Page III-4b-1 / Chapter Four Part II Lecture Notes. Chemistry 221 Professor Michael Russell MAR. Ba(NO3)2(aq)? soluble. BaCl2(aq)?

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Page III-4b-1 / Chapter Four Part II Lecture Notes Solution Stoichiometry and Chemical Reactions Chapter 3 & Chapter 4, or Chapter 4 Part II Chemistry 221 Professor Michael Russell Terminology In

when they stay as solids Water Solubility of Ionic Compounds If one ion from the Soluble Compd. list is present in a compound, the compound is water soluble. Ba(NO3)2(aq)? soluble BaCl2(aq)?

Many ions, however, make compounds SOLUBLE all of the time. Examples: Na +, K +, Li +, NH 4 +, NO 3 -, ClO 3 -, ClO 4 -, CH 3 CO 2 -, and most SO 4 2-, Cl -, Br - and I - compounds.

1 Page III-4b-1 / Chapter Four Part II Lecture Notes Solution Stoichiometry and Chemical Reactions Chapter 3 & Chapter 4, or Chapter 4 Part II Chemistry 221 Professor Michael Russell Terminology In solution we need to define the - SOLVENT the component whose physical state is preserved when solution forms SOLUTE the other solution component Compounds are soluble when they dissolve, insoluble when they stay as solids Water Solubility of Ionic Compounds If one ion from the Soluble Compd. list is present in a compound, the compound is water soluble. Ba(NO3)2(aq)? soluble BaCl2(aq)? soluble BaSO4(aq)? insoluble should write BaSO4(s)! Use this solubility guide in CH ! WATER SOLUBILITY OF IONIC COMPOUNDS Not all ionic compounds dissolve in water. Some are INSOLUBLE. Many ions, however, make compounds SOLUBLE all of the time. Examples: Na +, K +, Li +, NH 4 +, NO 3 -, ClO 3 -, ClO 4 -, CH 3 CO 2 -, and most SO 4 2-, Cl -, Br - and I - compounds. IONIC COMPOUNDS Compounds in Aqueous Solution Many reactions involve soluble ionic compounds, especially reactions in water - aqueous solutions. KMnO 4 in water K + (aq) + MnO 4 -(aq) Aqueous Solutions How do we know ions are present in aqueous solutions? The solutions conduct electricity! They are called ELECTROLYTES HCl, KMnO 4, MgCl 2, and NaCl are strong electrolytes. They dissociate completely (or nearly so) into ions. KMnO 4 (aq) ---> K + (aq) + MnO 4 -(aq) Page III-4b-1 / Chapter Four Part II Lecture Notes

Page III-4b-2 / Chapter Four Part II Lecture Notes Aqueous Solutions HCl, MgCl 2, and NaCl

Aqueous Solutions Acetic acid ionizes only to a small extent, so it is a weak electrolyte

ethanol, acetone, etc.) dissolve in water but do not conduct electricity.

ACIDS Some strong acids include: HCl hydrochloric HNO 3 nitric HClO 4 perchloric H 2 SO 4

strong acids are strong electrolytes The Nature of Acids HCl Cl - Weak Acids All weak acids

2 Page III-4b-2 / Chapter Four Part II Lecture Notes Aqueous Solutions HCl, MgCl 2, and NaCl are strong electrolytes. They dissociate completely (or nearly so) into ions. Aqueous Solutions Acetic acid ionizes only to a small extent, so it is a weak electrolyte CH 3 CO 2 H(aq) ---> CH 3 CO 2 -(aq) + H + (aq) Aqueous Solutions Some compounds (sugar, ethanol, acetone, etc.) dissolve in water but do not conduct electricity. They are called nonelectrolytes. ACIDS Some strong acids include: HCl hydrochloric HNO 3 nitric HClO 4 perchloric H 2 SO 4 sulfuric An acid > H + in water See "Dissolve, Dissociate and Electrolyte" Guide All strong acids are strong electrolytes The Nature of Acids HCl Cl - Weak Acids All weak acids are weak electrolytes CH 3 CO 2 H acetic acid H 2 CO 3 carbonic acid H 3 PO 4 phosphoric acid H 2 O H 3 O + hydronium ion Acetic acid Page III-4b-2 / Chapter Four Part II Lecture Notes

