius Definition
Acid
Base
Arrhenius Definition
Whenever an acid dissociates (ionizes) in water,
solvent molecules participate in the reaction
HA (g or aq) + H2O(l) A- (aq) + H3O+(aq)
The H3O+ is
called
hydronium ion
The terms hydrogen
ion = proton = H+
are used
interchangeably
Arrhenius Definition
Strong acids: dissociate/ionize completely
into ions in water.
Eg:HNO3
Acid
donor.
Any species that donates an
H+ such as HCl, HNO3, H3PO4
All
Base
acceptor.
Any species that accepts an H+,
must contain lone pair of electrons
to bind the H+, such as NH3, CO32-, Fand OHBrnsted-Lowry bases are not
Arrhenius bases, but all Arrhenius
bases contain Brnsted-Lowry base
OH-. -
Example
Determine acid and base in the following reactions:
1. HCO3- (aq) + HF (aq) H2CO3 (aq) + F- (aq)
2. HCO3- (aq) + OH- (aq) CO32- (aq) + H2O (aq)
3. SO32- (aq) + NH4+ (aq) HSO3- (aq) + NH3 (aq)
4. HSO3- (aq) + NH3 (aq) SO32- (aq) + NH4+ (aq)
Answer
Acid
Base
1.
HF (aq)
HCO3- (aq)
2.
HCO3- (aq)
OH- (aq)
3.
NH4+ (aq)
SO32- (aq)
4.
HSO3- (aq)
NH3 (aq)
Acid
Conjugate
base
Base
Add H+
Conjugate
acid
Conjugate
base of HCl
Conjugate
acid of NH3
Note:
NH3
base
Add H+
NH4+
Conjugate
acid
H 2O
Acid
Remove H+
OH-
Conjugate Base
Example
a) What is the conjugate base of the following acids:
HClO4 ; HCO3- remove one proton ( H+) from the formula.
ClO4- ; CO32b) What is the conjugate acid of the following bases:
CN- ; H2O ; HCO3- add one proton to the formula
HCN ; H3O+ ; H2CO3
Note: Hydrogen Carbonate ion, HCO3- is amphoteric: a
substance that can act as an acid or as a base.
Example
Determine the conjugate acid-base pairs
in the following:
1. HCO3- (aq) + HF (aq) H2CO3 (aq) + F- (aq)
2. HCO3- (aq) + OH- (aq) CO32- (aq) + H2O (aq)
3. SO32- (aq) + NH4+ (aq) HSO3- (aq) + NH3 (aq)
4. HSO3- (aq) + NH3 (aq) SO32- (aq) + NH4+ (aq)
Answer
Acid
Base
Conj. Base
Conj. acid
HF (aq)
HCO3- (aq)
H2CO3 (aq)
F- (aq)
HCO3- (aq)
OH- (aq)
H2O (l)
CO32- (aq)
NH4+ (aq)
NH3 (aq)
SO32- (aq)
HSO3- (aq)
HSO3- (aq)
SO32- (aq)
NH3 (aq)
NH4+ (aq)
Remove H+
HSO3- (aq) + H2O(l)
H3O+
SO32-(aq) +
Add H+
Base
Remove H+
HSO3- (aq) + H2O(l)
(aq)
Add H+
H2SO3(aq) + OH-
Base
H
Lewis base
F
Lewis acid
Fe
+ 6
Fe C
36
Definitions Comparison
Theory
Arrhenius
Arrhenius
BrnstedBrnstedLowry
Lowry
Acid
+
Forms
Forms HH33O
O+ ions
ions in
in
water
water
Proton
Proton donor
donor
+
HCl
HCl+
+HH22OOH
H33OO++
+Cl
Cl-
Base
Base
Forms
Forms OH
OH- ions
ions in
in
water
water
Proton
Proton acceptor
acceptor
NH
NH33(aq)
(aq)+
+HH22OO
NH
NH4 +
+OH
OH4
Lewis
Lewis
Electron
Electron pair
pair acceptor
acceptor Electron
Electron pair
pair donor
donor
H
F
B
F
N
H
Strong Acids
Hydrohalic acids
Oxoacids
(number of O exceeds no. of
ionisable H atoms by two or
more)
HCl,
HBr,
HI
HNO3
H2SO4
HClO4
HClO3
Weak acids
Hydrohalic acids
HF
HCN
H2S
Oxoacids
(in which no. of O equals or
exceed by one the no. of
ionizable H)
HClO,
HNO2
H3PO4
Organic acids
(general formula RCOOH)
CH3COOH
C6H5COOH
Example
HF (aq) + H2O (l) H3O+ (aq) + F- (aq)
CH3COOH (aq) + H2O (l) H3O+ (aq) + CH3COO- (aq)
HNO2 (aq) + H2O (l) H3O+ (aq) + NO2- (aq)
Weak acid will partially ionize in water
Strong Base
Soluble
Soluble
compounds
compounds
containing
containing
2O
O2- or
or OH
OH-
Ionic
Ionic
hydrides
hydrides
and
and nitrides
nitrides
The
The cations
cations are
are
usually
usually those
those
of
of the
the most
most
active
active metals
metals
MO
MO or
or M(OH)
M(OH)22;;
Where
Where M=
M= Group
Group
IIA
IIA metal
metal
(Be,
(Be, Mg,
Mg, Ca,
Ca, Sr,
Sr, Ba)
Ba)
M
M22O
O or
or MOH;
MOH;
Where
Where M=
M= Group
Group
IA
IA metal
metal
(Li,
(Li, Na,
Na, K,
K, Rb,
Rb, Cs)
Cs)
HH- - (aq)
(aq) +
+ HH22O
O (l)
(l)
HH22 (g)
(g) +
+ OH
OH- (aq)
(aq)
NN3-3- (aq)
(aq) +
+ 33 HH22O
O (l)
(l)
NH
NH33 (aq)
(aq) +
+ 3OH
3OH(aq)
(aq)
Weak Bases
Compounds
with an
electron-rich
nitrogen are
weak bases
(none are
Arrhenius
bases).
