CHAPTER 4

AQUEOUS REACTIONS & SOLUTION STOICHIOMETRY

CONTENTS
4.1 General Properties of Aqueous Solutions 4.2 Precipitation Reactions 4.3 Acid-Base Reactions 4.4 Oxidation-Reduction Reactions 4.5 Concentrations of Solutions 4.6 Solution Stoichiometry and Chemical Analysis
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Learning Outcomes
Able to identify types of metathesis reaction Able to determine the precipitate forms in a reaction Able to calculate oxidation number of element and identify the oxidizing agent in a redox reaction Able to calculate unknown concentration in a titration of acid-base solutions (reaction).
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4.1 General Properties of Aqueous Solutions

A solution is a homogeneous mixture. Contains: a solvent (greater quantity) and solute(s). Solvent - substance in the mixture which acts as the dissolving medium. Whatever else is dissolved in the solution is called the solute(s).
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Cont: 4.1 General Properties of Aqueous Solutions

E.g. NaCl (s) + H2O (l) solute solvent NaCl (aq) aqueous solution

Solution in which water is the dissolving medium are called aqueous solutions.

Cont: 4.1 General Properties of Aqueous Solutions

All aqueous solutions can be classified in terms of its electrical conductivity. Solution conducts electricity: forms ions in solution is an electrolyte. e.g. NaCl (an ionic compound)
# conducts electricity well: strong electrolyte (NaCl) # conducts electricity poorly: weak electrolytes (CH3COOH)
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Cont: 4.1 General Properties o Aqueous Solutions

Solution does not conduct electricity does not form ions in solution is a non electrolyte e.g. sugar (a molecular compound)

4.1.1 Ionic Compounds in Water

Ionic compounds dissolve in water, dissociate into anions and cations. The solid no longer exists as a well ordered arrangement, each ion is surrounded by water molecules. The ions are dispersed uniformly throughout the solution. The relative concentrations of the ions depend on the chemical formula of the compound. (Sec: 4.5.2)
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H2O

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4.1.2 Molecular Compounds in Water

Molecular compounds (e.g. CH3OH, sugar etc.) dissolve and exist as dispersed molecules throughout the solution. The structural integrity of the compound is maintained. Does not form ions no ions to conduct electricity. they are non-electrolytes
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NaCl in water

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Cont: 4.1.2 Molecular Compounds in Water

Some important exceptions: NH3 dissolves in water to form NH4+ and OH HCl (g) in water ionizes to form H+ and Cl-

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4.1.3 Strong and Weak Electrolytes

Electrolyte: any substance whose aqueous solution contains ions that conduct electricity. Strong electrolytes - ionize 100 %in a solvent. E.g. (i) Most ionic compounds (salt) (ii) Strong acids and bases: HCl, HBr, HClO4
A single arrow (): ionization of strong electrolytes. A single arrow indicates that ions have no tendency to recombine.
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Cont: 4.1.3 Strong and Weak Electrolytes

Weak electrolytes - Incompletely ionization (small amount of ions). E.g. (i) Weak acid : HF, H2S, HC2H3O etc. (ii) Weak base : NH3, amine
A 1.0 M solution of acetic acid HC2H3O2: Small fraction (about 1 %) is present as H+ and C2H3O2 - ions. Most is present as HC2H3O2 molecules.
HC2H3O2 (aq)

(aq) + C2H3O2- (aq)

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Cont: 4.1.3 Strong and Weak Electrolytes

The double arrow () is significant: HC2H3O2 molecules are ionizing to form H+ and C2H3O2- and at the same time H+ and C2H3O2- ions are recombining.
Note: A double arrow electrolytes.

ionization of weak
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4.2 Precipitation Reactions

Precipitation: the reaction forming insoluble product (called precipitate).
caused by the attraction between the oppositely charged ions in the solid being too great for the water molecules to pull them apart.

