Chapter 3: Reactions in Water Solution
Studies on a physical and chemical
process which occurs in aqueous
solution such as, ionization of
electrolytes, acid-base reaction.
Concepts
Solution - is a mixture of 2 or more
substances in a single phase. One constituent
is usually regarded as the SOLVENT and the
others as SOLUTES.
Solution = Solute + Solvent
SOLUTE – the part of a solution that is being
dissolved (usually the lesser amount)
SOLVENT – the part of a solution that
dissolves the solute (usually the greater
amount)
Solute solid solid gas liquid gas gas
Solvent solid liquid solid liquid liquid gas
Concepts
Solutions can be classified as saturated or unsaturated or
supersaturated .
A saturated solution contains the maximum quantity of solute
that dissolves at that temperature.
An unsaturated solution contains less than the maximum
amount of solute that can dissolve at a particular temperature
A Supersaturated solution contain more solute than is
possible to be dissolved.
Precipitate: Solute (solid) that
falls out of solution
Solubility (S)
Solubility (S): A measure of how much of a solute can be dissolved in
a solvent at a given temperature
Units: grams solute/100 mL solvent
Example: Solubility of sugar in water at 20 oC is 204 g/100 mL H2O
Three factors that affect solubility: Temperature, Pressure and
Polarity
Rules:
- Most nitrates (NO3-) are soluble
- Most salts of alkali metals (Group 1A), ammonium (NH4+), acetates (C2H3O2-), and
perchlorates (ClO4-) are soluble
- Most salts containing Cl-, Br-, and I- are soluble. Exceptions: salts of Ag+, Hg22+, Pb2+
- Most sulfates (SO42-) are soluble Exceptions: BaSO4, PbSO4, Hg2SO4, SrSO4
- Most hydroxides (OH-) are slightly soluble. Exceptions: Hydroxides of Ba2+, Sr2+, and
Ca2+ are marginally soluble
- Most salts containing S2-, CO32-, PO43-, CrO42- are insoluble.
Molar Concentrations
Molarity (CM): The number of moles of solute per 1 liter of solution
n solute
CM
Vsolution
Where, nsolute is number of moles of solute (mol)
Vsolution is volume of solution (L)
Example 1: Calculate the molarity of a solution made by dissolving
2.56 g of NaCl in enough water to make 2.00 L of solution
Example 2: After dissolving 1.56 g of NaOH in a certain volume of
water, the resulting solution had a concentration of 1.60 M. Calculate
the volume of the resulting NaOH solution
% mass Concentrations
% mass (C%): The number of grams of solute per 100 grams of
solution
m solute
C% 100 %
m solution
Where, msolute is mass of solute (g)
msolution is mass of solution (g)
Example 1: A solution contains 15 g Na2CO3 and 235 g of H2O?
What is concentration of mass of the solution?
1) 15% Na2CO3
2) 6.4% Na2CO3
3) 6.0% Na2CO3
Example 2: How many grams of NaCl need to prepare 250 g of a
10.0 % (by mass) NaCl solution?
Relationship between CM and C%
10d solution .C% Where, d and M is density of solution
CM
M solute (g/mL) and molar mass (mol/g)
Example 2: Mixing 16g of glucose (C6H12O6) in 100g of H2O.
Calculate CM and C% (with dH2O = 1 g/mL)?
Other Concentrations
Molal concentration (Cm): The number of moles of solute per 1000
g of solvent
n solute 1000
Cm
msolvent
Where, nsolute is number of moles of solute (mol)
msolvent is mass of solvent (g)
Molar fraction (Ni) is defined as the amount of a constituent
(expressed in moles), ni, divided by the total amount of all
constituents (Σni) in a mixture
ni
Ni
ni
Example: Calculate molal concentration (Cm) and molar fraction (Ni)
of solution containing glucose C6H12O6 (C% = 5%)?
Other Concentrations
equivalent concentration (CN) of a solution is defined as the molar
concentration CM divided by an equivalence factor feq
C M nsolute
CN
f eq V . f eq
Example:
Sulfuric acid (H2SO4) is a diprotic acid. Since only 0.5 mol of H2SO4 are
needed to neutralize 1 mol of OH−, the equivalence factor is:
feq(H2SO4) = 0.5
If the concentration of a sulphuric acid solution is c(H2SO4) =
1 mol/L, then its CN is 2 N. It can also be called a "2 normal"
solution.
Similarly, for a solution with CM (H3PO4) = 1 mol/L, the CN is 3 N
because phosphoric acid contains 3 acidic H atoms.
Solution of electrolytes
Solution of electrolyte = electrolyte solute + Solvent
(acid, base, salt) (H2O)
In a solution, electrolytes are dissociated into cations and anions by
solvation process.
