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Advanced Chemistry

Types of Chemical Reactions and Solution Stoichiometry

Water
The Common Solvent

Water as a Solvent
Bent (V-shaped) molecule

with 105 bond angle.

Covalent bonds electron

sharing between oxygen and hydrogen.


Unequal sharing of electrons

due to electronegativity differences cause water to be a polar molecule.

Water as a Solvent
Partial charges () form on

the water molecule due to the unequal sharing of electrons.


be a solvent for ionic compounds.

Waters polarity causes it to

Polar Water Molecules Interact with the Positive and Negative Ions of a Salt Assisting in the Dissolving Process

Solubility
Solubility of ionic substances in water varies

greatly.

Solubility depends on the relative

attractions of the ions and water molecules for each other.

Once dissolved, an ionic compound

becomes hydrated, therefore ions disperse independent of one another.

Solubility
Water will dissolve non-ionic substances

depending upon their structure.

If a polar bond exists within the

structure, the molecule can be subject to being water soluble. polar solvents and nonpolar substances dissolve in nonpolar solvents.

In general, polar substances dissolve in

An Ethanol Molecule Contains a Polar OH Bond Similar to Those in the Water Molecule

The Polar Water Molecule Interacts Strongly with the Polar-O-H bond in Ethanol

Nature of Aqueous Solutions

Strong and Weak Electrolytes

Strong and Weak Electrolytes


A solution in which a substance is

dissolved in water; the substance is the solute and the solvent is the water. electrical conductivity. Its ability to conduct an electric current.

A common property for a solution is

Strong and Weak Electrolytes


Pure water is not an electrical conductor. Strong electrolytes conduct current very

efficiently.

Weak electrolytes conduct only a small

current.
flow.

Nonelectrolytes do not allow current to

Electrical Conductivity of Aqueous Solutions

Svante Arrhenius
1859-1927 Studied the nature of solutions and

theorized that conductivity of solutions arose from the presence of ions. conductivity is directly related to the number of ions present in solution.

Proved that the strength of

Strong Electrolytes
Strong electrolytes are substances

that are completely ionized when they are dissolved in water. Soluble salts Strong acids Strong bases

NaCl Dissolves

Acids
Arrhenius discovered in his studies of

solutions that when acids were dissolved in water they behaved as strong electrolytes. This result was directly related to an acids ability to ionize in water. H+ ions when it is dissolved in water.

An Acid is a substance that produces

HCl is Completely Ionized

Acids

HCl H
HNO3 H
H 2 SO4 H
H O 2 u u u u u x

H O 2 u u u u u x

( aq )

Cl

( aq )
3( aq )
4( aq )

H O 2 u u u u u x

( aq )
( aq )

NO

HSO

An Acid is a substance that produces H+ ions when it is dissolved in water.

Acids

HCl H
HNO3 H
H 2 SO4 H
H O 2 u u u u u x

H O 2 u u u u u x

( aq )

Cl

( aq )
3( aq )
4( aq )

H O 2 u u u u u x

( aq )
( aq )

NO

HSO

In conductivity studies, virtually every molecule ionizes. Therefore, strong electrolytes are strong acids.

Strong Acids
Sulfuric acid, nitric acid and hydrochloric

acid are aqueous solutions and should be written in chemical equations as such.
dissociates into its ions. In aqueous solutions, the HCl molecule does not exist. molecule. Only the first H+ ion completely dissociates. The anion HSO4- remains partially intact.

A strong acid is one that completely

Sulfuric acid can produce two H+ ions per

Strong Bases
Bases are soluble ionic compounds

containing the hydroxide ion (OH-). and these compounds ionize completely in water.

Strong bases are strong electrolytes

Strong Bases

NaOH ( s ) Na KOH ( s ) K
H2O

H2O

( aq )

OH

( aq )

( aq )

OH

( aq )

An Aqueous Solution of Sodium Hydroxide

Weak Electrolytes
Weak electrolytes are substances that

exhibit a small degree of ionization in water. They produce relatively few ions when dissolved in water Most common weak electrolytes are weak acids and weak bases.