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4.2.1 Solubility Guidelines for Ionic Compounds Know the solubilities of different compounds
Solubility guidelines are used to predict whether a precipitate will form when solutions are mixed.
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4.2.2 Metathesis Reaction

Metathesis reactions involve swapping ions in solution:
AX + BY AY + BX AgNO3(aq) + KCl (aq) AgCl (s) + KNO3(aq)
Positive ions (cations) and negative ions (anions) exchange partners. Sometimes known as double-displacement reaction.
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Cont: 4.2.2 Metathesis Reaction

Displacement reaction
Single displacement Double displacement (Metathesis) WX + YZ WZ + YX
Eg: Ppt Rxn Acid-Base Rxn
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X + YZ XZ + Y
Eg: Ox-Red Rxn (Activity Series) (Sec. 4.4)

Cont: 4.2.2 Metathesis Reaction

E.g: Acid-base neutralization reaction
HCl(aq) + NaOH(aq) NaCl(aq) + H2O(l) H+ + OH- H2O ions are removed from the solution

For a metathesis reaction to occur, ions must be removed from the solution (Sec. 4.2.3)
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Cont: 4.2.2 Metathesis Reaction: Driving Forces

Three chemical processes can lead to the removal of ions from solution (driving force for metathesis to occur): (i) The formation of an insoluble product (called a precipitate).(4.2) (ii) The formation of either a weak electrolyte or a non electrolyte.(4.3.4) (iii) The formation of a gas that escapes from solution.(4.3.3)
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Cont: 4.2.2 Metathesis Reaction (to predict products)

Metathesis reaction is used to predict whether two salts or two reactants can react to produce the products(s). Some Rules: 1. If one reactant is a salt containing the carbonate ion or the hydrogen carbonate ion and the other is a strong acid, the products will be a salt containing the anion of the acid, water and CO2.
HCl(aq) + NaHCO3(aq) NaCl(aq) + H2O(l) + CO2(g)
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Cont: 4.2.2 Metathesis Reaction (To predict products)

2. If the reactants are an acid and a base, carry out a neutralization reaction. HCl(aq) + NaOH(aq) NaCl(aq) + H2O(l)

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Cont: 4.2.2 Metathesis Reaction (To predict products)

3. Insoluble metal oxides react with strong acids
to form a salt (containing the anion of the acid) and water. MgO(s) + 2HCl(aq) MgCl2(aq) + H2O(l) 4. If both reactants are weak acids / weak bases, no reaction occurs.
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4.2.3 Ionic Equations

Chemical equations Molecular equation Ionic equation: complete ionic equation : net ionic equation
indicate whether dissolved substances are present in solution predominantly as ions or as molecules.
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Cont: 4.2.3 Ionic Equations

Molecular equation - list all species (reactants and products) in their molecular forms: HCl (aq) + NaOH (aq) H2O (l) + NaCl (aq)
Complete ionic equation - lists all ions in the reaction: H+ (aq) + Cl- (aq) + Na+ (aq) + OH- (aq) H2O (l) + Na +(aq) + Cl- (aq)
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Cont: 4.2.3 Ionic Equations

Spectator ions : ions that appear in identical form on both sides of the arrow (they play no role in the reaction). H+ (aq) + Cl- (aq) + Na+ (aq) + OH- (aq)
H2O (l) + Na +(aq) + Cl- (aq) Na+ (aq) and Cl- (aq) appear on both sides - spectator ions.
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Cont: 4.2.3 Ionic Equations

Omitting the spectator ions: Na+(aq) and Cl(aq)
Net ionic equation: H+ (aq) + OH- (aq) H2O (l)

Include only the ions and molecules directly involved in the chemical reaction. Charge is conserved in the reaction (sum of the charges are the same on both sides of the arrow).
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Cont: 4.2.3 Ionic Equations

To write an ionic equation:
Only strong electrolytes are written in ionic form. Weak electrolyte, Non electrolytes, insoluble are written in molecular form.
Note: take note on the difference between ionic equation and net ionic equation.
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Cont: 4.2.3 Ionic Equations

Guidelines for writing a balanced ionic equation: Write a balanced molecular equation for the reaction Rewrite the equation to show the ions formed from dissociation (for strong electrolytes). Identify and cancel spectator ions.
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Example 1
Write the net ionic equation for zinc metal with
hydrochloric acid to form hydrogen gas and aqueous solution of zinc chloride.