Page III-4b-3 / Chapter Four Part II Lecture Notes BASES Base ---> OH - in water Ammonia, NH 3 An Important Base Bases are often metal

electrolytes Common Acids and Bases Net Ionic Equations Mg(s) + 2 HCl(aq) --> H 2 (g) + MgCl 2 (aq) Know the strong acids & bases!

2 (g) + MgCl 2 (aq) Aqueous solutes (HCl, MgCl2) dissociate; we really should write: Mg(s) + 2 H + (aq) + 2 Cl - (aq) H 2 (g) + Mg 2+

See Net Ionic Reactions Handout Net Ionic Equations K 2 CrO 4 (aq) + Pb(NO 3 ) 2 (aq) --> PbCrO 4 (s) + 2 KNO 3 (aq) NET IONIC EQUATION

3 Page III-4b-3 / Chapter Four Part II Lecture Notes BASES Base ---> OH - in water Ammonia, NH 3 An Important Base Bases are often metal hydroxides NaOH(aq) ---> Na + (aq) + OH - (aq) NaOH is a strong base All strong bases are strong electrolytes All weak bases are weak electrolytes Common Acids and Bases Net Ionic Equations Mg(s) + 2 HCl(aq) --> H 2 (g) + MgCl 2 (aq) Know the strong acids & bases! We really should write: Mg(s) + 2 H + (aq) + 2 Cl - (aq) ---> H 2 (g) + Mg 2+ (aq) + 2 Cl - (aq) Net Ionic Equations Mg(s) + 2 HCl(aq) H 2 (g) + MgCl 2 (aq) Aqueous solutes (HCl, MgCl2) dissociate; we really should write: Mg(s) + 2 H + (aq) + 2 Cl - (aq) H 2 (g) + Mg 2+ (aq) + 2 Cl - (aq) We leave the spectator ions (Cl - ) out in writing the NET IONIC EQUATION: Mg(s) + 2 H + (aq) H 2 (g) + Mg 2+ (aq) See Net Ionic Reactions Handout Net Ionic Equations K 2 CrO 4 (aq) + Pb(NO 3 ) 2 (aq) --> PbCrO 4 (s) + 2 KNO 3 (aq) NET IONIC EQUATION Pb 2+ (aq) + CrO 4 2-(aq) ---> PbCrO 4 (s) K + and NO 3 - are spectators See Net Ionic Reactions Handout Page III-4b-3 / Chapter Four Part II Lecture Notes

Page III-4b-4 / Chapter Four Part II Lecture Notes CHEMICAL REACTIONS IN WATER We will look at EXCHANGE REACTIONS AX + BY

Fe(NO3)3(aq) + 3 NaOH(aq) -----> 3 NaNO3(aq) + Fe(OH)3(s) AY + BX The anions exchange places between cations Precipitation

Net ionic equation Fe3+(aq) + 3 OH-(aq) ---> Fe(OH)3(s) See "Five Types of Reactions" Handout Acid-Base Reactions Acids

NaOH(aq) + HCl(aq) ---> NaCl(aq) + H2O(liq) Net ionic equation: OH-(aq) + H+(aq) ---> H2O(liq) This applies to ALL

Acid-base reactions often called "neutralizations", water and "salt" created See "Five Types of Reactions" Handout

H2CO3(aq) ---> CO2(g) + water Another gas forming species: NH4OH(aq) ---> NH3(g) + water See "Five Types of Reactions"

special example of a gas-forming reaction Used in quantitative chemistry; high temperatures Reactants: oxygen (O2) and

