Zumdahl Chapter 4:Types of Chemical Reactions and Solution Stoichiometry

Aqueous solutions: water is the dissolving medium, or solvent.

4.1: Water, the Common Solvent
Has the ability to dissolve many different substances
Water is a bent v shaped molecule; 105 degrees H-O-H
O-H bonds are covalent formed by electron sharing between O and H atoms
Not shared equally
Delta indicated partial charge (less than one unit of charge)
Water is a polar molecule
Polarity gives water the ability to dissolve compounds
Hydration: water molecules are attracted to anions/cations causing salt to dissolve
When ionic substances (salts) dissolve in water, they break up into individual cations/anions
Solubility varies greatly
Depends on relative affinities of ions for each other and for water molecules
Water dissolves nonionic substances
Ethanol (C2H5OH)
Water cant dissolve substances that are non-polar (animal fat)
4.2: The Nature of Aqueous Solutions: Strong and Weak Electrolytes
Solution is a homogenous mixture (same throughout)
Composition of a solution can be varied by changing amount of dissolved substances
Weak, or strong coffee
Solute a substance dissolved in liquid, the solvent
Electrical conductivity: ability to conduct an electric current
Strong electrolytes: conduct current very efficiently
Weak electrolytes: conduct only a small current
Nonelectrolytes: conduct no current
Arrhenius: extent to which a solution can conduct an electric current depends on the number
of ions present.
Strong Electrolytes
1. Soluble salts
2. Strong acids
3. Strong bases
Solubility is measured in terms of mass of solute that dissolves per given volume of solvent or in
terms of the number of moles of solute that dissolves in a given volume of solution
NaCl, KCl and NH4Cl are very soluble in water
AgCl is only slightly soluble
Acids
Arrhenius found that when HCl, HNO3 and H2SO4 dissolved in water they behaved as
strong electrolytes
Proposed an acid is a substance that produces H+ ions (protons) when dissolved in water
When HCl, HNO3 and H2SO4 are put in water, virtually every molecule dissociates
Strong acids
Sulfuric acid (H2SO4)
Formula indicates should produce 2 H+ ions when dissolved
Only the first H+ ion is completely dissociated
Contains H+ ions and HSO4- ions

Strong Bases: soluble compounds containing the hydroxide ion (OH-) that completely
dissociate when dissolved in water
Solutions have a bitter taste and slippery feel
Common solutions are NaOH or KOH
Weak Electrolytes
Substances that produce relatively few ions when dissolved in water
Common weak electrolytes are weak acids and weak bases
Formula HC2H3O2 (acetic acid) indicates 1 acidic and 3 nonacidic hydrogen atoms
Only 1% dissociate
Weak electrolyte therefore a weak acid: any acid that dissociates only to a slight extent in
aqueous solution
Weak base: the resulting solution is a weak electrolyte (very few ions are present)
Most common weak base is ammonia (NH3)
Nonelectrolytes
Substances that dissolve in water but do not produce any ions
Ethanol; entire C2H5OH molecules dispersed in water
Sucrose (C12H22O11); very soluble in water, but produces no ions when it dissolves
4.3: The compositions of Solutions
To perform stoichiometric calculations we must know 2 things:
1. nature of the reaction
2. the amounts of chemicals present in the solutions
Molarity (M): moles of solute per volume of solution (in L)
M=moles of solute/liters of solution
A solution that is 1.0 molar contains 1.0 mole of solute per liter of solution
Solution concentration is always given in terms of the form of the solute before it dissolves
Liters of solution x Molarity = liters of solution x (moles solute/liters soln.)
= moles of solute
Standard solution: a solution whose concentration is accurately known
Dilution
Water is added to concentrated (stock solutions) to achieve the desired Molarity
Moles of solute after dilution = moles of solute before dilution
Dilution procedure involves 2 types of glassware: a pipet and a volumetric flask
Pipets
Measuring pipets: used to measure out volumes when a volumetric pipet is not available
Volumetric pipets (type we used in the first lab)
4.4: Types of Chemical Reactions
Precipitation reactions; acid-base reactions; oxidation reactions
4.5: Precipitation Reactions
A reaction that when 2 solutions are mixed, an insoluble substance (a solid which separates from
the solution) forms.
Reactants: K2CrO4(aq) and Ba(NO3)2(aq); a yellow solid is formed
Ba(NO3)2 contains separated Ba2+ and NO3- ions; KCrO4 contains K+ and CrO4 2Things that will help predict the products:
1. When ions form a solid compound, it must have a zero net charge. Thus the products of
this reaction must contain both anions and cations.