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Example 1 (Answer)
Molecular Equation (complete):
Zn (s) + 2HCl (aq) H2 (g) + ZnCl2 (aq) Ionic Equation (complete): Zn (s) + 2H+ (aq) + 2Cl- (aq) H2 (g) + Zn2+ (aq) + 2Cl- (aq)
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Example 1 (Answer)
Spectator ion is ClZn (s) + 2H+ (aq) + 2Cl- (aq)
H2 (g) + Zn2+ (aq) + 2Cl- (aq) Net Ionic Equation: Zn (s) + 2H+ (aq) H2 (g) + Zn2+ (aq) Reaction can occur when the net ionic

equation can be written.

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Example 2

Predict whether any reaction occurs when potassium chloride is mixed with sodium nitrate.

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Example 2 (Answer)
Molecular Equation (complete):
KCl(aq) + NaNO3(aq) KNO3(aq) + NaCl(aq)

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Example 2 (Answer)
Molecular Equation (complete):
KCl(aq) + NaNO3(aq) KNO3(aq) + NaCl(aq) Ionic Equation (complete): K+(aq) + Cl-(aq) + Na+(aq) + NO3-(aq) K+(aq) + NO3-(aq) + Na+(aq) + Cl-(aq)

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Example 2 (Answer)
Molecular Equation (complete):
KCl(aq) + NaNO3(aq) KNO3(aq) + NaCl(aq) Ionic Equation (complete): K+(aq) + Cl-(aq) + Na+(aq) + NO3-(aq) K+(aq) + NO3-(aq) + Na+(aq) + Cl-(aq)

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Example 2 (Answer)
Molecular Equation (complete):
KCl(aq) + NaNO3(aq) KNO3(aq) + NaCl(aq) Ionic Equation (complete): K+(aq) + Cl-(aq) + Na+(aq) + NO3-(aq) K+(aq) + NO3-(aq) + Na+(aq) + Cl-(aq) No net ionic equation. No reaction occurs.
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Example 3
Write balanced molecular, ionic and net ionic equations for the precipitation reactions (if any) for the following compounds:
(a) Mg(NO3)2 and NaOH (b) KCl and Na2SO4

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Example 3 (Answer)
(a) Write balanced molecular equation:
Mg(NO3)2 (aq) + 2NaOH (aq) Mg(OH)2 (s) + 2NaNO3(aq) Note: From guidelines table Mg(OH)2 will precipitate.

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Example 3 (Answer)
(a) Write balanced molecular equation:
Mg(NO3)2 (aq) + 2NaOH (aq) Mg(OH)2 (s) + 2NaNO3(aq)

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Example 3 (Answer)
Ionic equation: Mg2+ (aq) + 2NO3- (aq) + 2Na+ (aq) + 2OH- (aq) Mg(OH)2 (s) + 2Na+ + 2NO3-(aq)
Net ionic equation: Mg2+ (aq) + 2OH- (aq) Mg (OH)2 (s) Note: Na+ and NO3- are spectator ions.
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Example 3 (Answer)
(b) Write balanced molecular equation:
2KCl (aq) + Na2SO4 (aq) K2SO4 (aq) + 2NaCl (aq) Note: Both K2SO4 and NaCl are soluble and dissociate in solution.

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Example 3 (Answer)
(b) Write balanced molecular equation:
2KCl (aq) + Na2SO4 (aq) K2SO4 (aq) + 2NaCl (aq)

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Example 3 (Answer)
Ionic equation:
2K+ (aq) + 2Cl- (aq) + 2Na+ (aq) + SO42- (aq)

2K+ (aq) + SO42- (aq) + 2Na+ (aq) + 2Cl- (aq)

No reaction; the solutes merely mix in the solution.

