AQUEOUS-SOLUTION CHEMISTRY

WHY AQUEOUS (WATER)?

 PLENTIFUL AVAILABLE
 EASILY PURIFIED
 NON TOXIC
WHAT IS ELECTROLYTE?

 ELECTROLYTE FORM IONS WHEN

DISSOLVED IN WATER OR CERTAIN
OTHER SOLVENT AND CONDUCT
ELECTRICITY.
– STRONG ELECTROLYTE
– WEAK ELECTROLYTE
ACIDS AND BASES

 1923: BRONSTED AND LOWRY

 ACID = PROTON DONOR
 BASE = PROTON ACCEPTOR
– ACID1 === BASE1 + PROTON
– BASE2 + PROTON === ACID2
 COMBINED:
– ACID1 + BASE2 === BASE1 + ACID2
EXAMPLE

 NH3 + H2O ======== NH4+ + OH-

 TRY FOR:
– H2O + HNO2

– H2PO4-
– NH2CH2COOH
AMPHIPROTIC SOLVENT

 AMPHIPROTIC SOLVENTS BEHAVE AS

ACIDS IN THE PRESENCE OF BASIC
SOLUTES AND BASES IN THE PRESENCE
OF ACIDIC SOLUTES.
 NH3 + CH3OH === NH4+ + CH3O-
 CH3OH + HNO2 === CH3OH2+ + NO2-
WATER

 H+
 H3O+
 H9O4+
 (H2O)nH+
AUTOPROTOLYSIS = self-ionization

 H2O + H2O === H3O+ + OH-

 CH3OH + CH3OH === CH3OH2+ + CH3O-
 CH3COOH + CH3COOH === CH3COOH2+ +
CH3COO-
 NH3 + NH3 === NH4+ + NH2-
STRENGTHS OF ACIDS AND BASES
DIFFERENTIATING SOLVENTS

 HClO4 + CH3COOH === CH3COOH2+ + ClO4-

– 5000 TIMES GREATER
THAN
 HCl + CH3COOH === CH3COOH2+ + Cl-
Chemical equilibrium

 Chemical equilibrium = a state in which the

ration of concentrations of reactans and
products is constant.
 Equilibrium-constants expression = algebraic
equations that describe the concentration
relationships among reactans and products
at equilibrium.
The equilibrium state

 H3AsO4 + 3I- + 2H+ === H3AsO3 + I3- + H2O

ORANGE-RED COLOR
 H3AsO3 + I3- + H2O === H3AsO4 + 3I- + 2H+
Equilibrium-constant Expression

 wW + xX ==== yY + zZ

y z
[Y ] [ Z ]
K w x
[W ] [ X ]
Type of equilibrium constant in
analytical chemistry

1) Dissociation of water, Kw,

2) Solubility, Ksp
3) Dissociation of weak acid or base, Ka or Kb
4) Formation of a complex ion, n
5) Redox eq., Kredox
6) Distribution eq., Kd
Kw = f(T)

Temperature (oC) Kw
0 0.114 x 10-14
25 1.01 x 10-14
50 5.47 x 10-14
100 49 x 10-14
Example:

 Calculate the hydronium and hydroxide ion

concentrations of pure water at 25 oC.
Ksp

 How many grams of Ba(IO3)2 (487 g/mol) can

be dissolved in 500 mL of water at 25 oC?
Ksp = 1.57 x 10-9.
 Calculate the molar solubility of Ba(IO3)2 in a
solution that is 0.0200 M in Ba(NO3)2.
 Calculate the molar solubility of Ba(IO3)2 in a
solution prepared by mixing 200 mL 0.0100
M in Ba(NO3)2 with 100 mL of 0.100 M NaIO3.
Ka and Kb

 Calculate the hydronium ion concentration in

0.120 M Nitrous acid. Ka = 7.1 x 10-4.
 Calculate the hydronium ion concentration in
in solution that is 2.0 x 10-4 M in aniline
hydrochloride, C6H5NH3Cl. Ka = 2.51 x 10-5.
Ka and Kb

 Calculate the hydroxide ion concentration of

a 0.0750 M NH3. Kb = 1.75 x 10-5.
 Calculate the hydroxide ion concentration in
a 0.0100 M sodium hypochlorite. Ka for HOCl
= 3.0 x 10-8.
Equation without assumption vs with
assumption

2

 K a  K  4 K a C HA
a
[ H 3O ] 
2


[ H 3O ]  K a C HA
Error Introduce by assumption
 Relative
Error
resulting
from the
assumption
 Exercises:

1) What hydroxide concentration is required to initiate

precipitation of Fe3+ from a 1.00 x 10-3 M solution of
Fe2(SO4)3? Ksp = 2 x 10-39.

1) At 25 oC, what are the molar hydronium ion

concentration in:
a) 0.100 M trimethylamine (Ka for trimethyl
amonium ion = 1.58 x 10-10)
b) 0.0100 M methylamine hydrochloride (Ka = 2.3 x
10-11).