2. Most ionic materials contain only 2 types of ions: one type of cation and one type of
anion (NaCl, KOH, etc.)
Possible combinations are: K2CrO4, KNO3, BaCrO4, and Ba(NO3)2
Has to be KNO3 and BaCrO4 as the other options were reactants
Which is the yellow solid?
K+ and NO3- colorless
CrO4 2- is yellow
K+ and NO3- are left dissolved in the solution; dont for a solid; (aq)
Simple Rules for Solubility of Salts in Water
1. Most nitrate (NO3-) salts are soluble.
2. Most salts of Na+, K+ and NH4+ are soluble.
3. Most chloride salts are soluble. Notable exceptions are AgCl, PbCl2, and Hg2Cl2
4. Most sulfate salts are soluble. Notable exceptions are BaSO4, PbSO4, and CaSO4
5. Most hydroxide salts are only slightly soluble. The important soluble hydroxides are
NaOH, KOH and Ca(OH)2
6. Most sulfide (S 2-), carbonate (CO3 2-) and phosphate (PO4 3-) salts are only slightly
soluble.
Ion interchange: cation from one reactant combines with the anion from the other reactant
4.6: Describing Reactions in Solution
Molecular equation: shows reactants and products
Complete ionic equation: represents the actual forms of the reactants and products in a solution.
All substances that are strong electrolytes are represented as ions.
Spectator ions: ions that do not participate directly in a reaction in solution.
Net ionic equation: includes only those solution components directly involved in the reaction.
Spectator ions are not included.
4.7: Selective Precipitation
Separating the cations by precipitating them one at a time.
Cations Ag+, Ba 2+ and Fe3+
1. Add an aqueous solution of NaCl to solution containing all the cations. Solid AgCl will
form, and can be removed, leaving Ba 2+ and Fe 3+ ions in the solution.
2. Add an aqueous solution of Na2So4 to solution containing Ba 2+ and Fe 3+ ions. Solid
BaSO4 will form and can be removed, leaving only Fe 3+ ions.
3. Add an aqueous solution of NaOH to the solution containing Fe 3+. Solid Fe(OH)3 will
form and can be removed.
Qualitative Analysis: process whereby mixtures of ions are separated and identified.
4.8: Stoichiometry of Precipitation Reactions
Solving a Stoichiometry Problem Involving Reactions in Solution
Identify the species present in the combined solution and determine which reaction occurs
Write the balanced equation for the reaction
Calculate the moles of reactants
Determine which reactant is limiting
Calculate the moles of product or products, as required
Convert to grams or other units, as required
Gravimetric analysis: a method where the amount of a given substance is determined by
forming a precipitate, which is then filtered, dried and weighed.
4.9: Acid-Base Reactions

Bronstead Lowry definition

Acid is a proton donator
Base is a proton acceptor
OH- + HC2H3O2 H2O + C2H3O2Hydroxide ion is such a strong base that for purposes of stoichiometry it is assumed to react
completely with any weak acid dissolved in water.
Calculations for Acid-Base Reactions
List the species present in the combined solution before reaction, and decide which
reaction will occur.
Write the balanced net ionic equation for the reaction.
Change the given quantities of reactants to moles. For reactions in solution, use the
volumes of the original solutions and their molarities.
Determine the limiting reactant where appropriate.
Calculate the moles of the required reactant or product.
Convert to grams or a volume of solution, as required by the problem.
Neutralizing reaction: just enough base is added to react exactly with all of the acid in a
solution (acid has been neutralized).
Acid-Base Titrations
Example of volumetric analysis: a technique in which one solution is used to analyze another.
Titrant: solution used to carry out the analysis; delivered in a buret which accurately measures
the volume.
Equivalence point (stoichiometric point): point in the titration at which enough titrant has been
added to react exactly with the substance being determined.
Indicator: name of a chemical that changes color; marks equivalence point.
The following requirements must be met for a titration to be successful:
The concentration of the titrant must be known; called a standard solution.
The exact reaction between titrant and substance being analyzed must be known.
The stoichiometric point must be known. An indicator that changes color is often used.
The point at which the color change occurs is called the endpoint.
Goal is to choose an indicator whose endpoint coincides with the stoichiometric point.
Common indicator is phenolphthalein; colorless in acid, but turns pink at the endpoint
when an acid is titrated with a base.
The volume of titrant required to reach the stoichiometric point must be known.
The key to success is to write down all of the components in the solution and to focus on the
chemistry of each one.
4.10: Oxidation-Reduction Reactions
2Na + Cl2 2 NaCl
Neutral sodium atoms react with chlorine gas (diatomic Cl2 molecules) to form ionic solid
NaCl which contains Na+ and Cl- ions.
Redox reactions: reactions in which one or more electrons are transferred.
Combustion, oxidation of sugars, fats, proteins
Oxidation States
Provides a way to keep track of electrons in redox reactions
Rules for Assigning Oxidation States
1. The oxidation state of an atom in an element is 0. For example, the oxidation state of each
atom in the substances Na(s), O2(g), etc. is 0.