Weak Acids
HC2 H 3O2( aq ) H 2 O(l ) H O C H O 3 (aq ) 2 3 2( aq )

Formulas for acids are often written with

the acidic hydrogen atom or atoms (the hydrogen atoms that will produce H+ ions in solution) listed first. If any nonacidic hydrogens are present they are written later in the formula.

Weak Acids
HC2 H 3O2( aq ) H 2 O(l ) H O C H O 3 (aq ) 2 3 2( aq )

In Acetic acid, only 1% of its molecules

ionize.

The double arrow indicates that the

reaction can occur in either direction. therefore a weak acid because it dissociates (ionizes) only to a slight extent in aqueous solutions.

Acetic acid is a weak electrolyte and

Acetic Acid (HC2H3O2)

Weak Bases
The most common weak base is NH3.
In an aqueous solution, ammonia results

in a basic solution.

NH 3(aq) H 2O(l ) NH 4(aq) OH(aq )

The Reaction of NH3 in Water

Nonelectrolytes
Nonelectrolytes are substances that

dissolve in water but do not produce any ions.

Concentration:

The Composition of Solutions

Solutions
Most chemical reactions take place in the

environment of solutions. In order to perform stoichiometric calculations in solutions, one must know two things. The nature of the reaction; which depends on the exact forms the chemicals take when dissolved. The amounts of the chemicals present in the solutions, usually expressed as concentrations.

Concentration
Molarity (M) is moles of solute

per volume of solution in liters:

moles of solute M molarity liters of solution


Example: 1.0M= 1.0 molar = 1.0moles solute/1liter of solution

Example
Calculate the molarity of a solution

prepared by dissolving 11.5g of solid NaOH in enough water to make 1.50L of solution.
.192 M NaOH

Example
Calculate the molarity of a solution

prepared by dissolving 1.56g of gaseous HCl in enough water to make 26.8 ml of solution. 1.60M HCl

Example
Give the concentration of each type

of ion in 0.50M Co(NO3)2.

Co2+ = 0.50 M Co2+ NO3- = 1.0 M NO3-

Example
Calculate the number of moles of Cl-

ions in 1.75L of 1.0 x 10-3 M ZnCl2.

3.5 x 10-3 mol Cl-

Dilution
The process of changing the molarity of a

solution from a more concentrated solution to a lesser concentrated solution. Moles of solute after dilution = moles of solute before dilution. M x V= moles M1V1=M2V2

Example
What volume of 16M sulfuric acid must

be used to prepare 1.5L of 0.10 M H2SO4 solution?

9.4 ml solution

Steps Involved in the Preparation of a Standard Aqueous Solution

Types of Chemical Reactions

Types of Solution Reactions


Most solution reactions can be
Precipitation Reactions
Acid-Base Reactions Oxidation-Reduction Reactions

put into three types of reactions:

Precipitation Reactions
When two solutions are mixed, an

insoluble substance sometimes forms; that is, a solid forms and separates from the solution. The solid that forms is called a precipitate.

Precipitation Reaction Example


K 2CrO4( aq ) Ba( NO3 )2( aq )
A more accurate representation is:

2K

( aq )

CrO

2 4( aq )

Ba

2 ( aq )

2 NO

3( aq )

Reactant Solutions

Solution PostReaction

Precipitation Reaction Example


2 2 2K(aq ) CrO4( Ba 2 NO aq ) ( aq ) 3( aq )

We look at all the possible combinations of the ions to check for compounds that form solids. K2CrO4 KNO3 BaCrO4 Ba(NO3)2

Precipitation Reaction Example


2 2 2K(aq ) CrO4( Ba 2 NO aq ) ( aq ) 3( aq )

Two of these combinations are the reactants and can be ruled out: K2CrO4 KNO3 BaCrO4 Ba(NO3)2

Solubility
Predicting the identity of a solid product in a

precipitation reaction requires knowledge of the solubilities of common ionic substances.


