Chapter 5: 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.
Electrolytes vs Nonelectrolytes
 Electrolytes are substances that yield ions and conduct an electric
current in solution.
 The strength with which substances conduct an electric current
is related to their ability to form ions in solution.

 Strong and weak electrolytes differ in the degree of ionization or

dissociation.
- Strong: Large
amount of ions
- Weak: small
amount of ions

Nonelectrolytes
without ions
Solution of Nonelectrolytes
 On adding a solute to a solvent, the properties of the solvent are
modified.
Vapor pressure decreases
Melting point decreases
Boiling point increases
Osmosis is possible (osmotic pressure)

 These changes are called COLLIGATIVE PROPERTIES.

 They depend only on the NUMBER of solute particles relative to

solvent particles, not on the KIND of solute particles.
Solution of Nonelectrolytes
 Vapor-Pressure: is pressure on the interface between gas and
liquid layers, induced by gas compounds

At equilibrium state, Volatilization

saturated vapor- Liquid Gas
pressure (Ps) condensation

 Ps = constant at
certain T

 Ps,solvent > Ps,solution

Solution of Nonelectrolytes
 Freezing-Point (tf): is temperature when Ps of liquid phase =
Ps of solid phase

 The freezing-point depression, ∆tf , is the difference between the

freezing points of the pure solvent and a solution of a
nonelectrolyte in that solvent, and it is directly proportional to the
molal concentration (Cm) of the solution.
∆tf = tfsolution – tfsolvent = Kf .Cm
Where, freezing-point constant (Kf ) is the freezing-point
depression of the solvent in a 1-molal solution of a nonvolatile,
nonelectrolyte solute.

 Because of tfsolution < tfsolvent → ∆tf < 0

Example
What is the freezing-point depression of water in a solution of 17.1 g
of sucrose, C12H22O11, in 200 g of water? What is the actual freezing
point of the solution? (given Kf of H2O = −1.86°C/m)

We have,

a. Moreover, ∆tf = Kfm

∆tf = 0.250 m × (−1.86°C/m) = −0.465°C

b. f.p. solution = f.p. solvent + ∆tf

f.p. solution = 0.000°C + (−0.465°C) = −0.465°C

Solution of Nonelectrolytes
 Boiling-Point (tb): is temperature when Ps of liquid phase =
Ps of gas phase

 The boiling-point elevation, ∆tb, is the difference between the

boiling points of the pure solvent and a nonelectrolyte solution of
that solvent, and it is directly proportional to the molal
concentration of the solution.
∆tb = tbsolution – tbsolvent = Kb .Cm
Where, boiling-point constant (Kb) is the boiling-point elevation
of the solvent in a 1-molal solution of a nonvolatile,
nonelectrolyte solute.

 Because of tb solution > tb solvent → ∆tb > 0

Example
What is the boiling-point elevation of a solution made from 20.1 g of a
nonelectrolyte solute and 400.0 g of water? What is the actual boiling
point of the solution? The molar mass of the solute and Kb of H2O are
62.0 g/mol and 0.51°C/m .

We have,

a. Moreover, ∆tb = Kbm

∆tb = (0.51°C/m)x 0.81 m= 0.41°C

b. b.p. solution = b.p. solvent + ∆tb

b.p. solution = 100°C + (0.41°C) = 100.41°C

Solution of Nonelectrolytes
Table of Freezing-Point and Boiling-Point Constants
for some normal solvents
Osmotic Pressure of nonelectrolyte Solution
 A semipermeable membrane (màng bán thấm) allows the passage
of some particles while blocking the passage of others.

 Osmotic process (hiện tượng thẩm thấu) is the movement of

solvent through a semipermeable membrane from the side of
lower solute concentration to the side of higher solute
concentration.
 Osmotic Pressure (π) is
the external pressure that
must be applied to stop
osmosis.
 Vant’Hoff Law:
π = CM.R.T (atm)
R = 0.082 L. atm. Mol-1.K-1
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
Colligative properties of electrolyte solution
 Because sum of particles in an electrolyte solution is increased,
the prince in the colligative properties of nonelectrolyte solution is
unsuitable for this solution.
Using a van 't Hoff factor, i to calculate freeze-point, boiling point
and Osmotic pressure

Nonelectrolyte solution Electrolyte Solution

∆tf = Kf .Cm ∆tf’ = Kf .Cm. i
∆tb = Kb .Cm ∆tb’ = Kb .Cm. i
π = CM.R.T π' = CM.R.T .i

With i =1, it is solution of nonelectrolytes.

With i >1, it is solution of electrolytes.
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
Solubility equilibrium
 Some of ionic compounds (acid, base and salts) are marginally
soluble in water Solubility equilibrium

AmBn (s) ↔ mAn+ (l) + nBm- (l)

K
A  B 
n m m n

Am Bn (s)
Due to concentration of solid ≈ 1, Solubility product constant
expression:
T A   B 
n m m n

 Relationship between Solubility (S) and T:

AmBn (s) ↔ mAn+ (l) + nBm- (l)
S (mol/L) mS nS

T A   B 
n m m n
 mS  .(nS ) n  m m .n n .S m  n
m
Conditions obtaining a precipitate
For a general reaction,
mAn+ (l) + nBm- (l) ↔ AmBn (s)

 Step 1: Determine concentration of ions An+ and Bm-

 Step 2: Calculate ionic product by expression: Tx = [An+]mx.[Bm-]nx

 Step 3: Comparison between T and Tx

If Tx > T: obtaining precipitate
Tx = T: saturated solution
Tx < T: did not have precipitate