CHM 1045 FALL 2001

Chemistry: A Molecular Approach, 1st Ed. Nivaldo Tro

Chapter 4 Palmer Graves, Instructor

Chapter 4 Chemical Quantities and Aqueous Reactions

2008, Prentice Hall

4.1 Determine the amount one reactant needed to react with another reactant and to the amount of product produced in a reaction. (in moles, grams, and # of particles) [Reading 4.1-4.2 Problems 25-36]

Mole to Mole Calculations

Calculate the mass of NH3 produced from the reaction of .365 g of hydrogen in excess nitrogen.

CHM 1045 FALL 2001

Chapter 4 Palmer Graves, Instructor

Correct Conversion Pathway

Calculations & Equations

__NH3(g) + __O2(g) ! __H2O(l) + __N2(g) (a) 3 moles of NH3 will produce ? moles N2? (b) 1.7 g of NH3 will produce ? moles H2O? (c) 1.6 g of O2 will produce ? grams H2O?

Example Estimate the mass of CO2 produced in 2004 by the combustion of 3.4 x 1015 g gasoline
assuming that gasoline is octane, C8H 18, the equation for the reaction is: 2 C8H 18(l ) + 25 O2 (g) ! 16 CO2 (g) + 18 H2 O(g) the equation for the reaction gives the mole relationship between amount of C8H 18 and CO2 , but we need to know the mass relationship, so the Concept Plan will be:

g C8H18

mol C8H18

mol CO2

g CO2

CHM 1045 FALL 2001

Example Estimate the mass of CO2 produced in 2004 by the combustion of 3.4 x 1015 g gasoline
Given: Find: Concept Plan: 3.4 x 1015 g C8 H 18 g CO2 g C8H 18 mol C8H18 mol CO2 g CO2

Chapter 4 Palmer Graves, Instructor

Relationships: 1 mol C8H18 = 114.22g, 1 mol CO2 = 44.01g, 2 mol C8H 18 = 16 mol CO2 Solution:

Check:

Practice
According to the following equation, how many milliliters of water are made in the combustion of 9.0 g of glucose? C6H12O6(s) + 6 O2(g) ! 6 CO2(g) + 6 H2O(l)
! " convert 9.0 g of glucose into moles (MM 180) # " convert moles of glucose into moles of water $ " convert moles of water into grams (MM 18.02) % " convert grams of water into mL
& ' How? what is the relationship between mass and volume? density of water = 1.00 g/mL

Practice
According to the following equation, how many milliliters of water are made in the combustion of 9.0 g of glucose? C6H12O6(s) + 6 O2(g) ! 6 CO2( g) + 6 H2 O(l)

CHM 1045 FALL 2001

Chapter 4 Palmer Graves, Instructor

Example Problem
Laundry Bleach is prepared by reacting sodium hydroxide with chlorine gas according to the reaction:
2 NaOH (aq) + Cl2 (g) ! NaOCl (aq) + NaCl (aq) + H2O(l)

How much (g) of NaOH would be required to react with 12.563 g of Cl2 (g) How much NaOCl would be produced?

4.2 Calculate the percent yield of a reaction [Reading 4.3 ]

Assumptions in Stoichiometry
1. All reactions go to completion 2. There are ample quantities of all reactants 3. Only the main reaction takes place These assumptions are rarely true

CHM 1045 FALL 2001

Chapter 4 Palmer Graves, Instructor

Percent Yield
Stoichiometry gives the theoretical amount of product produced by a reaction Actual yield is usually measured

Example
Aspirin can be made according to the following reaction
C7H 6O3(s) + C4 H 6 O 3 (l) > C9H 80 4(S) + CH3CO2H(l) salicylic acid+ acetic anhydride > aspirin acetic acid

You begin with 14.4 g of salicylic acid and excess acetic anhydride 6.26g of aspirin are produced Calculate the percent yield

4.3 Identify the limiting and excess reactants in a reaction mixture , determine the mass of excess reactant remaining at the end of a reaction and the mass of product(s) produced [Reading 4.3 Problems 37 - 48]

CHM 1045 FALL 2001

Chapter 4 Palmer Graves, Instructor

Limiting Reactant
Suppose you had 10 bicycle wheels and 50 frames. How many bicycles could you produce? One frame yields one bicycle, thus, 50 bicycles? The amount of wheels limits the number of bicycles which can be produced! How many excess frames are there?