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Extra Example
NaOH(aq) + H3PO4(aq)

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Extra Example
3NaOH(aq) + H3PO4(aq) Na3PO4 (aq) + 3H2O(l)

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Extra Example
3NaOH(aq) + H3PO4(aq) Na3PO4 (aq) + 3H2O(l)

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4.3 Acid-Base Reactions

Acids Definitions (based on Arrhenius) Substance that is able to ionize to form a hydrogen ion (H+) in solution, e.g. HCl, HNO3 etc. Increase the concentration of H+(aq) ions. H+ is a proton. Acids are called proton donors.
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Cont: 4.3 Acid-Base Reactions

Acids that ionize to form one H+ are called monoprotic acids. E.g: HCl and HNO3 Acids that ionize to form two H+ ions are called diprotic acids. E.g:H2SO4 - yields two H+ ions per molecule: H2SO4 (aq) H+ (aq) + HSO4- (aq) HSO4- (aq) H+ (aq) + SO4 2- (aq) Aqueous solution of sulfuric acid contains a mixture of H+ (aq), HSO4- (aq) and SO4 2- (aq).
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Cont: 4.3 Acid-Base Reactions

Acids that ionize to form more than two H+ ions are called polyprotic acids.

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Cont: 4.3 Acid-Base Reactions

Acids that ionize to form more than two H+ ions are called polyprotic acids. Bases: Soluble ionic compounds containing the hydroxide ions, OH-, eg. NaOH, Ca(OH)2, KOH etc. Increase the concentration of OH- (aq) when added to water.
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Cont: 4.3 Acid-Base Reactions

React with the H+ ions to form water(proton acceptor) H+ (aq) + OH- (aq) H2O (l) (neutralization rxn) Note: NH3 (ammonia) Compounds do not contain OH- ion BUT when added to water, accepts H+ ion from the water molecules increase the concentration of OHions in water. E.g. NH3 (aq) + H2O(l) NH4+ (aq) + OH- (aq)
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4.3.1 Strong and Weak Acids and Bases

Strong Acids and Bases
Strong electrolytes Completely ionized in solution Definition : Acids - proton donor Bases - proton acceptor
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Cont: 4.3.1 Strong and Weak Acids and Bases

Exception: Hydrofluoric acid, HF, is a weak acid. HF is very reactive, attacks many substances (cannot store in glass container). The reactivity is due to the combined action of H+ (aq) and F- (aq). Weak Acids and Bases Weak electrolytes Partially ionized in solution
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H
nnnnnn

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Cont: 4.3.1 Strong and Weak Acids and Bases

How to classify non-electrolyte, weak electrolyte or strong electrolyte:
Electrolyte Compounds Strong Weak Non

Ionic Molecular

All

None

None

Strong Weak acids All other acids and bases compounds

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Example 4
Classify each of the following aqueous solution as a non-electrolyte, weak electrolyte or strong electrolyte. (a) HBrO (b) HF (c) HNO3 (d) KOH (e) CoSO4 (f) Sucrose (g) O2

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Example 4 (Answer)
(a) HBrO - weak acid - weak electrolyte (b) HF - weak acid - weak electrolyte (c) HNO3 - strong acid - strong electrolyte (d) KOH - strong base - strong electrolyte (e) CoSO4 - salt - strong electrolyte (f) Sucrose - molecular - non electrolyte (g) O2 - molecular - non electrolyte
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Example 5
Classify the followings as a strong electrolyte, weak electrolyte or non electrolyte. HBr; H2S; NH3; Ba(OH)2; KCl; C6H6; I2

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Example 5 (Answer)
If a substance is a salt (metallic cation and a

non-metallic anion) strong electrolyte.

Ba (OH)2 strong electrolyte HBr is a strong acid strong electrolyte H2S is a weak acid - weak electrolyte NH3 is a weak base - weak electrolyte C6H6 is a hydrocarbon- non electrolyte I2 is a homonuclear diatomic element - not salts and not listed as acids or bases non electrolyte
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4.3.2 Neutralization Reactions and Salts

Neutralization Reactions and Salts
A neutralization reaction occurs when an acid and a base react to form a salt. E.g. HCl (aq) + NaOH (aq) H2O (l) + NaCl (aq) A salt is an ionic compound whose cation comes from a base and anion from an acid. Net ionic equation: H+ (aq) + OH- (aq) H2O (l)
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4.3.3 Acid-Base Reaction with Gas Formation

One of the driving force for metathesis reaction to occur. One of the products is a gas. Carbonates and hydrogen carbonates (bicarbonates) react with acids to form CO2 gas. Example : Sodium hydrogen carbonate (NaHCO3) reacts with HCl
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Cont: 4.3.3 Acid-Base Reaction with Gas Formation

