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THE AQUEOUS PHASE

Q: What happens to salt when it is dissolved in water? - It is a physical change, but how can that be? A: i) Solid salt is a collection of ions, Na+ and Cl-, assembled in a lattice. - Ions are surrounded by each other. ii) When dissolved, the ions are surrounded by water. - Thus, the ions themselves dont change, only their environment.
+ + + + + + + H + H O H H O + O H H O H H

ion surrounded by other ions

ion surrounded by water molecules (solvent cage)

Ions (or sometimes molecules) that are surrounded by water are in the aqueous phase. Ionic compounds which are soluble (that is, dissolve in water) dissociate (that is, break apart) into dissolved cations and anions. Examples: NaCl (aq) = Na+ (aq) + Cl- (aq) K2O (aq) = 2 K+ (aq) + O2- (aq) - note 2 K+ ions dissociate for every K2O unit. Ca(NO3)2 (aq) = Ca2+ (aq) + 2 NO3- (aq) - ions dissociate, but polyatomic ions remain covalently bonded. Fe2(SO4)3 (aq) = 2 Fe3+ (aq) + 3 SO42- (aq) Rb3PO4 (aq) = 3 Rb+ (aq) + PO43- (aq) *Not all compounds dissociate into ions when in the aqueous phase, as we shall soon see.* Aside: phases of reactants and products (g) gas (l) liquid (s) solid

(aq) aqueous

TYPES OF SOLUTES
1. electrolytes - when dissolved, solution conducts electricity - H2O without ions is a poor conductor. - are ionic compounds or acids (usually) a) strong electrolytes - Ions completely dissociate from formula unit or lattice. NaCl (aq) = Na+ (aq) + Cl- (aq) - Water surrounds ions to dissolve lattice. b) weak electrolytes - Ions partially dissociate from formula unit. HC2H3O2 (l) + H2O (l) HC2H3O2 (aq) + H+ (aq) + C2H3O2- (aq) a lot a little a little - Equilibrium (balance) exists between dissociated ions and undissociated compounds. More in 1190. 2.) nonelectrolytes - when dissolved, solution is still electrical insulator - usually molecular compounds C12H22O11 (s) + H2O (l) C12H22O11 (aq) Subtle point: Relatively insoluble compounds can be strong electrolytes.

ACIDS, BASES AND SALTS

Water (H2O) is made of two ions H+ (aq) hydrogen ion OH- (aq) hydroxide ion Acids substances that increase H+ (aq) conc. Strong acids - strong electrolytes, i. e., completely dissociate HCl (aq) = H+ (aq) + Cl- (aq) - memorize list HCl, HBr, HI, HNO3, H2SO4, HClO3, HClO4 Weak acids - weak electrolytes HF (aq) H+ (aq) + F- (aq) HF (aq) HF (aq) + H+ (aq) + F- (aq) a lot a little a little H3PO4 (aq) H+ (aq) + H2PO4- (aq)

Bases substances that increase OH- concentration Strong bases - strong electrolytes - all alkali metal hydroxides LiOH, NaOH, KOH, RbOH, CsOH - some alkaline earth metal hydroxides Ca(OH)2, Sr(OH)2, Ba(OH)2 Weak bases - weak electrolytes - usually increase OH- (aq) conc. indirectly by decreasing H+ (aq) conc. NH3 (aq) + H2O (l) C5H5N (aq) + H2O (l) NH4+ (aq) + OH- (aq) C5H5NH+ (aq) + OH- (aq)

Neutralization reaction Acid + Base Water + Salt Salt - ionic compound - cations and anions remaining after water is made HNO3 (aq) + KOH (aq) H2O (l) + KNO3 (aq)

IONIC EQUATIONS
- molecular equations where all ions in aqueous solution are written in dissociated form

NET IONIC EQUATIONS

- ionic equations where spectator ions (ions unchanged in reaction) are not included Example: Molecular Equation 2 KBr (aq) + Pb(NO3)2 (aq) 2 KNO3 (aq) + PbBr2 (s) Ionic Equation 2 K+ (aq) + 2 Br- (aq) + Pb2+ (aq) + 2 NO3- (aq) Net Ionic Equation Pb2+ (aq) + 2 Br- (aq) PbBr2 (s) Note removing spectator ions clarifies important part of reaction. 2 K+ (aq) + 2 NO3- (aq) + PbBr2 (s)

Example: Molecular Equation HClO4 (aq) + NaOH (aq) H2O (l) + NaClO4 (aq) Ionic Equation Net Ionic Equation

Example: Molecular Equation Fe (s) + CuSO4 (aq) FeSO4 (aq) + Cu (s) Ionic Equation