Limiting Reactant
2AgNO3(aq) + K2CrO4(aq) ! Ag2CrO4(s) + 2KNO3 (aq)
AgNO3 is limiting K2CrO4 is limiting

Click picture to play movie.

Limiting Reactant - The reactant that is completely consumed limits the amount of product formed.

Calculations & Equations

__NH3(g) + __O2(g) ! __H2O(l) + __N2(g) 4NH3(g) + 3O2(g) ! 6H2O(l) + 2N2(g) (d) 2 moles of NH3 and 3 moles of O2 will produce ? moles N2? (e) 5.0 g of NH3 and 5.0 g of O2 will produce ? g of H2O? How many H2O molecules?

CHM 1045 FALL 2001

Chapter 4 Palmer Graves, Instructor

Limiting Reactant

Example Problem
Suppose you add 125g of C and 125g of Cl2 to an excess amount of TiO2, how much TiCl4 can be produced according to the following reaction.
TiO2(s) + 2 Cl2(g) + C(s) > TiCl4(l) + CO2 (g)

Step 1: Calculate the moles of product formed from each reactant Step 2: The lesser number is the maximum product.

Practice How many grams of N2(g) can be made from 9.05 g of NH3 reacting with 45.2 g of CuO? 2 NH3(g) + 3 CuO(s) ! N2(g) + 3 Cu(s) + 3 H2 O(l)

CHM 1045 FALL 2001

Practice How many grams of N2(g) can be made from 9.05 g of NH3 reacting with 45.2 g of CuO? 2 NH3(g ) + 3 CuO( s) ! N2( g) + 3 Cu(s) + 3 H2 O(l ) Given: Find: 9.05 g NH3, 45.2 g CuO g N2 mol NH3 mol N2 g N2

Chapter 4 Palmer Graves, Instructor

Concept Plan: g NH 3

g CuO

mol CuO

mol N2

g N2

Relationships:

1 mol NH3 = 17.03g, 1 mol CuO = 79.55g, 1 mol N2 = 28.02 g 2 mol NH3 = 1 mol N2, 3 mol CuO = 1 mol N2

Practice How many grams of N2(g) can be made from 9.05 g of NH3 reacting with 45.2 g of CuO? 2 NH3(g ) + 3 CuO( s) ! N2( g) + 3 Cu(s) + 3 H2 O(l ) Solution:

Check:

Example Problem
Methanol is produced according to the following reaction CO(g) + 2 H2(g) > CH3OH(l) If 356g CO are mixed with 65.0g hydrogen, how much methanol can be produced? What is the limiting reagent.? How much of the excess remains after the reaction?

CHM 1045 FALL 2001

Chapter 4 Palmer Graves, Instructor

4.4 Describe how to prepare a solution of known molarity by dissolving a solid in a solvent and by diluting a more concentrated solution [Reading 4.4 Problems 49 - 58]

Concentrations
It is convenient to measure amounts of dissolved materials by volume of the solution. Concentration: a measure of how much solute dissolved in what amount of solvent or solution. Most common concentration unit in chemistry: Molar Unit = M = # moles solute/# L solution

Problem
H2O

250 mL volumetric flask

What is the concentration of a solution made by dissolving 55.3 g of Cu(NO3)2 in enough water to make 250 mL of solution?

CHM 1045 FALL 2001

Example 4.5 Find the molarity of a solution that has 25.5 g KBr dissolved in 1.75 L of solution
Sort Information Strategize Given: Find: Concept Plan: 25.5 g KBr, 1.75 L solution Molarity, M
g KBr mol KBr L soln M

Chapter 4 Palmer Graves, Instructor

Relationships: Follow the Concept Plan to Solve the problem Check Solution:

1 mol KBr = 119.00 g, M = moles/L

Check: since most solutions are between 0 and

18 M, the answer makes sense

Example 4.6 How many liters of 0.125 M NaOH contains 0.255 mol NaOH?
Sort Information Strategize Given: 0.125 M NaOH, 0.255 mol NaOH Find: liters, L Concept Plan:
mol NaOH L soln

Relationships: Follow the Concept Plan to Solve the problem Check Solution:

0.125 mol NaOH = 1 L solution

Check: since each L has only 0.125 mol NaOH,

it makes sense that 0.255 mol should require a little more than 2 L

Problem

How would you make 150 mL of a 2.70 M solution of NaC2H3O2?