Molecular equation: HCl (aq) + NaHCO3 (aq) NaCl (aq) + H2O (l) + CO2 (g) Ionic equation: H+ (aq) + Cl-(aq) + Na+ (aq) + HCO3 -(aq) Na+ (aq) + Cl- (aq) + H2O (l) + CO2 (g)

Net ionic equation: H+ (aq) + HCO3- (aq) H2O (l) + CO2 (g)
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H
nnnnnn

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H
nnnnnn

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4.3.4 Acid-Base Reactions with Weak Electrolyte or Nonelectrolyte Formation

Common weak electrolyte : H2O Example : Neutralization reaction: H++ OH- H2O Example: Mg(OH)2 - white suspension dissolves when reacts with HCl (aq)
Molecular equation: Mg(OH)2 (s) + 2HCl (aq) MgCl2 (aq) + 2H2O (l)
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Cont: 4.3.4 Acid-Base Reactions with Weak Electrolyte or Nonelectrolyte Formation

Ionic equation: Mg(OH)2 (s) + 2H+ (aq) + 2Cl- (aq) Mg2+ (aq) + 2Cl- (aq) + 2H2O (l)
Net ionic equation: Mg(OH)2 (s) + 2H+ (aq) Mg2+ (aq) + 2H2O (l) Note: H2O is the driving force
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Example 6
Write balanced net ionic equation for the reaction (if any) that may occur and indicate the driving forces when the following pair is mixed. Cr(C2H3O2)2 (aq) and HNO3 (aq)

Answer
Molecular equation: Cr(C2H3O2)2 (aq) + 2HNO3 (aq) Cr(NO3)2 (aq) + 2HC2H3O2 (aq)
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Example 6 (Answer)
Ionic equation: Cr2+ (aq) + 2C2H3O2- (aq) + 2H+ (aq) + 2NO3- (aq) Cr2+ (aq) + 2HC2H3O2 (aq) + 2NO3- (aq)
Net ionic equation: 2C2H3O2- (aq) + 2H+ (aq) 2HC2H3O2 (aq) C2H3O2- (aq) + H+ (aq) HC2H3O2 (aq) Note: HC2H3O2 is a driving force
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4.4 Oxidation-Reduction Reactions (Redox)

Corrosion - conversion of a metal into a metal compound.
When a metal undergoes corrosion, it loses electrons and form cations. E.g. Ca (s) + 2H+ (aq) Ca2+ (aq) + H2 (g)

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Cont: 4.4 Oxidation-Reduction Reactions

When atom, ion or molecule becomes more positively charged (has lost electrons) - it has been oxidized. Loss of electrons by a substance is called oxidation.

OIL RIG (Oxidation Is Losing, Reduction Is Gaining- in term of electrons)

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Cont: 4.4 Oxidation-Reduction Reactions

Example: Metal react with O2 in air to form metal oxides. The metal loses electrons to oxygen, forming metal ion and oxide ion. 2Ca (s) + O2 (g) 2CaO (s) Oxygen is transformed from neutral O2 to the O 2- ion.
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Cont: 4.4 Oxidation-Reduction Reactions

When an atom, ion or molecule become more negatively charged, it is reduced. The gain of electrons by a substance is called reduction. One reactant loses electrons, another reactant must gain electrons. This is called oxidation-reduction or redox reactions.
Substance oxidised (loses electron) eSubstance reduced (gains electron)
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77

4.4.1 Oxidation Number

Oxidation number of an atom in a substance is the actual charge of the atom if it is a monatomic ion; otherwise, it is the hypothetical charge assigned to the atom using a set of rules.
1. Atom in elemental form, the oxidation number is zero. E.g. S, Ar. 2. Monatomic ion, the oxidation number equals the charge on the ion. E.g. K+ ox. no. = +1, O2- ox. no. = -2.
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Cont: 4.4.1 Oxidation Number

3. Group 1A elements always have ox. no. = +1. Similarly, Group 2A = +2, Group 3A = +3.
4. The ox. no. of oxygen is usually -2 in both ionic and molecular compounds (except peroxides O22with ox. no. =-1). 5. The ox. no. of hydrogen is +1 when bonded to nonmetals and -1 when bonded to metals. 6. The ox. no. of fluoride ion is 1 for all compounds.
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Cont: 4.4.1 Oxidation Number