4 Page III-4b-4 / Chapter Four Part II Lecture Notes CHEMICAL REACTIONS IN WATER We will look at EXCHANGE REACTIONS AX + BY The "driving force" is the formation of an insoluble compound - a precipitate. Fe(NO3)3(aq) + 3 NaOH(aq) -----> 3 NaNO3(aq) + Fe(OH)3(s) AY + BX The anions exchange places between cations Precipitation Reactions Pb(NO3)2(aq) + 2 KI(aq) ----> PbI2(s) + 2 KNO3(aq) Exchange reactions often called Double Displacement Reactions Net ionic equation Fe3+(aq) + 3 OH-(aq) ---> Fe(OH)3(s) See "Five Types of Reactions" Handout Acid-Base Reactions Acids react readily with bases. The "driving force" is the formation of water. NaOH(aq) + HCl(aq) ---> NaCl(aq) + H2O(liq) Net ionic equation: OH-(aq) + H+(aq) ---> H2O(liq) This applies to ALL reactions of STRONG acids and bases. Acid-base reactions often called "neutralizations", water and "salt" created See "Five Types of Reactions" Handout Gas-Forming Reactions CaCO3(s) + 2 HCl(aq) ---> CaCl2(aq) + H2CO3(aq) Carbonic acid is unstable and forms CO2 & H2O H2CO3(aq) ---> CO2(g) + water Another gas forming species: NH4OH(aq) ---> NH3(g) + water See "Five Types of Reactions" Handout Oxidation-Reduction Reactions Combustion Reactions REDOX = reduction & oxidation 2 H2(g) + O2(g) ---> 2 H2O(liq) A special example of a gas-forming reaction Used in quantitative chemistry; high temperatures Reactants: oxygen (O2) and "something organic" (C, H, sometimes O or N) Products: water and carbon dioxide (also NO2 if N present) Examples: C2H4(g) + 3 O2(g) 2 H2O(g) + 2 CO2(g) 4 C6H5NO O2(g) 10 H2O(g) + 24 CO2(g) + 4 NO2(g) See "Five Types of Reactions" Handout See "Five Types of Reactions" Handout Page III-4b-4 / Chapter Four Part II Lecture Notes

Page III-4b-5 / Chapter Four Part II Lecture Notes LEO says GER LEO says GER Lose Electrons Oxidized Zn(s) Zn 2+ + 2e- Cu 2+ + 2e- Cu(s) Gain Electrons Reduced Oxidized Reduced Can also use "OIL

Ag + (aq) Cu 2+ (aq) + 2 Ag(s) Redox reactions incredibly useful (fuels, batteries, much more) Oxidation numbers help visualize electron transfer pathways Use oxidation number rules to determine

= 0 Zn(s), O 2 (g), Br 2 (liq) In simple ions, ox. no.

5 Page III-4b-5 / Chapter Four Part II Lecture Notes LEO says GER LEO says GER Lose Electrons Oxidized Zn(s) Zn e- Cu e- Cu(s) Gain Electrons Reduced Oxidized Reduced Can also use "OIL RIG": OIL = "Oxidation is Losing" (electrons) RIG = "Reduction is Gaining" (electrons) REDOX REACTIONS In all reactions: if something has been oxidized then something has also been reduced: Cu(s) + 2 Ag + (aq) Cu 2+ (aq) + 2 Ag(s) Redox reactions incredibly useful (fuels, batteries, much more) Oxidation numbers help visualize electron transfer pathways Use oxidation number rules to determine redox activity: Atoms in free element have ox. no. = 0 Zn(s), O 2 (g), Br 2 (liq) In simple ions, ox. no. = charge on ion -1 for Cl -, +2 for Mg 2+ O is -2 (except peroxides (O = -1) and with F) H is +1 (except hydrides (H = -1)) Sum of oxidation numbers = 0 for a compound or equals the overall charge for an ion OXIDATION NUMBERS OXIDATION NUMBERS Determining oxidation numbers takes practice Recognizing a Redox Reaction 2 Al(s) + 3 Cu 2+ (aq) ---> 2 Al 3+ (aq) + 3 Cu(s) Al(s) --> Al 3+ (aq) + 3 e - Ox. no. of Al increases as e - are donated by the metal; Al is OXIDIZED (or the REDUCING AGENT) HF H: +1 F: -1 ClO 4 - Cl: +7 O: -2 Cu 2+ (aq) + 2 e - --> Cu(s) Page III-4b-5 / Chapter Four Part II Lecture Notes Ox. no. of Cu decreases as e - are accepted by the ion; Cu is REDUCED (or the OXIDIZING AGENT)