CHM 1045 FALL 2001

Chapter 4 Palmer Graves, Instructor

Dilution
solutions are often described as dilute or concentrated dilute solutions - a lot of solvent compared to particles concentrated solutions small amount of solvent compared to particles Adding solvent changes the concentration

Dilution Problems
# moles solute before dilution = # moles solute after dilution # moles = M V

MiVi = MfVf

How much water needs to be added to 100mL of a 0.400 M NaBr(aq) solution to make a 0.100 M solution?

Dilution Problems
Calculate the concentration of a HCl solution when 25.0 ml of water is added to 30.0 ml of a 0.05M HCl solution How much water would you need to add to 10.0 ml of a 16.0 M solution in order to make a 0.050 M HCl solution?

CHM 1045 FALL 2001

Chapter 4 Palmer Graves, Instructor

Working with Molarity

Calculate the moles of chloride ions contained in 25.00 mL of a .0500 M copper(II) chloride solution

4.5 Determine the volume of one reactant solution needed to react with a given volume of a second reactant solution. [Reading 4.4 Problems 59-62]

Solution Stoichiometry
since molarity relates the moles of solute to the liters of solution, it can be used to convert between amount of reactants and/or products in a chemical reaction

CHM 1045 FALL 2001

Example 4.8 What volume of 0.150 M KCl is required to completely react with 0.150 L of 0.175 M Pb(NO3)2 in the reaction 2 KCl(aq) + Pb(NO3)2(aq) ! PbCl2(s) + 2 KNO3(aq)
Sort Information Strategize
Given: Find: Concept Plan:
L Pb(NO3)2

Chapter 4 Palmer Graves, Instructor

0.150 M KCl, 0.150 L of 0.175 M Pb(NO3)2 L KCl

mol Pb(NO3)2 mol KCl L KCl

Relationships:

1 L Pb(NO3)2 = 0.175 mol, 1 L KCl = 0.150 mol, 1 mol Pb(NO3) 2 = 2 mol KCl

Follow the Concept Plan to Solve the problem Check

Solution:

Check:

since need 2x moles of KCl as Pb(NO3 ) 2, and the molarity of Pb(NO3 ) 2 > KCl, the volume of KCl should be more than 2x volume Pb(NO3)2

Solution Stoichiometry
What is the molarity of a HClO3 solution if 45.36 mL is needed to completely react with 51.53 mL of a 0.0945 M NaOH solution. HClO3 + NaOH ! H2O + NaClO3

4.6. Identify and distinguish between precipitation, acid-base, and redox reactions [Readings 4.5-4.9]

CHM 1045 FALL 2001

Chapter 4 Palmer Graves, Instructor

Precipitation Reaction
A reaction between solutions in which a solid product drops out of the solution combining of a cation and an anion
Pb(NO3) 2 (aq) + 2KI(aq) ! PbI2 (s) + 2KNO3 (aq)

Acid-Base Neutralization
An acid and a base react to produce water and a salt
2HCl (aq) + Ca(OH)2(aq) ! 2H2O(l) + CaCl2(aq)

The acid produces H+ OH comes from the base Produces water, thus, neutralization

Redox Reactions
Reactions in which an electron or electrons are transferred from one species to another More on this later

CHM 1045 FALL 2001

Chapter 4 Palmer Graves, Instructor

4.7 Classify substances as electrolytes or non electrolytes [Readings4.2 Problems 2, 3, & 36-39]

Electrolytes
Dissociation - ionic compounds dissolve to yield SEPARATE ions in solution The solutions will conduct electricity