7. The ox. no. of halides (Group 7A other than fluoride) is 1 in binary compounds BUT positive values in oxyanions.
8. The sum of ox. no. of all atoms in a neutral compound is zero. 9. The sum of ox. no. in a polyatomic ion equals the charge of the ion.
10. Oxidation process will lead to increase in ox. no., while reduction process decrease in ox. no.
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4.4.2 Oxidation of Metals by Acids and Salts

Acids Metal react with acids to form salts and hydrogen gas. Example: Mg (s) + 2HCl (aq) MgCl2 (aq) + H2 (g)
Complete ionic equation: Mg (s) + 2H+ (aq) + 2Cl- (aq) Mg2+ (aq) + 2Cl- ( aq) + H2 (g)
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Cont: 4.4.2 Oxidation of Metals by Acids and Salts

Net ionic equation:
Mg (s) + 2H+ (aq) Mg2+ (aq) + H2 (g) Metal is oxidized by acid.

H+ ions are reduced to H2.

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Cont: 4.4.2 Oxidation of Metals by Acids and Salts

Salts Metal can be oxidized by aqueous solution of various salts. A + BX AX + B Displacement reaction occur if A is more easily oxidized than B.
Example: Fe (s) + Ni(NO3)2 (aq) Fe(NO3)2 (aq) + Ni (s)
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Cont: 4.4.2 Oxidation of Metals by Acids and Salts

Net ionic equation:
Fe (s) + Ni2+ (aq) Fe2+ (aq) + Ni (s) Oxidation of iron is accompanied by the reduction of Ni2+ to Ni.

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4.4.3 The Activity Series

Activity series is a list of metals arranged in order of decreasing ease of oxidation. (i) Metals at the top of the table are most easily oxidized - react to form compounds. (ii) Alkali metals and alkaline earth metals are at the top - active metals. (iii) The transition elements from group 1B and 8B are at the bottom - noble metals.
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Cont: 4.4.3 The Activity Series

How to use The Activity Series ??
(i) Any metal on the list can be oxidized by the ions of elements below it. E.g. Cu (s) + 2Ag+ (aq) Cu 2+ (aq) + H2 (g) (ii) Metals above hydrogen are able to react with acids to form H2.
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H
nnnnnn

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Example 7
Use the activity series to predict which of the following reactions will occur.
(a) Hg (l) + MnSO4 (aq) HgSO4 (s) + Mn (s) (b) 2Ag (s) + H2SO4 (aq) Ag2SO4 (aq) + H2 (g) (c) Ca (s) + 2H2O (l) Ca(OH)2 (aq) + H2 (g)

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Example 7 (Answer)
M + HX MX + H
M must be higher in the activity series than H. (a) Hg (l) + MnSO4 (aq) no reaction

Hg lies below Mn in the activity series, thus the reaction does not occur.
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Example 7 (Answer)
(b) 2Ag (s) + H2SO4 (aq) no reaction
Ag lies below hydrogen, thus the reaction does not occur. (c) Ca (s) + 2H2O (l) Ca(OH)2 (aq) + H2 (g) Ca lies above hydrogen, thus the reaction occurs.
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4.5 Concentrations of Solutions

Concentration - to designate the amount of solute dissolved in a given quantity of solvent or solution. The greater the amount of solute dissolved in a certain amount of solvent, the more concentrated the solution.

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4.5.1 Molarity
Quantitative measurement of concentration requires accurate determination of the amounts of solvent and solute present in a solution. Molarity (M) is used to measure the amount of solute in a solution.

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Cont: 4.5.1 Molarity

M =

number of moles of solute, n volume of the solution in liters, V

Molarity can be used as a conversion factor to change between volume of solution and number of moles of substance.
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Example

What is the molarity of an 0.217 mol ethanol (C2H6O) in 100 mL of water?

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Example 8

What is the molarity of an ethanol (C2H6O) solution containing 10.0 g of ethanol in water with a total volume of 100 mL.