Page III-4b-6 / Chapter Four Part II Lecture Notes Agents of Redox!

Cl 2 = oxidizing agent 2 Fe + 3 Cl 2 2 FeCl 3 Reduced = Oxidizing Agent Oxidized = Reducing Agent reducing

given by its concentration. PROBLEM: Dissolve 5.00 g of NiCl 2 6 H 2 O in enough water to make 250.

Molarity (M) = moles solute liters of solution Concentration (M) = [ ] PROBLEM: Dissolve 5.

00 g 1 mol 237.7 g 0.0210 mol 0.250 L = 0.0210 mol Step 2: Calculate molarity = 0.

6 Page III-4b-6 / Chapter Four Part II Lecture Notes Agents of Redox! Examples of Redox Reactions NO = reducing agent O 2 = oxidizing agent 2 NO + O 2 2 NO 2 Fe = reducing agent Cl 2 = oxidizing agent 2 Fe + 3 Cl 2 2 FeCl 3 Reduced = Oxidizing Agent Oxidized = Reducing Agent reducing agent = oxidized oxidizing agent = reduced Concentration of Solute The amount of solute in a solution is given by its concentration. PROBLEM: Dissolve 5.00 g of NiCl 2 6 H 2 O in enough water to make 250. ml of solution. Calculate molarity. Molarity (M) = moles solute liters of solution Concentration (M) = [ ] PROBLEM: Dissolve 5.00 g of NiCl 2 6 H 2 O in enough water to make 250. ml of solution. Calculate molarity. Step 1: Calculate moles of NiCl 2 6H 2 O 5.00 g 1 mol g mol L = mol Step 2: Calculate molarity = M [NiCl 2 6 H 2 O] = M The Nature of a CuCl 2 Solution Ion Concentrations CuCl 2 (aq) --> Cu 2+ (aq) + 2 Cl - (aq) If [CuCl 2 ] = 0.30 M, then [Cu 2+ ] = 0.30 M [Cl - ] = 2 x 0.30 M = 0.60 M Page III-4b-6 / Chapter Four Part II Lecture Notes

Page III-4b-7 / Chapter Four Part II Lecture Notes USING MOLARITY What mass of oxalic acid, H 2 C 2 O 4, is required to make 250. ml of a 0.0500 M solution?

13 g Preparing Solutions Weigh out a solid solute and dissolve in a given quantity of solvent or Dilute a concentrated solution to give one that is less concentrated. You have 50.0 ml of 3.

How much water should be added? The important point: moles of NaOH in ORIGINAL solution = moles of NaOH in FINAL solution 3.0 M NaOH 0.50 M NaOH Concentrated Dilute You have 50.0 ml of 3.