Testing Conductivity of Aqueous Solutions

Click pictures to view animations

Animation of Cond. Tester

electrolyte

CHM 1045 FALL 2001

Chapter 4 Palmer Graves, Instructor

Electrolytes and Nonelectrolytes

Solutes which yield electrically conducting solutions are called electrolytes Dissociation - ionic compounds dissolve in water to yield separate ions in solution. Strong electrolyte- when dissociation is complete Weak electrolyte - a significant amount of non-dissociated compound is present Nonelectrolyte - dont conduct electricity

Weak Electrolytes
Weak electrolytes do not dissociate completely Therefore, the number of conducting ions is lower than a strong electrolyte

Weak Electrolytes
Dissociation is incomplete CH3COOH + H2O " H3O+ + CH3COO All three species exist in solution

CHM 1045 FALL 2001

Chapter 4 Palmer Graves, Instructor

Non-electrolytes
Nonelectrolytes do not release ions in solution Do not conduct Do they dissolve? Do they dissociate?

Solutions of Electrolytes & Nonelectrolytes

Dissociation of an ionic compound as it dissolves in water. Hydrated ions more freely in solution making solution able to conduct electricity.

Molecular compounds dissolve in water as intact molecules. Solutions of molecular compounds are nonelectrolytes which cant conduct electricity.

Electrolytes vs. Nonelectrolytes

CHM 1045 FALL 2001

Chapter 4 Palmer Graves, Instructor

4.8 Predict whether a precipitate will form and identify the precipitate when aqueous solutions are mixed [Readings 4.5 - 4.6 Problems 63-70]

Soluble Cations
Solutions made of salts containing these cations are almost always soluble

Group 1A cations & NH4+

Soluble Anions
Solutions made of salts containing these anions are almost always soluble This table is more complete than the information in the book

Nitrate Chlorate Perchlorate Acetate

NO3 ClO3 ClO4 CH3CO2

CHM 1045 FALL 2001

Chapter 4 Palmer Graves, Instructor

Solubility Rules
Halide salts are soluble Cl Br I

Exceptions! Salts with the following cations Ag+ Pb2+ Hg22+ [mercury(I)]

Solubility Rules
Sulfate salts (SO42) are usually soluble Exceptions!

Exceptions! Sulfate salts of Ca2+,Sr2+, Ba2+ Pb2+ Ag+

Salts that are NOT Soluble

Carbonate CO32 Phosphate PO43 Oxalate C 2O42 Chromate CrO42 Sulfide S 2 Most hydroxides OH Exceptions !! Salts of Group IA metals NH4+ salts Salts of Ca2+, Ba2+, Sr2+

CHM 1045 FALL 2001

Chapter 4 Palmer Graves, Instructor

Predicting Precipitation reactions

Write the ionic equation for the reaction of lead(II) nitrate and sodium chloride. What species would be the precipitate

Predicting Precipitation reactions

Write the ionic equation for the reaction of lead(II) nitrate and sodium chloride. What species would be the precipitate Pb2+ + NO3 + Na+ + Cl ! ?

Practice with the concept

Predict which of the following combinations would produce a precipitate and name the precipitate. Mixing NaCl with Ba(NO3)2 Mixing lead(II) acetate with sodium bromide Calcium chloride with sodium sulfide Potassium nitrate with ammonium carbonate

CHM 1045 FALL 2001

Chapter 4 Palmer Graves, Instructor

4.9 Write molecular, ionic, and net ionic equations for precipitation, acid-base, and redox reactions [Readings 4.7 Problems 71-74]

Electrolytes Salts
Dissociation - ionic compounds dissolve to yield SEPARATE ions in solution

Dissociation Equations
Equations show solid phase and dissolved phase. KBr (s) ! K+ (aq) + Br (aq) Na2CO3 (s) ! 2 Na+ (aq)+ CO32-(aq)

CHM 1045 FALL 2001

Chapter 4 Palmer Graves, Instructor

Practice
Write the dissociation equations for the dissolving of the following salts. MgCl2 Calcium phosphate Sodium hypochlorite

Practice with the concept

Sodium sulfite reacts with barium nitrate to produce solid barium sulfite. Write the molecular equation for the reaction.

Practice with the concept

Sodium sulfite reacts with barium nitrate to produce solid barium sulfite. Write the ionic equation for the reaction.