Slightly soluble the tiny amount of solid that

dissolves is not noticeable. The solid appears insoluble to the naked eye. Insoluble and slightly soluble are often used interchangeably.

Simple Rules for the Solubility of Salts in Water

Precipitation Reaction Example


2 2 2K(aq ) CrO4( Ba 2 NO aq ) ( aq ) 3( aq )

Two of these combinations are the reactants and can be ruled out: K2CrO4 KNO3 BaCrO4 Ba(NO3)2

Precipitation Reactions
Precipitation reactions move forward

due to the decrease in energy state of the compound. Bonds forming in the compound increase stability and push the reaction forward.

Solutions

Describing Reactions in

Formula Equation
Although the formula equation shows

the reactants and products of the reaction, it does not give a correct picture of what actually occurs in solution.
Gives the overall reaction

stoichiometry but not necessarily the actual forms of the reactants and products.

Complete Ionic Equation


The complete ionic equation better

represents the actual forms of the reactants and products in solution. All substances that are strong electrolytes are represented as ions. Complete ionic equation shows all ions in a reaction, even those that do not participate in the reaction. These ions are called spectator ions.

Net Ionic Equation


The net ionic equation includes only

those solution components that are directly involved in the reaction. Commonly used because it gives the actual forms of the reactants and products and includes only the species that undergo a change. Spectator ions are not included.

Example Problem
For the following reaction, write the formula

equation, the complete ionic equations, and the net ionic equation. Aqueous potassium chloride is added to aqueous silver nitrate to form a silver chloride precipitate plus aqueous potassium nitrate.
KCl(aq) AgNO3(aq ) AgCl( s ) KNO 3(aq )

K(aq ) Cl(aq ) Ag(aq ) NO3( AgCl K NO (s) ( aq ) 3( aq ) aq )

Cl ( aq ) Ag

( aq )

AgCl( s )

Stoichiometry

of Precipitation Reactions

Solution Stoichiometry
The rules of stoichiometry and limiting

reactant apply to chemical reactions in solutions. But two rules need special emphasis. Always write a balanced equation of the reaction and give special attention to the products that are formed and the true form of the ions in solution. Moles must still be calculated, but molarity and volume must be used in the calculation.

Determining the Mass of Product Formed

Example Problem
Determine the mass of solid NaCl that must be

added to 1.50L of a 0.100 M AgNO3 solution to precipitate all the Ag+ ions in the form of AgCl.

Ag( aq ) Cl

( aq )

AgCl ( s )

Determine the amount of Ag+ ions in solution.


0.100 M Ag 1.50 L x .15 molesAg 1L

Determine the amount of Cl- needed to react with Ag+


.15 molesAg 1Cl 1NaCl 58.44 g x x x 8.77 gNaCl 1Ag 1Cl 1mole

Steps to Solution Stoichiometry


1. Identify the species present in the combined solution,

and determine what reaction occurs.


reaction.

2. Write the balanced net ionic equation for the 3. Calculate the moles of reactants. 4. Determine which reactant is limiting. 5. Calculate the moles of product or products, as

required.

6. Convert to grams or other units, as required.

Reactions

Acid-Base

Acids
Arrheniuss concept of acids and bases:

An acid is a substance that produces H+ ions when dissolved in water and a base is a substance that produces OH- ions. Fundamentally correct but doesnt include all bases.

Brnsted-Lowry Acids
Johannes Brnsted (1879-1947) and

Lowry (1874-1936) gives a more general definition of a base that includes substances that do not contain OH-. An acid is a proton donor. A base is a proton acceptor.

Acid-Base Reactions
An Acid-Base reaction often forms two

things: A salt (sometimes soluble) Water Since water is a nonelectrolyte, large quantities of H+ and OH- cannot coexist in solution. The net ionic equations is:

( aq )

OH

( aq )

H 2O(l )

Acid-Base Reactions
When a strong acid and a strong base

react, we expect both substances to completely ionize. We then check to see what will form that is soluble.