Net Ionic Equation

METATHESIS REACTIONS
- Cations and anions in two ionic compounds switch places to form precipitate or nonionic compound. - Also known as double replacement reactions. - Compulsion of ions to combine to form other substances is called chemical driving force. - Three driving forces in metathesis reactions 1.) formation of a precipitate (solid) 2.) formation of a nonelectrolyte or weak electrolyte 3.) formation of gas H2, CO2, H2S 1. Formation of precipitate **To determine if precipitate is formed, solubility rules must be memorized.** Solubility Rules Generally Soluble Compounds Anion Exceptions NO3 , C2H3O2 None ClO3-, ClO4None Cl-, Br-, IAg+, Pb2+, Hg22+ Pb2+, Hg22+, Ca2+, Sr2+, Ba2+ SO42Generally Insoluble Compounds Anion Exceptions 2S All alkali metals, NH4+, and Ca2+, Sr2+, Ba2+ All alkali metals, NH4+ CO32-, PO432OH , O All alkali metals and Ca2+, Sr2+, Ba2+ ** Note all alkali metal and ammonium compounds are soluble.**

Using solubility rules to predict reaction occurring - Reaction happens if precipitate is formed. - Reaction does not happen if precipitate is not formed. Example: Does the following reaction occur and what are its products? Na2S (aq) + Fe(NO3)2 (aq) To answer question, switch ions to form potential products. Na2S (aq) + Fe(NO3)2 (aq) NaNO3 ( ) + FeS ( ) Is NaNO3 or FeS insoluble? According solubility rules, FeS is insoluble. Therefore reaction occurs. Balanced molecular equation is Na2S (aq) + Fe(NO3)2 (aq) 2 NaNO3 (aq) + FeS (s) Ionic equation is

Net ionic equation is

Example: Does the following reaction occur and if so, what are its products? Cesium chloride (aq) + Calcium nitrate (aq) CsCl (aq) + Ca(NO3)2 (aq) CsNO3 ( ) + CaCl2 ( ) Is CsNO3 or CaCl2 insoluble? According solubility rules, both are soluble. No driving force is present; therefore, no reaction occurs. Balanced molecular equation is

Ionic equation is

Net ionic equation is

Zip, zero, nothing, nada!!! - All the ions are spectator ions, no reaction occurs.

Example: Does the following reaction occur and what are its products? Ammonium sulfate (aq) + Barium acetate (aq) (NH4)2SO4 (aq) + Ba(C2H3O2)2 (aq) NH4C2H3O2 ( ) + BaSO4 ( ) Is NH4C2H3O2 or BaSO4 insoluble? According solubility rules, all sulfates are soluble, except Ca2+, Sr2+ and Ba2+. Therefore reaction occurs. Balanced molecular equation is

Ionic equation is

Net ionic equation is

2. Formation of nonelectrolyte (weak electrolyte) Example Ba(OH)2 (aq) + 2 HI (aq) 2 H2O (l) + BaI2 (aq) Net ionic equation OH- (aq) + H+ (aq) H2O (l) - Formation of nonelectrolyte (water) is the driving force of the neutralization reaction. Example Hg2(C2H3O2)2 (aq) + 2 HNO3 (aq) 2 HC2H3O2 (aq) + Hg2(NO3)2 (aq) Ionic equation

Net ionic equation

- Formation of weak electrolyte (acetic acid) is the driving force of the reaction. 3. Formation of gas - Common gases formed in metathesis reactions are CO2 (via H2CO3), H2S, H2. - Carbonic acid is unstable at high concentrations. H2CO3 (aq) H2O (l) + CO2 (g) - Addition of acid to all carbonates causes formation of CO2 via decomposition of carbonic acid. Example 2 HClO4 (aq) + MgCO3 (s) H2CO3 (aq) +Mg(ClO4)2 (aq) or considering decomposition of carbonic acid 2 HClO4 (aq) + MgCO3 (s) H2O (l) + CO2 (g) +Mg(ClO4)2 (aq)

Example 2 HNO3 (aq) + CaS (aq) H2S (g) + Ca(NO3)2 (aq) Net ionic equation 2 H+ (aq) + S2- (aq) H2S (g) - reaction of sulfide with acid results in formation of hydrogen sulfide gas.

SINGLE REPLACEMENT REACTIONS

- also known as oxidation-reduction reactions - also known as redox reactions Definitions oxidation process of substance losing ereduction process of substance gaining eMnemonic: OIL RIG Oxidation Is Loss Reduction Is Gain *Oxidation and reduction must occur together.* - e- lost by substance must equal e- gained by other substance. Example 2 Na (s) + 2 HCl (aq) 2 NaCl (aq) + H2 (g) Net ionic equation 2 Na (s) + 2 H+ (aq) 2 Na+ (aq) + H2 (g) - Na is losing electrons, it is being oxidized - H+ is gaining electrons, it is being reduced Example Fe (s) + CuSO4 (aq) FeSO4 (aq) + Cu (s) Net ionic equation Fe (s) + Cu2+ (aq) Fe2+ (aq) + Cu (s) - Fe is oxidized - Cu2+ is reduced

