CHAPTER 4

Chemical Reactions

John A. Schreifels 1
Chemistry 211-notes
 Overview
• Ions in Aqueous Solution
– Ion theory in solutions; precipitation reactions
– Molecular and ionic equation
• Typical Reactions
– Precipitation
– Acid-Base
– Oxidation-Reduction (Balancing)
• Working with solutions
• Quantitative analysis

John A. Schreifels 2
Chemistry 211-notes
 Ionic Thory of Solutions
• Pure water is a very poor conductor of electricity.
• Solutions from dissolving NaCl or KCl in water are very
conductive.
• Solutions from dissolving substances such as sugar (sucrose)
C12H22O11 are non-conductive.
• Electrolyte: substance that produces ions when dissolved in
water.
– Strong- good electrical conductor when dissolved in water (completely
ionized). E.g. NaCl, KNO3, Mg(NO3)2, etc.
H O
NaCl( s) 2 Na  (aq)  Cl  (aq)
– Weak-poor conductor when dissolved in water (partial ionization):
NH3 (aq)  H 2 O(l)  NH 4 (aq)  OH 
• Non-electrolyte: substance that does not produce ions when
dissolved in water.

John A. Schreifels 3
Chemistry 211-notes
 Aqueous Reactions and Net
Ionic Equations
Three forms for writing chemical reaction:
• Molecular: :
– AgNO3(aq) + NaCl(aq)  AgCl(s) + NaNO3(aq).
• Ionic:
– Spectator ions are not directly involved in the
reaction
Ag  (aq)  NO 3
 (aq)  Na  (aq)  Cl  (aq)  Na  (aq)  NO  (aq)  AgCl(s)
3

• Net ionic: exclude spectator ions:

– Ag+(aq) + Cl(aq)  AgCl(s).

John A. Schreifels 4
Chemistry 211-notes
 Precipitation Reactions
• Metathesis reaction: reaction in which two
substances react through exchange of their
components. Driving force is often a precipitation.
AX + BY  AY + BX
E.g. Predict if precipitation occurs for the mixture:
AgNO3(aq) + KI(aq)
NaClO4(aq) + Pb(NO3)2(aq)
Na2SO4(aq) + BaCl2(aq),
Ni(NO3)2(aq) + (NH4)2S(aq)
Hint: Use the solubility rules to determine if either
product is insoluble.

John A. Schreifels 5
Chemistry 211-notes
 Solubility Rules
Rule Exception
Soluble
Group 1 elements, NH4+
NO3 , ClO3, ClO4 
Chlorides, bromides, iodides Ag+, Pb2+, Hg22+
Acetates Ag+, Hg22+
Sulfates Sr2+, Ba2+, Pb2+, Ca2+
Insoluble Compounds
Carbonates, phosphates, oxalates, Group 1, NH4+
chromates, sulfides
Hydroxides, oxides Group 1, Ba2+

John A. Schreifels 6
Chemistry 211-notes
 Metathesis Reaction (cont.)
Driving force is
• sometimes formation of weak or non – electrolyte.
E.g. acid – base reactions
CuO(s) + 2HNO3(aq)  Cu(NO3)2(aq) + H2O(l)
– CuO is normally insoluble in water, but readily dissolves in
aqueous nitric acid.
• sometimes formation of gas;
– most common is CO2 from carbonates or H2S from sulfides
E.g.
CuCO3(s) + 2HNO3(aq)  CO2(g) + Cu(NO3)2(aq) + H2O(l)
CuS(s) + 2HNO3(aq)  Cu(NO3)2(aq) + H2S(g)

John A. Schreifels 7
Chemistry 211-notes
 Acids, Bases, and Salts
Arrhenius definition most often used:
• Acid = a hydrogen containing compound that
releases hydrogen ions (H+) in solution.
– HA(aq) + H2O(l)  H3O+(aq) + A(aq) where
• HA = HCl, HNO3,etc. and
• H3O+ = hydronium ion often written as H+.
• Base = compound that releases hydroxide ions
(OH) in solution. The general reaction for a base is:
– MOH(s)  OH(aq) + M+(aq) where
• M = some metal such as Na, K, etc.
• Acids and bases can be strong or weak electrolytes.
• A base/acid that is a strong electrolyte is a strong
base/acid.