7 Page III-4b-7 / Chapter Four Part II Lecture Notes USING MOLARITY What mass of oxalic acid, H 2 C 2 O 4, is required to make 250. ml of a M solution? moles = M V Step 1: Calculate moles of acid required. ( mol/l)(0.250 L) = mol Step 2: Calculate mass of acid required. ( mol )(90.00 g/mol) = 1.13 g Preparing Solutions Weigh out a solid solute and dissolve in a given quantity of solvent or Dilute a concentrated solution to give one that is less concentrated. You have 50.0 ml of 3.0 M NaOH and you want 0.50 M NaOH. What do you do? You have 50.0 ml of 3.0 M NaOH and you want 0.50 M NaOH. What do you do? H2O But how Add much water! water do Dilute we add? the solution! How much water should be added? The important point: moles of NaOH in ORIGINAL solution = moles of NaOH in FINAL solution 3.0 M NaOH 0.50 M NaOH Concentrated Dilute You have 50.0 ml of 3.0 M NaOH and you want 0.50 M NaOH. What do you do? You have 50.0 ml of 3.0 M NaOH and you want 0.50 M NaOH. What do you do? Moles of NaOH in original solution = M * V = (3.0 mol/l)(0.050 L) = 0.15 mol NaOH Therefore, moles of NaOH in final solution must also = 0.15 mol NaOH (0.15 mol NaOH)(1 L/0.50 mol) = 0.30 L or 300 ml = volume of final solution Conclusion: H2O add 250 ml 3.0 M NaOH 0.50 M NaOH of water to 50.0 ml of 3.0 M NaOH to make 300 ml of 0.50 M NaOH. Concentrated Page III-4b-7 / Chapter Four Part II Lecture Notes Dilute

Page III-4b-8 / Chapter Four Part II Lecture Notes Preparing Solutions by Dilution A shortcut SOLUTION STOICHIOMETRY Zinc reacts with acids to produce H 2 gas. What volume of 2.

M initial * V initial = M final * V final Often abbreviated: MiVi = MfVf Zn(s) + 2 HCl(aq) --> ZnCl 2 (aq) + H 2 (g) Step 2: Use the stoichiometric factor 2 mol HCl 0.153 mol Zn = 0.

8 Page III-4b-8 / Chapter Four Part II Lecture Notes Preparing Solutions by Dilution A shortcut SOLUTION STOICHIOMETRY Zinc reacts with acids to produce H 2 gas. What volume of 2.50 M HCl is needed to convert 10.0 g of Zn? M initial * V initial = M final * V final Often abbreviated: MiVi = MfVf Zn(s) + 2 HCl(aq) --> ZnCl 2 (aq) + H 2 (g) Step 2: Use the stoichiometric factor 2 mol HCl mol Zn = mol HCl 1 mol Zn Step 3: Calculate volume of HCl required 1.00 L mol HCl = L HCl 2.50 mol Zinc reacts with acids to produce H 2 gas. What volume of 2.50 M HCl is needed to convert 10.0 g of Zn? Step 1: Calculate moles of Zn 10.0 g Zn 1.00 mol Zn g Zn = mol Zn Zn(s) + 2 HCl(aq) --> ZnCl 2 (aq) + H 2 (g) ACID-BASE REACTIONS Titrations H 2 C 2 O 4 (aq) + 2 NaOH(aq) ---> acid base Na 2 C 2 O 4 (aq) + 2 H 2 O(liq) Carry out this reaction using a TITRATION. Oxalic acid, H 2 C 2 O 4 Setup for titrating an acid with a base Setup for Titrating an acid with a base LAB PROBLEM #1: Standardize a solution of NaOH - i.e., accurately determine its concentration g of H 2 C 2 O 4 (oxalic acid) requires ml of NaOH for titration to an equivalence point. What is the concentration of the NaOH? Page III-4b-8 / Chapter Four Part II Lecture Notes H 2 C 2 O 4 (aq) + 2 NaOH(aq) ---> Na 2 C 2 O 4 (aq) + 2 H 2 O(liq)

Page III-4b-9 / Chapter Four Part II Lecture Notes 1.065 g of H 2 C 2 O 4 (oxalic acid) requires 35.62 ml of NaOH for titration to an equivalence point. What is the concentration of the NaOH?