CHM 1045 FALL 2001

Chapter 4 Palmer Graves, Instructor

Practice with the concept

Sodium sulfite reacts with barium nitrate to produce solid barium sulfite. Write the net ionic equation for the reaction.

4.10 Identify common strong acids and bases and write a balanced equation, ionic equation, and net ionic equation for a neutralization reaction [Readings 4.8 Problems 75-82]

Defining acids and bases

Arrhenius definition of acid/base theory An acid is any substance which delivers an H+ in solution
H+ really exists as H3O+ in aqueous solutions (hydronium ion)

A base is any substance which delivers an OH in solution.

CHM 1045 FALL 2001

Chapter 4 Palmer Graves, Instructor

Memorize 7 Strong Acids

HCl HBr HI HClO3 HClO4 HNO3 H2SO4 Hydrochloric acid Hydrobromic acid Hydroiodic acid Chloric acid Perchloric acid Nitric acid Sulfuric acid

Memorize 4 Strong Bases

Metal hydroxides
NaOH KOH Ca(OH)2

Metal hydroxides
Sodium hydroxide Potassium hydroxides Calcium hydroxide

Metal hydrides
NaH KH CaH2

Metal hydrides
Sodium hydride Potassium hydride Calcium hydride

Memorize 4 Strong Bases

Metal amides
NaNH2 KNH2 Ca(NH2)2

Metal amides
Sodium amide Potassium amide Calcium amide

Metal oxides
Na2O K2O CaO

Metal hydrides
Sodium oxide Potassium oxide Calcium oxide

CHM 1045 FALL 2001

Chapter 4 Palmer Graves, Instructor

Strong Acids and Strong Bases

HCl (aq)
Base ! #+ (aq) + Cl (aq)

KOH (aq)

! $+ (aq) + OH (aq)

Acid Base Neutralization

Acids react with bases to produce a neutral solution neither acid nor base Produces water and a salt Complete equation

Acid Base Neutralization

Acids react with bases to produce a neutral solution neither acid nor base Complete equation HCl(aq) + NaOH(aq) ! H2O(l) + NaCl (aq)

CHM 1045 FALL 2001

Chapter 4 Palmer Graves, Instructor

Acid Base Neutralization

Acids react with bases to produce a neutral solution neither acid nor base Ionic equation H+ + Cl + Na+ +OH ! H2O + Na + + Cl

Acid Base Neutralization

Acids react with bases to produce a neutral solution neither acid nor base Net Ionic equation H+ + OH ! H2O (l)

Diprotic Acids
Some acids can donate more than one hydrogen ion e.g. H2SO4 and H3PO4 H2SO4 + 2 H2O ! 2 H3O++ SO42

CHM 1045 FALL 2001

Chapter 4 Palmer Graves, Instructor

Bases
Bases deliver OH in solution Metal hydroxides MOH and M(OH)2 NaOH and Ca(OH)2 Metal hydrides NaH etc. H + H2O > H2(g) + OH Metal oxides (MO) contain O2 O2 + H2O ! 2 OH

Weak Acids
Do not dissociate completely CH3COOH + H2O <> H3O+ + CH3CO2 H3O+ vs. H+ Weak acids are in equilibrium Both the forward and the reverse reaction occur at the same time

Weak Bases
Some bases react with water to produce an OH in solution NH3 + H2O % NH4+ + OH Weak bases are in equilibrium Both the forward and the reverse reaction occur at the same time

CHM 1045 FALL 2001

Chapter 4 Palmer Graves, Instructor

4.11 Calculate the molarity of an unknown solution or the amount of solution needed in an acid/base titration. [Readings 4.8 Problems 75-82]

Titration
Titration - used to determine a solutions concentration stoichiometry and the chemical equation unknown solution is added to a known amount of a standardized solution Endpoint - the reactants are in their stoichiometric ratio 2 HCl + Ca(OH)2 > 2 H2 O + CaCl2

Acid-Base Titrations
Indicator - changes color at end point endpoint - the number of moles of H+ = the number of moles of OH&
aka the equivalence point

CHM 1045 FALL 2001

Chapter 4 Palmer Graves, Instructor

Titration
Titrant the base solution in the burette. As the base is added the H+ reacts with the OH to form water. still excess acid present so the color does not change. At the endpoint - all the acid is neutralized. The indicator changes color.