John A. Schreifels 8
Chemistry 211-notes
 Polyprotic acids and weak
bases
• Some acids have more than one acidic proton.
– Sulfuric: H 2 SO 4 (l)  H 2 O(l)  HSO 
4 (aq)  H 3 O  (aq)

HSO 
4 (aq)  H 2 O(l)  SO 2  (aq)  H O  (aq)
4 3

– Phosphoric: H3PO4 (l)  H2O(l)  H2PO4 (aq)  H3O (aq)

H2PO4 (aq)  H 2O(l)  HPO 2  (aq)  H O (aq)
4 3
HPO24  (aq)  H2O(l)  PO34  (aq)  H3O (aq)

• Most weak bases produce hydroxide ions by

reaction with water.  
– Ammonia NH3(aq)  H2O  NH4 (aq)  OH (aq)

John A. Schreifels 9
Chemistry 211-notes
 Strong and Weak Acids and
Bases
• Organic acids are weak (usually have –COOH).
• Amines (containing nitrogen) are weak.
• In water they are completely dissociated:
– HCl(aq) + H2O(l)  H3O+(aq) + Cl(aq)

Strong Acids Strong Bases

Chloric, HClO3 Grp 1A hydroxides (LiOH,
Hydrobromic, HBr NaOH, KOH, RbOH, CsOH)
Hydroiodic, HI Grp 2A metal hydroxides
Perchloric, HClO4 (Ca(OH)2, Sr(OH)2, Ba(OH)2
Sulfuric, H2SO4
Nitric, HNO3
John A. Schreifels 10
Chemistry 211-notes
 Neutralization Reaction
• Acids react with bases to form a salt and
possibly water (called the neutralization
reaction):
– HA(aq)+MOH(aq)M+(aq)+A(aq)+H2O(l).
– If either the acid or base is a strong electrolyte,
exclude spectator ions in the ionic form.
E.g. HCN = weak acid; NaOH = strong base;
neutralization reaction is
– HCN(aq) + OH(aq)  CN(aq) + H2O(l)
Eg. 2 HCl neutralized by NaOH; net ionic
equation:
– H+(aq) + OH(aq)  H2O(l)
John A. Schreifels 11
Chemistry 211-notes
 Oxidation – Reduction
• Oxidation = loss of at least one electron during a
reaction..
– Ni(s) + H+(aq)  Ni2+(aq) + H2(g)
• Reduction = gain of at least one electron during a
reaction.
– In above example, H+ gains an electron to become reduced.
• Every reaction must have an oxidation and reduction.
• Metals react with acids to form salts and hydrogen
gas.
– Cu(s) + 2HNO3(aq)  Cu(NO3)2(aq) + H2(g)
• Metals also oxidized with salts
– Fe(s) + Cu(NO3)2(aq)  Fe(NO3)2(aq) + Cu(s)

John A. Schreifels 12
Chemistry 211-notes
 Oxidation Number
• Oxidation number (state): the charge on an
atom in a substance or monatomic ion. Ca in CaO +2
• Rules:
– Elemental form: 0 Ca2+(aq) +2
– Monatomic ions: charge of ion Cl(aq) 1
– Oxygen: 2, except in H2O2 and other
peroxides.
– Hydrogen: +1, except with metal
hydrides when it is 1.
– Halogens: 1 (except when bound to Cr in CrO3 +6
oxygen or a halide above it)
– Alkali and alkaline earth metal ions have Fe in Fe2O3 +3
a charge of +1 and +2, respectively.
– Compounds and ions: sum of the Cr in K2Cr2O7 +6
charges on the atoms in a compound
add up to 0 and to the ion charge in the
ion.

John A. Schreifels 13
Chemistry 211-notes
 Displacement Reactions:
Activity series of the elements
• A relative reactivity scale allows us to predict if Li
reaction will occur when two substances are
mixed together. K
E.g. Copper ions in solution are reduced to the metal Ba Reacts
when an iron nail is placed in the solution. Reacts
– Cu2+(aq) + Fe(s)  Fe2+(aq) + Cu(s)  Iron Ca vigorously with H2O
displaces copper. with acids to give
– Fe2+(aq) + Cu(s) NR  copper will not Na to give H2 H2
displace iron.
• Iron more reactive than copper.
E.g. Predict which reaction will occur when:
– Li is mixed with K+ and
– Li+ is mixed with K. Mg Reacts Reacts
E.g. In which of the following mixtures will reaction with acids slowly
occur: Al
– Li+ + Mg to give H2 with H2O
Zn
– Al + Mn2+ to give
– Fe + Cd2+ Cr H2; more
– Cr + Zn2+ vigorous
Fe
with
John A. Schreifels
Cd 14
steam
Chemistry 211-notes
 Balancing: Oxidation-Number
Method
• Determine oxidation # for each atom- both sides of equation.
• Determine change in oxidation state for each atom.
• Left side: make loss of electrons = gain.
• Balance other side.
• Insert coefficients for atoms that don't change oxidation state.
E.g. Balance
– FeS(s)+CaC2(s) + CaO(s)  Fe(s)+ CO(g)+ CaS(s)
• In acidic or basic solution balance as above, then balance
charge with H+ or OH on one side and water on other side.
E.g. Balance:
  
– Acidic solution: ClO  CrO2  Cl  CrO4
2

John A. Schreifels 15
Chemistry 211-notes
 Balancing: Half-Reaction
Method
Write unbalanced half reactions for the oxidation and the reduction
• Balance the number of elements except O and H for each.
• Balance O's with H2O to the deficient side.
• Balance H's with H+ to the hydrogen deficient side
– Acidic: add H+
– Basic: add H2O to the deficient side and OH to the other side.
• Balance charge by adding e to the side that needs it.
• Multiply each half-reaction by integers to make electrons
cancel.
• Add the two half-reactions and simplify.
E.g. Balance:
– Acidic: Zn(s) + VO2+(aq)  Zn2+(aq) + V3+(aq).
– Basic: Ag(s) + HS(aq) + CrO42(aq)  Ag2S(s) + Cr(OH)3(s).