2. The oxidation state of a monatomic ion is the same as its charge. For example, the ON of the
Na+ ion is +1.
3. In its covalent compounds with nonmetals, hydrogen is assigned an ON of +1. For example,
in compounds HCl, NH3, H20, etc.
4. Oxygen is assigned an oxidation state of -2 in its covalent compounds, such as CO, CO2,
SO2, etc. The exception to this rule occurs in peroxides (O2 2- group), where each oxygen is
assigned an oxidation state of -1; H2O2.
5. In binary compounds the element with the greater attraction for electrons in the bond is
assigned a negative oxidation state equal to its charge in its ionic compounds. For example, F
is always -1. N is usually -3, therefore in NH3, H is +3.
6. The sum of the oxidation states must be zero for all electrically neutral compounds and must
be equal to the overall charge for an ionic species. For example, the sum of the oxidation
states of H and O in water is 0; sum of oxidation states for C and O atoms in CO3 2- is -2.
Attraction for electrons
F>O>N=Cl
Sometimes oxidation state can be a fraction
Fe3O4; 4(-2) = 8 8/3 for Fe
The Characteristics of Oxidation-Reduction Reactions
Characterized by transfer of electrons
Oxidation: an increase in oxidation (a loss of electrons)
Reduction: a decrease in oxidation state (a gain of electrons)
LEO GER
2Na + Cl2 2NaCl
Sodium goes from 0 to +1; oxidized
Chlorine goes from 0 to -1; reduced
Oxidizing agent: electron acceptor
Reducing agent: electron donator.
Whole compound is specified as agent
4.11: Balancing Oxidation-Reduction Equations
Two methods
Oxidation state
reaction method
Oxidation States Method
Find the coefficients for the reactants that will make the total increase in oxidation state balance
the total decrease.
Assign the oxidation states of all atoms
Decide which element is oxidized and determine the increase in oxidation state
Decide which elements is reduced and determine the decrease in oxidation state
Choose coefficients for the species containing the atom oxidized and the atom reduced such that
the total increase in oxidation state equals the total decrease in oxidation state
Balance the remainder of the equation by inspection
Half-Reaction Method
Separate the reaction into 2 half-reactions, one involving oxidation and the other reduction.
Balancing redox Eq. in Acid soln. using half-reaction Method
Write the equations for the oxidation and reduction half-reactions
For each half-reaction

o Balance all the elements except hydrogen and oxygen

o Balance oxygen using H20
o Balance hydrogen using H+
o Balance the charge using electrons
If necessary, multiply one or both balanced half-reactions by integers to equalize the number of
electrons transferred in the two half-reactions.
Add the half-reactions, and cancel identical species
Check to be sure that the elements and charges balance.
Balancing Redox. Eq. in Basic sol. Using half-reaction Method
Use the half-reaction method as specified for acidic solutions to obtain the final balanced
equation as if H+ ions were present.
To both sides of the equation obtained by the procedure above, add the number of OH- ions that
is equal to the number of H+ ions.
Form H2O on eh side containing both H+ and OH- ions and eliminate the number of H2O
molecules that appear on both sides of the equation.
Check that the elements and charges balance.
4.12: Simple Oxidation-Reduction Titrations
Used for volumetric analysis
Most frequently used oxidizing agents
Potassium permanganate (KMnO4), Potassium dichromate (K2Cr2O7); cerium hydrogen
sulfate (Ce(HSO4)4)
Potassium permanganate
MnO4- + 8H+ + 5e- Mn2+ + 4H2O
Permanganate is intensely purple (can act as own indicator)
As long as some reducing agent remains in solution, the solution remains colorless.
When all the reducing agent has been consumer, the next drop of permanganate titrant
will turn the solution light purple. The endpoint thus occurs one drop beyond the
stoichiometric point.