9 Page III-4b-9 / Chapter Four Part II Lecture Notes g of H 2 C 2 O 4 (oxalic acid) requires ml of NaOH for titration to an equivalence point. What is the concentration of the NaOH? g of H 2 C 2 O 4 (oxalic acid) requires ml of NaOH for titration to an equivalence point. What is the concentration of the NaOH? Step 1: Calculate moles of H 2 C 2 O g * mol acid 1 mol g 2 mol NaOH 1 mol acid = mol Step 2: Calculate moles of NaOH req d = mol NaOH H 2 C 2 O 4 (aq) + 2 NaOH(aq) ---> Na 2 C 2 O 4 (aq) + 2 H 2 O(liq) Step 1: Calculate moles of H 2 C 2 O 4 = mol acid Step 2: Calculate moles of NaOH req'd = mol NaOH Step 3: Calculate concentration of NaOH mol NaOH L [NaOH] = M = M H 2 C 2 O 4 (aq) + 2 NaOH(aq) ---> Na 2 C 2 O 4 (aq) + 2 H 2 O(liq) LAB PROBLEM #2: Use standardized NaOH to determine the amount of an acid in an unknown. Apples contain malic acid, C 4 H 6 O 5. C 4 H 6 O 5 (aq) + 2 NaOH(aq) ---> Na 2 C 4 H 4 O 5 (aq) + 2 H 2 O(liq) g of apple requires ml of M NaOH for titration. What is weight % of malic acid? g of apple requires ml of M NaOH for titration. What is weight % of malic acid? Step 1: Calculate moles of NaOH used. M * V = ( M)( L) = mol NaOH Step 2: Calculate moles of acid titrated mol NaOH = mol acid 1 mol acid 2 mol NaOH C 4 H 6 O 5 (aq) + 2 NaOH(aq) ---> Na 2 C 4 H 4 O 5 (aq) + 2 H 2 O(liq) g of apple requires ml of M NaOH for titration. What is weight % of malic acid? Step 1: moles of NaOH = Step 2: moles of acid titrated = Step 3: Calculate mass of acid titrated. ph, a Concentration Scale ph: a way to express acidity -- the concentration of H + in solution mol acid g mol = g Step 4: Calculate % malic acid. (1.539 g acid / g apple) *100 = % C 4 H 6 O 5 (aq) + 2 NaOH(aq) ---> Na 2 C 4 H 4 O 5 (aq) + 2 H 2 O(liq) Low ph: high [H + ] High ph: low [H + ] Page III-4b-9 / Chapter Four Part II Lecture Notes Acidic solution ph < 7 Neutral ph = 7 Basic solution ph > 7

Page III-4b-10 / Chapter Four Part II Lecture Notes The ph Scale [H+]

In a neutral solution, [H+] = [OH-] = 1.

(1.00 x 10-7) ph= - log (1.6 x 10-3) = - (-7) = 7 ph = - (-2.80) ph = 2.

Four Part 2 If the ph of Coke is 3.12, it is.

Guide Because ph = - log [H+] then log [H+] = - ph Take antilog and get

10 Page III-4b-10 / Chapter Four Part II Lecture Notes The ph Scale [H+] and ph ph = - log [H+] If the [H+] of soda is 1.6 x 10-3 M, the ph is? In a neutral solution, [H+] = [OH-] = 1.00 x 10-7 M at 25 oc Because ph = - log [H+] then ph = - log [H+] = -log (1.00 x 10-7) ph= - log (1.6 x 10-3) = - (-7) = 7 ph = - (-2.80) ph = 2.80 Søren Sørensen, creator of the ph scale ph and [H+] End of Chapter Four Part 2 If the ph of Coke is 3.12, it is. See also: Chapter Four Part 2 Study Guide Chapter Four Part 2 Concept Guide Because ph = - log [H+] then log [H+] = - ph Take antilog and get [H+] = 10-pH [H+] = [H+] = 7.6 x 10-4 M more on acids, bases and ph in CH 223 Page III-4b-10 / Chapter Four Part II Lecture Notes

Compounds in Aqueous Solution

1 Compounds in Aqueous Solution Many reactions involve ionic compounds, especially reactions in water KMnO 4 in water K + (aq) ) + MnO 4- (aq) 2 CCR, page 149 3 How do we know ions are present in aqueous