John A. Schreifels 16
Chemistry 211-notes
Solution Composition, Molarity
• Most reactions performed in solution (homogeneous mixture) since
reactants mobile.
• Solute dissolved substance.
• Solvent substance in which solute is dissolved.
• Concentration: amount of solute dissolved in a given amount of
solvent.
• Concentrated solution: large amount of solute in solvent.
• Dilute solution: very little solute in solvent. Often obtained by dilution.
• Molar concentration ( Molarity, M ): moles of solute dissolved in a liter
of solution.
E.g. An aqueous solution of 0.25 M NaCl can be prepared by dissolving:
– 0.25 mol NaCl in a 1-Liter flask
– 0.50 mol NaCl in a 2-Liter flask
– 0.125 mol in 1/2 liter flask (500 mL).
E.g. 1 Determine mass needed to prepare exactly 2 liters of 0.150M NaCl.
E.g. 2 Determine the concentration when 12.5 g NaCl is dissolved and
diluted to 500.0 mL.

John A. Schreifels 17
Chemistry 211-notes
 Ion Concentrations in Solutions
• Concentrations of ions after dissolution
depends on formula
• Determine concentration of each ion in
the following solutions: 0.100 M CaSO4,
0.100 M Cu(NO3)2, 0.100 M FeCl3

John A. Schreifels 18
Chemistry 211-notes
 Mass % To Molarity
Often manufacturers provide us with mass % of a
compound in solution, but it is more convenient to
use molarity.
E.g. Determine the molarity of NH3(aq) if the mass% =
28.0 % NH3 and the density = 0.898 g/mL.
– Assume 100g of solution
– From mass of solute (28 g NH3) in 100 g determine .
– From the mass of solution (100 g) and the density,
determine V = the volume of the solution.
– From above steps determine the molar concentration:
[NH3] = n(NH3)/V = 1.65 mol NH3/ 0.111L = 14.96 M NH3.

John A. Schreifels 19
Chemistry 211-notes
 DILUTIONS
• Dilute solutions are prepared from more concentrated
ones by adding solvent to the concentrated one.
• The concentration of the dilute solution can be
determined if we know:
– The volume of the concentrated solution, Vi.
– The concentration of the concentrated solution, Mi.
– The volume of the dilute solution, Vf.
• The relationship between the molarities and volumes
is:
moles of solute  MiVi  Mf Vf
• E.g. Determine the volume needed to prepare 500.0
mL of a 0.100 M HCl solution from a 12.40 M stock
solution.

John A. Schreifels 20
Chemistry 211-notes
 REACTIONS IN SOLUTION
• Reactions usually carried out in solution.
• Amounts of reactants and products (m or n) must be determined from the
volume and molarity of the solution.
• Start with the stoichiometric relationship for any reaction:
– aA + bB  cC a a
mol A  mol B   mol A  mol C 
b c
• Depending upon what is given in the problem substitute for mol A, B or C.
E.g., if we are dealing with a solution we substitute MAVA for the mol A.
E.g. Calculate the volume of 0.200 M KI required to react with 50.0 mL of 0.300
M Pb(NO3)2.
• Strategy:
• Balance reaction: Pb(NO3)2 + 2KI 2 PbI2 + 2KNO3.
• From stoichiometry: mol K  mol Pb  1
2
MK  VK  MPb  VPb 
• Substitute for mol: 1
• Solve

John A. Schreifels 21
Chemistry 211-notes
 TITRATIONS
• Titration: a procedure for determining the amount of one
substance A by adding a carefully measured amount of a
solution B until A is just consumed.
• Calculations are the same as in the last overhead.
• E.g. What is the molarity of HCl if 25.00 mL of it was titrated to
the equivalence point with 33.33 mL of 0.1000 M Ba(OH)2?
VBa(OH)
MHCl  MBa(OH)  2 2
• The stoichiometric relationship is: 2 VHCl 1
• Substitute the given quantities and solve for the [HCl].
• The ratio of stoichiometric coefficients tells how much of one
compound will react if we know the amount of the other:
aA + bB  cC ? a
n
B b
– Solutions: n = MV; solids: n = m/FM

John A. Schreifels 22
Chemistry 211-notes