The
common
structural
feature is
an N atom
that has a
lone pair
Ammonia
: NH3
Amines
such as
CH3CH2 : NH2
C5H5N:
Example
Autoionization of water
Water ionises into H+ and OH- (v. small extent). This
process is called the autoionization of water.
Keq
H O OH
H 2 O 2
H 2O
K eq H 3O
OH K
1 10 14 K w H 3O OH
In neutral solution:
[H3O+] = [OH-]
In acidic solution
In basic solution
Example
H O OH 1.0 x 10
1.0 x 10
1.0 x 10
H O OH 2.0 x 10
14
14
14
9
5.0 x 10 6 M
The pH scale
+
pH
pH =
= -log
-log [H
[H+ ]] =
= -log
-log
+
[H
[H33O
O+]]
+
[H
[H+]] (M)
(M) [OH
[OH-]-] (M)
(M)
>1.0x10-7 <1.0x10-7
pH
pH value
value
<7.00
<7.00
Neutral
=1.0x10-7 =1.0x10-7
Basic
Basic
-7
-7
<1.0x10
<1.0x10-7 >1.0x10
>1.0x10-7
=7.00
=7.00
>7.00
>7.00
[OH
[OH]-]
-14
11 10
10-14
-13
11 10
10-13
-12
11 10
10-12
-11
11 10
10-11
-10
11 10
10-10
-9
11 10
10-9
-8
11 10
10-8
Acidic
Acidic
[H3O+]
+
[H
[H33O
O+]]
-7
11 10
10-7
[OH
[OH]-]
-7
11 10
10-7
Neutral
Neutral
1 10-8
1 10-9
1 10-10
1 10-11
1 10-12
1 10-13
-14
11 10
10-14
[OH
[OH]-]
-6
11 10
10-6
-5
11 10
10-5
-4
11 10
10-4
-3
11 10
10-3
-2
11 10
10-2
-1
11 10
10-1
11
Basic
Basic
Example
KW
1.0 10 14
12
5
.
0
10
M
3
OH
2.0 10
Other p scale
The concentration of OH- can be expressed as pOH
pOH
pOH =
= -log
-log [OH
[OH- ]]
pH
+
pOH
=
pK
-log
KKww =
pH
+
pOH
=
pK
ww=
=
-log
=
Example:
14.00
14.00
Example
Calculate [H+] for a solution with pOH of 4.75
pH = 9.25
Acid-base indicator
pH paper
pH meter
Strong Acids
Strong acids are strong electrolytes and they ionize
completely in solution.
HNO3 (aq) + H2O (l) H3O+ (aq) + NO3-(aq)
Example
What is the pH of a 0.04 M solution HClO4?
HClO4 is completely ionized: [H+] = 0.04 M
Hence, pH= -log (0.040) = 1.40
Strong Bases
Most ionic hydroxides are strong bases (eg. NaOH, KOH
and Ca(OH)2.)
Strong bases are strong electrolytes and dissociate
completely in solution:
Example
What is the pH of a 0.011 M solution of Ca(OH)2?
Ca(OH)2 is a strong base.