HCl( aq ) NaOH ( aq ) NaCl( aq ) H 2O(l ) H (aq ) Cl(aq ) Na(aq ) Cl(aq ) Na(aq ) Cl(aq ) H 2O(l ) H (aq ) OH (aq ) H 2O(l )
In this case, the salt is soluble and remains as ions. But water, a nonelectrolyte, will form since H+ and OH- have a strong attraction for each other and do not ionize.

Acid-Base Reactions
When a weak acid and a strong base react, the weak acid usually doesnt ionize. However, the hydroxide ion is such a strong base that for the purposes of stoichiometric calculations it can be assumed to react completely with any weak acid.
HC2 H 3O2( aq ) KOH ( aq ) OH (aq ) HC2 H 3O2( aq ) H 2O(l ) C2 H 3O2( aq )

Performing Calculations for Acid-Base Reactions


1. List the substances present in the combined

solution before any reaction occurs and decide what reaction will occur. this reaction.

2. Write the balanced net ionic equation for

3. Calculate the moles of reactants. For

reactions in solution, use the volumes of the original solutions and their molarities.

Performing Calculations for Acid-Base Reactions


4. Determine the limiting reactant where

appropriate.

5. Calculate the moles of the required

reactant or product.
required.

6. Convert to grams or volume (of solution), as

Acid-Base Reaction
An acid-base reaction is often called

a neutralization reaction.

When just enough base is added to

react exactly with the acid in a solution, we say the acid has been neutralized.

Step by Step Example


What volume of a .100 M HCl solution is

needed to neutralize 25.0ml of .350 M NaOH?

What ions are present? What are the possible reactions?

Na

( aq )

Cl

( aq )

NaCl( s )

H (aq ) OH (aq ) H 2O(l )

Example
What volume of a .100 M HCl solution is

needed to neutralize 25.0ml of .350 M NaOH?


NaCl is soluble. Na+ and Cl- are spectators. Write a balanced net ionic equation.

( aq )

OH

( aq )

H 2O(l )

Example
What volume of a .100 M HCl solution is

needed to neutralize 25.0ml of .350 M NaOH?


What are the moles of reactant present in solution?

1L 0.350 mol OH x x 1000 ml LNaOH 8.75 x10 3 molOH 25.0 ml NaOH

Example
What volume of a .100 M HCl solution is
How many moles of H+ are needed?

needed to neutralize 25.0ml of .350 M NaOH?

The mole ratio is 1:1

8.75 x10 molH

Example
What volume of a .100 M HCl solution is
What volume of HCl is required?

needed to neutralize 25.0ml of .350 M NaOH?

0.100 molH 3 Vx 8.75 x10 molH L 2 V 8.75 x10 L

Example
In a certain experiment, 28.0ml of 0.250 M HNO3

and 53.0ml of .320 M KOH are mixed. Calculate the amount of water formed in the resulting reaction. What is the concentration of H+ or OHions in excess after the reaction goes to completion?

H+ is limiting 7.00x10-3mol H2O .123 M OHexcess

Acid-Base Titrations
Volumetric analysis is a technique for

determining the amount of a certain substance by doing a titration.

A titration involves delivery (from a buret)

of a measured volume of a solution of known concentration (the titrant) into a solution containing the substance being analyzed (the analyte).

Acid-Base Titrations
The point in the titration where enough

titrant has been added to react exactly with the analyte is called the equivalence point or the stoichiometric point. a substance added at the beginning of the titration that changes color at the equivalence point.

This point is often marked with an indicator,

Acid-Base Titrations
The point at which the indicator actually

changes color is called the endpoint of the titration. accurately the concentration of a solution is called standardizing the solution.

The procedure for determining

Indicators
A common indicator for acid-base

titrations is phenolphthalein, which is colorless in an acidic solution and pink in a basic solution.