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Example 8 (Answer)
MW of C2H6O = 46.07 g
10.0 g C2H6O 1 mol C2H6O 46.07 g C2H6O = 0.217 mol C2H6O

M = 0.217 mol C2H6O = 2.17 M 0.100 L

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Example 9
How many grams of HCl are contained in 500 mL
of a 0.250 M HCl solution?

1 mol HCl = 36.45 g HCl

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Example 9 (Answer)
HCl is the solute, M = moles solute volume in liters mol solute = M volume in liters = 0.250 M x 0.500 L = 0.125 mol mass (g) = 0.125 mol molar mass HCl = 0.125 mol 36.45 g/mol = 4.56 g HCl

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4.5.2 Expressing the Concentration of Electrolyte

When an ionic compound dissolves, the relative concentrations of the ions depend on the chemical formula of the compound. Examples: (i) 1.0 M solution of sodium sulfate, Na2SO4 : Na2SO4 2Na+ + SO422.0 M in Na+ ions, 1.0 M in SO42- ions
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Cont: 4.5.2 Expressing the Concentration of Electrolyte

(ii) 0.025 M aqueous solution of calcium nitrate, Ca (NO3)2:
Ca (NO3)2 Ca2+ + 2NO3-

0.025 M in Ca2+ ions 2 0.025 M in NO3- ions

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QUESTION
A solution is prepared by adding 1.60 g of solid NaCl to 50.0 mL of 0.100 M CaCl2. Calculate the molarity, M of chloride ion in the final solution. Assume that the volume of the final solution is 50.00 mL. (Answer = 0.748 M)

4.5.3 Dilution
Solutions of known concentration may be diluted with the solvent to produce a more diluted (less concentrated) solution. The number of moles of solute - unchange. Moles of solute before dilution = moles of solute after dilution. moles solute = molarity volume Minitial Vinitial = Mfinal Vfinal
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Example 10
What is the molarity of a solution of NaOH formed by diluting 125 mL of a 3.0 M NaOH solution to 500 mL?

Solution

M iVi M f V f

M iVi 3.0 M 125 mL Mf 0.75 M 500 mL Vf

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4.6 Solution Stoichiometry and Chemical Analysis

4.6.1 Titration
A titration is an experiment in which the unknown molarity of a substance is measured by using the known molarity of another substance.

104

Cont: 4.6.1 Titration

Example: To determine the unknown concentration of HCl solution . Standard solution: NaOH solution, 0.100 M Prepare 0.100 M NaOH
(i) Take a specific volume of HCl solution (example: 20 ml) (ii) Slowly add the standard 0.100 M NaOH until the neutralization reaction between HCl and NaOH is completed.
105

H
nnnnnn

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Cont: 4.6.1 Titration

The point at which stoichiometrically equivalent quantities are brought together is known as the equivalence point of the titration. In acid-base titration, dyes known as acid-base indicators are used to determine the end point. e.g. Phenolphthalein is colorless in acidic solution, red in basic solution. The color change from colorless to red end point of the titration.
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Cont: 4.6.1 Titration

The equivalence point of the titration is the point where the stoichiometrically correct number of the moles of each reactant is present. The end point of the titration is the point where the indicator changes.
Note: The equivalence point and end point are not the same, but coincide closely.
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Example 11

What is the molarity of a solution of H2SO4 if 20.00 mL of a 0.100 M NaOH solution is required to react completely with 25.00 mL of the H2SO4 solution.

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Example 11 (Answer)
The chemical reaction describing the reaction.
H2SO4(aq) + 2NaOH(aq) Na2SO4(aq) + 2H20(l) Note: H2SO4 has two ionizable H+ ions that react with OH- ions from NaOH.

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Example 11 (Answer)

M NaOH VNaOH 2 M H 2 SO4 VH 2 SO4 1 M H 2 SO4 M NaOH VNaOH VH 2 SO4 2

0.100 M 20 .00 mL 0.04 M 25 .00 mL 2

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Example 12
A 10g solid sample containing Zn(OH)2 is

added to 0.400L of 0.550M solution of HBr.

The solution that remains is still acidic. It is then titrated with 0.5M NaOH solution which requires 165 mL to reach the equivalence point. What is the actual mass of Zn(OH)2 in

the sample? What is its mass percentage?