Ca(OH)2 Ca2+
+ 2OH0.011M 0.011M 2 0.011M
pOH = -log (0.022) = 1.66
pH + pOH = 14.00
pH = 14.00 - pOH = 14.00 - 1.66 = 12.34
H O A
HA
Ka
H A
or K eq
HA
H O A
HA
Acid Ka
% HA dissociated
1.8 x10-5
0.42 %
[H ] [A ]
Ka
[HA]
H3O+(aq) + A- (aq)
x
[H3O ] [A ]
x2
Ka
[HA]
fx
[H 3O ]eqm
[HA] initial
x100
Example
H CHO
Ka
HCHO2
pH log H 2.38
H 4.2 10
log H 2.38
Example
Calculate Ka
H CHO
Ka
HCHO2
HCHO (aq)
H 4.2 10
Answer
HCHO2(aq) H+(aq) + CHO2-(aq)
Initial
Change
Eqm
0.10 M
-4.2 10-3M
+4.2 10-3M
+4.2 10-3M
4.2 10-3M
4.2 10 4.2 10
1.8 10
3
Ka
0.10
% ionisation
equilibrium
HCHO2 initial
100%
The percent
ionisation of a
weak acid
decreases as its
concentration
increases.
Percent ionised
4.2 10 3
100% 4.2%
0.10
5.0
4.0
3.0
2.0
1.0
0.0
0.1
0.1
5 concentration
0
5 (M)
Acid
Example
Polyprotic Acid
Acids have more than one ionizable H atom
Example: Sulfurous acid, H 2SO3.
H2SO3 (aq) H+(aq) + HSO3- (aq)
Ka1 = 1.7 x 10-2
HSO3- (aq) H+(aq) + SO32- (aq)
Ka2 = 6.4 x 10-8
Ka2 is much smaller than Ka1 ; easier to remove the first
proton from polyprotic acid than the second
Ka1 is much larger than Ka2 ; can estimate the pH by
considering only Ka1.
Example
CO2 dissolved in water at 25C and 0.1 atm to form H 2CO3 with conc. 0.0037
M.
What is the pH ?
CO2(aq) + H2O(l) H2CO3(aq)
[H2CO3] = 0.0037 M
H2CO3 is a polyprotic acid:
H2CO3(aq) H+(aq) + HCO3-(aq) ka1= 4.3 10-7
HCO3-(aq) H+ (aq) + CO32- (aq)ka2= 4.710-11
ANSWER = 4.40
Weak Bases
There is an equilibrium between the base and the resulting
ions
Weak base + H2O(l) conjugate acid + OH- (aq)
Eg: NH3(aq) + H2O
NH4+(aq) + OH-(aq)
[NH
][OH
[NH
44 ][OH ]]
K
Kbb
[NH
[NH33]]
Example
Calculate the concentration of OH- in a 0.15 M
solution of NH3. (Kb = 1.8 x 10-5)
NH3(aq) + H2O(l) NH4+(aq) + OH-(aq)
0.15 -x
[NH4 ][OH ]
(x)(x)
Kb
1.8 x 105
[NH3]
0.15 x
Example
A solution is made by adding Sodium Hypochlorite,
NaClO, to water (2.0 L soln). The pH of solution is 10.50.
How many moles of NaClO were added?
Note:
NaClO is an ionic compound, strong electrolyte.
NaClO Na+ + ClOClO-(aq) + H2O HClO(aq) + OH-(aq)
Kb = 3.3 x 10-7.
Answer
Unit in molarity
pOH + pH = 14
pOH = - log [OH-]
pH = - log [ H+]
Given: pH = 10.50 ; base. Whats the [OH-]
Knowing the [OH-] then we know the Molarity of ClO-.
Molarity of NaClO mole ( in the same volume: 2.0 L
)
NaClO
Na+ +
ClO1 mole
1 mole
1 mole
Answer
ClO-(aq) + H2O(l) HClO(aq) + OH-(aq)
Let say we start with 1.0 M NaClO : conc. of ClO- is 1.0 M.
Then,
ClO-(aq) + H2O(l) HClO(aq) + OH-(aq)
1-x
Answer
Given pH = 10.50
from : pH + pOH = 14.0
pOH = 14.0 - 10.50 = 3.50
pOH = - log [OH-]
[OH-] = 10
-3.50
= 3.2 x 10-4 M
x = 3.2 x 10-4 M
Initial
Change
final
ClO-(aq)
H2O(l)
HClO(aq)
OH-(aq)
-3.2 10-4
3.2 10-4
3.2 10-4
z - 3.2 10-4
3.2 10-4
[HClO][OH ]
Kb
[ClO ]
(3.2 x 10 4 )2
z 3.2 x 104
z 0.31M
3.3 x 107
3.2 10-4
Answer
Z = [ClO- ] = 0.31 M
NaClO = 0.31 M
Mol
Mol
Molarity, M
0.31
Volume(L)
2L
Mol of NaClO = 0.31 (mol/ L) x (2 L)
= 0.62 mol
[NH 3 ][H ]
K a K b
[NH 4 ]
[NH 4 ][OH ]
[NH 3 ]
[H ][OH ] K w
Ka Kb Kw
Therefore , the larger the Ka the smaller the Kb. That
is, the
stronger the acid, the weaker the conjugate base.
Taking negative logarithms:
pKa = -log (Ka) and pKb = -log(Kb)
then pKa + pKb = pKw
END of CHAPTER 13