NaCl(aq) → Na+(aq) + Cl-(aq)
Strong Electrolytes: Solutes that completely or nearly completely
ionize when dissolved in water
Salts: NaCl, NH4Cl, KBr, NaNO3
Strong acids: HCl, HNO3, H2SO4
Strong Bases: NaOH, KOH, Ca(OH)2
Weak Electrolytes: Only a small fraction of solutes ionize when
dissolved in water
Weak acids: acetic acid (C2H4O2), citric acid (C6H8O7)
Weak bases: ammonia (NH3) methylamine, cocaine, morphine
Solvation Process
Ions in aqueous solution are
surrounded by the H2O molecules
KMnO4 in water
Cations and anions are prevented
from recombining
Ions disperse uniformly throughout
the solution (homogeneous)
Rule: The compounds having the same characteristics can be dissolved
each other
Polar Solvent – Polar Solute
Nonpolar solvent – Nonpolar solute
Properties of Electrolyte solution
Degree of dissociation (α)
n C
Or 0≤α≤1
n0 C0
Where, n, C: number and concentration of molecules which are
dissociated.
n0, C0: number and concentration of molecules which are
initial
α > 0.3 : Strong electrolyte
At CN = 0.1 N 0.3 > α > 0.03: Average electrolyte
α < 0.03: Weak electrolyte
AB ↔ A+ + B-
Initial: C0 0 0
Dissociated: C C C
Equilibrium: C0 - C C C
Properties of Electrolyte solution
Electrolyte Constant (K): is equilibrium constant of dissociation
process
AmBn ↔ mAn+ + nBm-
K
A B
n m m n
Am Bn
Where, [ ] is concentration of compounds at equilibrium state
If α ↑ and K ↑ → Strong electrolytes
If α ↓ and K ↓ → Weak electrolytes
Note: For a weak acid (or base), electrolyte constant is acidic
constant Ka (or basic constant, Kb)
Relationship between α and K
AB → A+ + B-
Initial: C0 0 0
Dissociated: C0α C0α C0α
Equilibrium: C0 (1 - α ) C0α C0α
K
A
. B C .C C
0 0 0
2
AB C0 1 1
If weak electrolyte, α <<<1 → 1 – α = 1 → K = C0α2
Dissociation of Water
H 2O ↔ H+ + OH-
At 25oC, We have
K H 2O
H
. OH
1.8 10 16
H 2O
KH2O . [H2O] = [H+].[OH-] = 10-14
Ionization constant of water: Kw = [H+].[OH-] = 10-14
lg[H+] + lg[OH-] = -14
With pH = -lg [H+] and pOH = - lg[OH-], We have: pH + pOH = 14
If pH = 7 → neutral
pH < 7 → acidic
pH > 7 → basic
Calculation of pH value
For strong acid or base, we have α = 1 → [H+] or [OH-] = C0 → pH
For weak acid or base, we have α < 1
HB ↔ H+ + B-
Initial: C0 0 0
Dissociated: C0α C0α C0α
Equilibrium: C0 (1 - α ) C0α C0α
[H+] or [OH-] = C0 α→ pH
Example: Calculate pH of following solutions:
a. 0.01 mol HCl in 50 mL of solution.
b. 6 g CH3COOH in 1 L of solution, given Ka = 1.8x10-5
c. 8 g NaOH in 500 mL of solution.
d. 0.02 mol NH3 in 0.1 L of solution, given Kb = 1.79x10-5
Salts
Salts are ionic compounds
The positive ion is a metal or polyatomic ion
The negative ion is a nonmetal or polyatomic ion [exception is the
hydroxide ion (OH-)]
Salts dissociate completely into ions in solution
Solutions of salts may be acidic, basic, or neutral
Strong acid – weak base (Acidic), such as NH4Cl, (NH4)2SO4, …
NH4Cl → NH4+ + Cl-
NH4+ + H2O ↔ NH4OH + H+
Weak acid – strong base (basic), such as HCOONa, CH3COOK, …
HCOONa → HCOO- + Na+
HCOO- + H2O ↔ HCOOH + OH-
Salts
Strong acid – strong base (neutral), such as BaCl2, Na2SO4, …
Weak acid – weak base (uncertain), such as NH4CN, CH3COONH4 …
NH4CN → NH4+ + CN-
NH4+ + H2O ↔ NH4OH + H+
CN- + H2O ↔ HCN + OH-
Buffer solution: is which solution pH changes very little when a
small or moderate amount of strong acid or base is added to it →
it is used to prevent changes in the pH of a solution
Acidic Buffer (pH < 7): consisting of a mixture of a weak acid and
its conjugate base (its salt). Such as, CH3COOH/CH3COONa
basic Buffer (pH > 7): consisting of a mixture of a weak base and
its conjugate acid (its salt). Such as, NH4OH /NH4Cl
Acid-base reaction titration
Using to determine concentration of acid (or base) by reacting with a
base (or acid) which has known concentration
Equation:
C1.V1 = C2.V2
Where, C is equivalent
concentration (CN)
Example: Calculate the concentration of NaOH solution if 24.50 mL
of this base is needed to neutralize 12.00 mL of 0.225 M HCl solution