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Example 12 (Answer)
Acid + Base water (neutralization rxn) H+ + OH- salt + H20 From Equation: Mol H+ (from HBr) = mol OH- (from Zn(OH)2 +
mol OH- (from NaOH)

H+ = 0.550M x 4.0L = 0.220 moles OH- (from NaOH) = 0.5M x (165/1000)L = 0.0825 moles OH- (from Zn(OH)2) = ? (x moles)
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(Answer)
X moles = 0.22 moles 0.0825 moles = 0.1375 moles OH- from Zn(OH)2
Zn(OH)2 Zn2+ + 2OHIf you we have 0.1375 moles of OH- = 0.1375/2 moles Zn(OH)2 = 0.06875 moles So Zn(OH)2 = 0.06875 mol x 99.41 g/mole = 6.8344 g
Mass percentage = 6.8344/10 x 100 = 68.34%
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4.6.2 Stoichiometry for Reactions in Solution

Step 1
Identify the species present and determine what reaction occurs. Step 2

Write the balanced net ionic equation for the reaction.

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Cont: 4.6.2 Stoichiometry for Reactions in Solution

Step 3 Calculate the moles of reactants.
Step 4 Determine which reactant is limiting. Step 5 Calculate the moles of product(s), convert to grams or other units as required.
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Example 13
Calculate the mass of PbSO4, when 1.25 L of 0.0500 M Pb(NO3)2 and 2.00 L of 0.0250M Na2SO4 are mixed.
Molecular Equation:

Pb(NO3)2(aq) + Na2SO4(aq) PbSO4(s) +

2NaNO3(aq)
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Example 13 (Answer)
Ionic Equation:
2Na+(aq) + SO42-(aq) + Pb2+(aq) + 2NO3-(aq) PbSO4(s) + 2Na+(aq) + 2NO3-(aq) Net ionic equation: SO42-(aq) + Pb2+(aq) PbSO4(s)

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Example 13 (Answer)
Moles of reactants
moles of Pb2+ = 1.25 L 0.0500 mol = 0.0625 mol Pb2+ L moles of SO42= 2.00 L 0.0250 mol = 0.0500 mol SO42L
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Example 13 (Answer)
Limiting Reactants
Pb2+ and SO42- react in a 1:1 ratio , the amount of SO42- will be the limiting factor. Grams of product
0.0500 mol PbSO4 303.3 g PbSO4 = 15.2 g PbSO4 1 mol PbSO4
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EXAMPLE 13
Calculate the mass of PbSO4, when 1.25 L of 0.0500 M Pb(NO3)2 and 2.00 L of 0.0250M Na2SO4 are mixed. Pb(NO3)2(aq) + Na2SO4(aq) PbSO4(s) + 2NaNO3(aq)

EXAMPLE 13
Calculate the mass of PbSO4, when 1.25 L of 0.0500 M Pb(NO3)2 and 2.00 L of 0.0250M Na2SO4 are mixed.
Pb(NO3)2(aq) + Na2SO4(aq) PbSO4(s) + 2NaNO3(aq)

mol Pb(NO3)2 = MV = 0.0500 1.25 = 0.0625 mol

Mol Na2SO4 = MV = 0.0250 2.00 = 0.050 mol

EXAMPLE 13
Calculate the mass of PbSO4, when 1.25 L of 0.0500 M Pb(NO3)2 and 2.00 L of 0.0250M Na2SO4 are mixed. Pb(NO3)2(aq) + Na2SO4(aq) PbSO4(s) + 2NaNO3(aq) mol Pb(NO3)2 = MV = 0.0500 1.25 = 0.0625 mol Mol Na2SO4 = MV = 0.0250 2.00 = 0.050 mol Therefore Na2SO4 is the limiting reactant and 0.050 mol

PbSO4 is produced.
mass PbSO4 = 0.050 mol 303.26g/mol = 15.16 g

Exercise 4.1

What mass of NaOH is required to precipitate all the Fe2+ ions from 50.0 mL of 0.200 M Fe(NO3)2

solution?

Answer: 0.800 g NaOH

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END of CHAPTER 4

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