Predicting Spontaneous Redox Reactions - A redox (single replacement) reaction occurs when a metal ion in a compound is replaced with another metal ion. - Some metal atoms are more willing to give away electrons than other metal atoms. - The willingness of a metal atom to give away its electrons is called its activity. - In a reaction between metal ion (in aqueous phase) and metal, if metal is more active than metal ion, reaction will proceed. - We need to have an activity series to assess relative activity of metals. Abbreviated Activity Series Na Al Zn Cr Fe Increasing activity Ni (willingness to be ionized) Sn Pb H Cu Ag Au Example SnSO4 (aq) + Ni (s) NiSO4 (aq) + Sn (s) - Ni replaces Sn2+ - Ni is more active than Sn Does the reverse reaction occur? NiSO4 (aq) + Sn (s) SnSO4 (aq) + Ni (s) - Sn is not more active than Ni NO!!

Example: Does the reaction Pb(NO3)2 (aq) + Cu(s) Pb (s) + Cu(NO3)2 (aq) occur? Look at reactant metals: Pb2+ and Cu. - Is copper more active than lead? - No, therefore reaction does not occur. Example: Does the reaction FeCl2 (aq) + Zn (s) Fe (s) + ZnCl2 (aq) occur? - reactant metals are Fe2+ and Zn Zn is more active than Fe, i.e., Zn is more willing to be an ion than Fe; therefore, yes, the reaction does occur. Example: Does the reaction Al2(SO4)3 (aq) + 2 Cr (s) 2 Al (s) + Cr2(SO4)3 (aq) occur? - reactant metals are Al3+ and Cr Al is more active than Cr; therefore, no, the reaction does not occur.

REACTION TYPE REVIEW

1) Combination recognize - formation reactions: predict products - hydration reactions: predict products 2) Combustion predict products

3) Decomposition recognize - decomposition of carbonates: predict products - decomposition of chlorates: predict products 4) Single replacement reactions: predict products 5) Metathesis (double replacement) reactions: recognize - neutralization: predict products - precipitation: predict products - recognize chemical driving forces - H2CO3 (aq) H2O (l) + CO2(g) 6) Addition: recognize 7) Substitution: recognize 8) Elimination: recognize

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SOLUTIONS
Definitions solvent bulk material used to dissolve substance solute material dissolved in solvent Examples 1) salt water solvent water solute salt 2) dish water solvent water solute dish soap 3) engine coolant solvent ethylene glycol solute water Concentration - amount of solute per amount of solvent - molarity
moles of solute mol = liters of solution L - molarity can be thought of a conversion factor between volume and # of moles. - well consider other concentration units in 1190 Definition: Molarity( M ) =

Molarity calculations Example: What is the molarity of a solution of NaCl that has 1.73 molNaCl dissolved in 2.14 L of solution?

Example: What is the molarity of a KBr solution when 114.8 g of KBr is dissolved in water to make 538.1 mL of solution? How many moles of solute are to be dissolved?

- note the conversion of mL to L Example: How many grams of gold are in 3.75 L of 0.024 M solution of Au(NO3)3? We can convert between volume of solution and moles of solute using molarity as a conversion factor.

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DILUTIONS
- making a solution of lower concentration from a solution of higher concentration Question: If a 5.0 M solution of NaCl is available, how does one make 250 mL of 2.0 M NaCl? 1) To make solution, we need to have the correct number of moles of NaCl.

Md =

mold mold = M d Vd Vd mol 0.250 L = 0.50 mol L

mold = 2.0

2) Now consider how to get 0.50 molNaCl from a 5.0 M solution.

Mc = Vc = molc molc Vc = Vc Mc

0.50 mol = 0.10 L 5.0 mol L

3) Therefore, to make 250 mL of 2.0 M NaCl, one needs 100 mL of 5.0 M NaCl. Then add water to make 250 mL solution. Reconsider step 2. Where did # of mold come from? **Number of moles of solute is the same before and after dilution.** i. e., mold = molc Knowing mol = M V yields Md Vd = Mc Vc

When generalized for any concentration unit, the result becomes the dilution equation. cd Vd = cc Vc c concentration

Example: Find the volume of 6.02 M HCl to make 500 mL of 0.125 M HCl.

Lab Safety Aside: Never add water to acid, always add acid to water.