Example
A student carries out an experiment to standardize a

sodium hydroxide solution. To do this, the student weighs out a 1.3009g sample of potassium hydrogen phthalate (KHC8H4O4 or KHP). KHP (molar mass 204.22g/mol) has one acidic hydrogen. The student dissolves the KHP is distilled water, add phenolphthalein as an indicator, and titrates the resulting solution with the sodium hydroxide solution to the phenolphthalein endpoint. The difference between the final and initial buret readings indicate that 41.20 ml of the sodium hydroxide solution is required to react exactly with the 1.3009g KHP. Calculate the concentration of the sodium hydroxide solution.

Example
1.3009g KHP, molar mass = 204.22g/mol 41.20 ml NaOH solution to neutralize KHP Calculate concentration of NaOH KHP has 1 acidic hydrogen so it should react in a 1 to 1

ratio:

KHC8 H4O4(aq) NaOH(aq) H2O(l ) C H O K Na

2 8 4 4(aq )

(aq )

(aq )

.1546 M

Reactions

OxidationReduction

Oxidation and Reduction


Oxidation Reduction reactions transfer

one or more electrons from one species to another. Called Redox reactions. Common and important type of reaction: photosynthesis, energy production and combustion

Oxidation States
Also called oxidation numbers provides a

way to keep track of electrons in oxidationreduction reactions. In a covalent compound when electrons are shared, oxidation numbers are based on the relative electron affinity of the elements involved.

Oxidation States
In a covalent compound: If the bond is between two identical

atoms, the electrons are divided equally. If the bond is between different atoms, the electrons are divided based on electron attraction.

Oxidation State Example


H2O Total electrons: 4 O has more electronegativity and

maintains a -. Therefore O is assumed to have taken both electrons, one from each of the Hydrogens. H has an oxidation state of +1 (each) O has an oxidation state of -2

Oxidation States
The sum of the oxidation states must

be zero for an electrically neutral compound.

The sum of the oxidation states must

equal the charge of the ion. Ion charges are written as n+ or n-, while oxidation numbers are written +n or -n

Examples
CO2
SF6 NO3-

C +4, O -2
S +6, F -1 N +5, O -2

Non- Integer Example


Fe3O4

Oxygen is assigned first, -2


Giving Fe a +8/3 state Acceptable because all Fe

is assumed to have the same charge within the compound. But the compound actually contains two Fe3+ ions and one Fe2+ ion.

Redox Reactions
Characterized by a transfer of electrons

2 Na( s ) Cl2( g ) 2 NaCl( s )

CH 4( g ) 2O2( g ) CO2( g ) 2 H 2O(l )

Redox Reactions
CH 4( g ) 2O2( g ) CO2( g ) 2 H 2O(l )
C -4

C +4 Carbon loses 8 electrons Increase in oxidation state is Oxidation O -2 Oxygen gains 8 electrons: 4 (-2) = -8 Decrease in oxidation state is Reduction

O 0

Redox Reactions
CH 4( g ) 2O2( g ) CO2( g ) 2 H 2O(l )
C -4

C +4 Carbon is Oxidized Oxygen gas is the oxidizing agent O -2 Oxygen is Reduced Methane is the reducing agent.

O 0

Example
Metallurgy, the process of producing a metal from its

ore, always involves oxidation-reduction reactions. In the metallurgy of galena (PbS), the principal leadcontaining ore, the first step is the conversion of lead sulfide to its oxide (a process called roasting):

2PbS( s ) 3O2( g) 2PbO( s ) 2SO2( g )


The oxide is then treated with carbon monoxide to

produce the free metal:

PbO( s ) CO( g ) Pb( s ) CO2( g )


For each reaction, identify the atoms that are oxidized

and reduced, and specify the oxidizing and reducing agents.

Example
2PbS( s ) 3O2( g) 2PbO( s ) 2SO2( g )
Pb +2 S -2 O 0 Pb +2 S +4 O -2

Sulfur is oxidized and oxygen is reduced. Oxygen gas is the oxidizing agent and lead sulfide is the reducing agent.