Example 4.14: The titration of 10.00 mL of HCl solution of unknown concentration requires 12.54 mL of 0.200 M NaOH solution to reach the end point. What is the concentration of the unknown HCl solution?

Write down the given quantity and its units.

Given:

10.00 mL HCl 12.54 mL of 0.200 M NaOH

Identify: the standard (known solution) the unknown solution

Example 4.14: The titration of 10.00 mL of HCl solution of unknown concentration requires 12.54 mL of 0.200 M NaOH solution to reach the end point. What is the concentration of the unknown HCl solution?

Information Given: 10.00 mL HCl 12.54 mL of 0.200 M NaOH

Write down the goal units for your answer.

Find: concentration HCl, M

CHM 1045 FALL 2001

Example 4.14: The titration of 10.00 mL of HCl solution of unknown concentration requires 12.54 mL of 0.200 M NaOH solution to reach the end point. What is the concentration of the unknown HCl solution?
Information Given: 10.00 mL HCl 12.54 mL of 0.200 M NaOH Find: mol HCl Known solution is NaOH

Chapter 4 Palmer Graves, Instructor

Collect Needed Equations and Conversion Factors: HCl(aq) + NaOH(aq) ! NaCl(aq) + H2O(l)

4.12 Assign oxidation numbers to atoms in a chemical species and use the oxidation numbers to identify and analyze a redox reaction. [Readings 4.9 Problems 83-90]

Redox Reactions
These are reactions in which there is a transfer of electrons

CHM 1045 FALL 2001

Chapter 4 Palmer Graves, Instructor

Redox Reactions
There is a transfer of electrons LEO - loss of electrons is oxidation GER - gain of electrons is reduction Oxidation and reduction must occur together

Redox Reactions
Oxidizing agent - the electron accepting substance The oxidizing agent is REDUCED Reducing agent - electron donating substance The reducing agent is OXIDIZED

Oxidation Numbers
A convenient method of bookkeeping for electrons Oxidation numbers do not imply ionic charge on an atom A change in the oxidation number implies a transfer of electrons Redox reactions can be recognized by the change in the oxidation numbers

CHM 1045 FALL 2001

Chapter 4 Palmer Graves, Instructor

Assigning Oxidation Numbers

1. An atom in its elemental state has an oxidation number of 0 2. A monatomic ion has an oxidation number equal to its charge 3. The sum of the oxidation numbers of the atoms must equal the net charge for a molecule or polyatomic ion. 4. Group 1A and 2A have oxidation states equal to their group - except in metalic form

Assigning Oxidation Numbers

5. Fluorine has an ox. # of -1 in compounds 6. Hydrogen has an ox. # number of +1 in most compounds (occasionally -1) 7. Oxygen has an ox. # of -2 in most compounds 8. Halogens usually have an oxidation number of -1
Except when Cl, Br, or I is bonded to oxygen.

Assign Oxidation Numbers

Fe O2 CO2 MnO4Fe2O3 Na2Cr2O7

CHM 1045 FALL 2001

Chapter 4 Palmer Graves, Instructor

When conflicts occur

When conflicts in the rules occur, assign the first rule and ignore the later, conflicting, rule

Oxidation Numbers

Molybdenum disulde, MoS2, is a black powder used as a lubricant.

Hydrogen peroxide, H2O2, shown as a 3% aqueous H2O2 is a strong oxidizing agent. What are the oxidation numbers of each element in these two compounds?

Oxidation Numbers in a Reaction

Identify which species is oxidized and which is reduced in the following reaction. 2 Fe2O3(s) + 3C (s) > 4 Fe(s) + 3 CO2(g)

CHM 1045 FALL 2001

Chapter 4 Palmer Graves, Instructor

Oxidation Numbers in a Reaction

Identify which species is oxidized and which is reduced in the following reaction. 2 Fe2O3(s) + 3C (s) > 4 Fe(s) + 3 CO2(g)