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SOLUTION STOICHIOMETRY
- Previously, we dealt with comparing components of a chemical reaction by converting mass of substances to moles. - Now we will consider solutions where we will need to convert volumes to moles to make comparisons. Scheme: Mass of reactant (g)
M Molar mass

Mass of product (g)

M Molar mass Balanced equation

Moles of reactant (mol)

M Molarity

Moles of product (mol)

M Molarity

Volume of reactant (L)

Volume of product (L)

Neutralization Reactions acid + base water + salt Example: How many milliliters of 0.176 M KOH is needed to neutralize 45.3 mL of 0.128 M HCl? KOH (aq) + HCl (aq) H2O (l) + KCl (aq)

Example: How many milliliters of 0.176 M KOH is needed to neutralize 45.3 mL of 0.128 M H2SO4? 2 KOH (aq) + H2SO4 (aq) 2 H2O (l) + K2SO4 (aq)

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Precipitation Reactions soluble salt + soluble salt soluble salt + insoluble salt Example: How many grams of Pb3(AsO4)2 are made when 22.8 mL of 0.0141 M Pb(NO3)2 reacts with an excess of aqueous Rb3AsO4? M(Pb3(AsO4)2) = 692.2 g/mol 3 Pb(NO3)2 (aq) + 2 Rb3AsO4 (aq) Pb3(AsO4)2 (s) + 6 RbNO3 (aq)

LIMITING REAGENT PROBLEMS

Recall the following about limiting reagent problems. - To find limiting reactant, calculate number of moles of product formed from each number of moles of reactant. - Limiting reactant will yield lowest number of moles produced. Example: How many grams of Zn(OH)2 are produced when 350 mL of 0.152 M of ZnSO4 is mixed with 250 mL of 0.275 M of LiOH? First write balanced equation ZnSO4 (aq) + 2 LiOH (aq) Zn(OH)2 (s) + Li2SO4 (aq) Now find number of moles of each reactant.

Now calculate possible amount of product that each reactant can produce.

Therefore, LiOH is the limiting reagent.

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Example: When 732 L of 1.81 M of Ag2SO4 is mixed with 1148 L of 2.07 M of KI, a) kilograms of AgI (s) formed b) concentration of all metal ions remaining a) Ag2SO4 (aq) + 2 KI (aq) 2 AgI (s) + K2SO4 (aq)

Ag 2 SO 4 : 732 L
KI: 1148 L

181 mol Ag 2SO 4 . L

2 mol AgI 1 mol Ag 2SO 4

= 2660 mol AgI

2.07 mol KI 1 mol AgI = 2380 mol AgI 1 mol KI L

KI is the limiting reactant.

KI: 2380 mol AgI 234.77 g AgI mol AgI = 558000 g AgI = 558 kg AgI

b) Find concentration of metal ions remaining. The metal ions we might have in solution are Ag+ and K+. i) Consider the concentration of K+ first. - K+ is a spectator ion. - It hasnt participated in any chemical change. Number of moles of K+ ion is same as number of moles of KI initially. Volume of solution is 732 L + 1148 L = 1880 L.

c K+ =

2380 mol K + 1880 L

= 1.26 M

Note that although KI is limiting reagent, none of the K+ is used. This means that we could be more precise by saying that I- is the limiting reagent. ii) Consider the concentration of Ag+. Once reaction is complete, most of the Ag+ ion is now part of AgI solid. But since Ag ion is not limiting reagent some of it remains.
+

How much remains? First of all how much Ag2SO4 went into AgI solid. 1 mol Ag 2 SO 4 2380 mol KI = 1190 mol Ag 2 SO 4 2 mol KI

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Therefore subtract Ag2SO4 used from Ag2SO4 total. total - used remaining 1330 mol -1190 mol 140 mol

We need to be careful about dissociation of Ag2SO4.

140 mol Ag 2SO 4

Thus concentration of Ag+ is

2 mol Ag + 1 mol Ag 2SO 4

= 280 mol Ag +

c Ag + =

280 mol Ag + 1880 L

= 015 M .

INTRODUCTION TO EQUILIBRIUM
Equilibrium is a condition where opposing processes occur at the same time. - I. e., process may proceed backwards and forwards. - Processes may be physical changes or chemical changes. Example: Ice slurry - Temperature of slurry is 0 C. - Melting of ice occurs at same rate as freezing of water. - At 0 C, the conversion of liquid to solid to liquid is an equilibrium process. - All phase transitions are equilibrium processes. Example: Saturated solution - Dissolving of crystal occurs at same rate as crystallization. - This is also an equilibrium process.

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Example: Ozonolysis Ozone = O3 2 O3 (g) 3 O2 (g) 3 O2 (g) 2 O3 (g) 2 O3 (g) 3 O2 (g)

- Decomposition and formation of ozone is happening at the same time. - double arrow indicates equilibrium - A balance exists between amount ozone and diatomic oxygen. Example: Ionization of Acetic Acid - Recall acetic acid (HC2H3O2) is a weak acid. - It does not fully disassociate. HC2H3O2 (aq) H+ (aq) + C2H3O2- (aq)

- Balance exists between associated and dissociated forms of weak acid.