Example
PbO( s ) CO( g ) Pb( s ) CO2( g )
Pb +2 O -2

Pb 0 O -2

C +2

C +4

Lead is reduced and carbon is oxidized. PbO is the oxidizing agent, and CO is the reducing agent.

Balancing

Oxidation-Reduction Equations

Balancing Redox Reactions


Two methods are normally used:
1. Balancing of Oxidation states 2. Separation of the reaction into two half-

reactions Normally used for more complex reactions

Oxidation States Balancing Method


We know that in a redox reaction we

must ultimately have equal numbers of electrons gained and lost, and we can use this principle to balance redox equations.

Balancing Redox Steps


1. Write the unbalanced equation.

2. Determine the oxidation states of all atoms.


3. Show electrons gained and lost.

4. Use coefficients to equalize the electrons

gained and lost.

5. Balance the rest of the equations by inspection.

6. Add appropriate states.

Example
2 H(aq) Cl(aq) Sn( s ) NO3( SnCl aq ) 6( aq ) NO2( g ) H 2O(l )

+1

-1

+5 -2

+4 -1

+4 -2

+1 -2

Note that hydrogen, chlorine, and oxygen do not change oxidation states and are not involved in electron exchange.
2 Sn( s ) NO3( SnCl aq ) 6( aq ) NO2( g )

+5 -2

+4 -1

+4 -2

Example
Sn( s ) NO
0
3( aq )

SnCl

2 6( aq )

NO2( g )
+4 -2

+5 -2

+4 -1

Tin lost 4 electrons and each Nitrogen gained 1 electron. Therefore each nitrogen must have a coefficient of 4.

H Cl Sn 4 NO3 SnCl6 4 NO2 H 2O


Balance the rest as usual
2 8 H(aq ) 6Cl(aq ) Sn( s ) 4 NO3( SnCl aq ) 6( aq ) 4 NO2( g ) 4 H 2O(l )

END

The

Figure 4.11a-b Measurin g Pipets and Volumetri c Pipets Measure Liquid Volume

Figure 4.12a-c A Measuring Pipet is Used to Add Acetic Solution to a Volumetric Flask

Figure 4.15 a&b The Reaction of K2CrO4 and Ba(NO3)2

Figure 4.17 Molecular-Level Representations Illustrating the Reaction of KCl (aq) with AgNO3 (aq) to Form AgCl (s)

Determini ng the Mass of Product Formed

Performing Calculatio ns for Acid-Base Reactions

Neutralizat ion Reactions I

Neutralizat ion Reactions II

Neutralizati on Titration

Figure 4.19 The Reaction of Solid Sodium and Gaseous Chlorine to Form Solid Sodium Chloride

Figure 4.20 A Summary of OxidationReduction Process

The Half-Reaction Method (Acidic Solution)

The Half-Reaction Method (Basic Solution)

Figure 4.4a-c Electrical Conductivity of Aqueous Solutions

An Aqueous Solution of Co(NO3)2.

Figure 4.10 Steps Involved in the Preparation of a Standard Aqueous Solution

Yellow Aqueous Potassium

Figure 4.14a-b Reactant Solutions

Figure 4.16 Addition of Silver Nitrate to Aqueous Solution of Potassium Chloride

Figure 4.17 Reaction of KCI(aq) with AgNO3(aq) to form AgCI(s).

Lead Sulfate

KOH and Fe(NO3)3 Mix to Create Solid Fe(OH)3.

Figure 4.18a-c The Titration of an Acid with a Base

Figure 4.19 The Reaction of Solid Sodium and Gaseous Chlorine to Form Solid Sodium Chloride

Oxidation of Copper Metal by Nitric Acid

Magnetite

Aluminum and Iodine Mix to Form Aluminum Iodide

Chocolate

When Potassium Dichromate Reacts with Ethanol, the Solution Contains Cr3+.

Table 4.2 Rules for Assigning Oxidation States

The End