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Chapter 4 Type of Chemical Reactions and Solution Stoichiometric Water, Nature of aqueous solutions, types of electrolytes, dilution. Types of chemical reactions: precipitation, acid-base and oxidation reactions. Stoichiometry of reactions and balancing the chemical equations. 1 Aqueous Solutions Water is the dissolving medium, or solvent. 2 Figure 4.1: (Left) The water molecule is polar. (Right) A space-filling model of the water molecule. 3 Figure 4.2: Polar water molecules interact with the positive and negative ions of a salt assisting in the dissolving process. 4 Some Properties of Water Water is “bent” or V-shaped. The O-H bonds are covalent. Water is a polar molecule. Hydration occurs when salts dissolve in water. 5 Figure 4.3: (a) The ethanol molecule contains a polar O—H bond similar to those in the water molecule. (b) The polar water molecule interacts strongly with the polar O—H bond in ethanol. This is a case of "like dissolving like." 6 A Solute dissolves changes in water (or other “solvent”) phase (if different from the solvent) is present in lesser amount (if the same phase as the solvent) 7 A Solvent retains its phase (if different from the solute) is present in greater amount (if the same phase as the solute) 8 General Rule for dissolution Like dissolve like Polar dissolve polar (water dissolve ethanol) Non-polar dissolve nonpolar (benzene dissolve fat) 9 Figure 4.5: When solid NaCl dissolves, the Na+ and Cl- ions are randomly dispersed in the water. 10 Electrolytes Strong - conduct current efficiently NaCl, HNO3 Weak - conduct only a small current vinegar, tap water Non - no current flows pure water, sugar solution 11 Figure 4.4: Electrical conductivity of aqueous solutions. 12 Acids Strong acids - dissociate completely to produce H+ in solution hydrochloric and sulfuric acid HCl , H2SO4 Weak acids - dissociate to a slight extent to give H+ in solution acetic and formic acid CH3COOH, CH2O 13 Bases Strong bases - react completely with water to give OH ions. sodium hydroxide Weak bases - react only slightly with water to give OH ions. ammonia 14 Figure 4.6: HCl(aq) is completely ionized. 15 Figure 4.7: An aqueous solution of sodium hydroxide. 16 Figure 4.8: Acetic acid (HC2H3O2) exists in water mostly as undissociated molecules. Only a small percentage of the molecules are ionized. 17 Molarity Molarity (M) = moles of solute per volume of solution in liters: moles of solute M molarity liters of solution 6 moles of HCl 3 M HCl 2 liters of solution 18 Common Terms of Solution Concentration Stock - routinely used solutions prepared in concentrated form. Concentrated - relatively large ratio of solute to solvent. (5.0 M NaCl) Dilute - relatively small ratio of solute to solvent. (0.01 M NaCl): (MV)initial=(MV)Final 19 Figure 4.10: Steps involved in the preparation of a standard aqueous solution. 20 Figure 4.12: Dilution Procedure (a) A measuring pipet is used to transfer 28.7mL of 17.4 M acetic acid solution to a volumetric flask. (b) Water is added to the flask to the calibration mark. (c) The resulting solution is 1.00 M acetic acid. 21 Practice Example How many moles are in 18.2 g of CO2? 22 Practice Example Consider the reaction N2 + 3H2 = 2NH3 How many moles of H2 are needed to completely react 56 g of N2? 23 Practice Example How many grams are in 0.0150 mole of caffeine C8H10N4O2 24 Practice Example A solution containing Ni2+ is prepared by dissolving 1.485 g of pure nickel in nitric acid and diluting to 1.00 L. A 10.00 mL aliquot is then diluted to 500.0 mL. What is the molarity of the final solution? (Atomic weight: Ni = 58.70). 25 Practice Example Calculate the number of molecules of vitamin A, C20H30O in 1.5 mg of this compound. 26 Practice Example What is the mass percent of hydrogen in acetic acid HC2H3O2 27 Types of Solution Reactions Precipitation reactions AgNO3(aq) + NaCl(aq) AgCl(s) + NaNO3(aq) Acid-base reactions NaOH(aq) + HCl(aq) NaCl(aq) + H2O(l) Oxidation-reduction reactions Fe2O3(s) + Al(s) Fe(l) + Al2O3(s) 28 Simple Rules for Solubility Most nitrate (NO3) salts are soluble. Most alkali (group 1A) salts and NH4+ are soluble. Most Cl, Br, and I salts are soluble (NOT Ag+, Pb2+, Hg22+) Most sulfate salts are soluble (NOT BaSO4, PbSO4, HgSO4, CaSO4) 5. Most OH salts are only slightly soluble (NaOH, KOH are soluble, Ba(OH)2, Ca(OH)2 are marginally soluble) 6. Most S2, CO32, CrO42, PO43 salts are only slightly soluble. 1. 2. 3. 4. 29 Figure 4.13: When yellow aqueous potassium chromate is added to a colorless barium nitrate solution, yellow barium chromate precipitates. 30 Describing Reactions in Solution Precipitation 1. Molecular equation (reactants and products as compounds) AgNO3(aq) + NaCl(aq) AgCl(s) + NaNO3(aq) 2. Complete ionic equation (all strong electrolytes shown as ions) Ag+(aq) + NO3- (aq) + Na+ (aq) + Cl(aq) AgCl(s) + Na+ (aq) + NO3- (aq) 31 Describing Reactions in Solution (continued) 3. Net ionic equation (show only components that actually react) Ag+(aq) + Cl(aq) AgCl(s) Na+ and NO3 are spectator ions. 32 Performing Calculations for Acid-Base Reactions 1. 2. 3. 4. 5. 6. List initial species and predict reaction. Write balanced net ionic reaction. Calculate moles of reactants. Determine limiting reactant. Calculate moles of required reactant/product. Convert to grams or volume, as required. Remember: n H+ = n OH- (MV) H+ = (MV) OH33 Neutralization Reaction acid + base salt + water HCl (aq) + NaOH (aq) NaCl (aq) + H2O H+ + Cl- + Na+ + OH-- Na+ + Cl- + H2O H+ + OH- H2O 34 4.3 Key Titration Terms Titrant - solution of known concentration used in titration Analyte - substance being analyzed Equivalence point - enough titrant added to react exactly with the analyte Endpoint - the indicator changes color so you can tell the equivalence point has been reached. movie 35 Oxidation-Reduction Reactions (electron transfer reactions) 2Mg (s) + O2 (g) 2Mg O2 + 4e- 2MgO (s) 2Mg2+ + 4e- Oxidation half-reaction (lose e-) 2O2- Reduction half-reaction (gain e-) 2Mg + O2 + 4e2Mg + O2 2Mg2+ + 2O2- + 4e2MgO 36 37 Redox Reactions • Many practical or everyday examples of redox reactions: – – – – – – – Corrosion of iron (rust formation) Forest fire combustion Charcoal grill Natural gas burning Batteries Production of Al metal from Al2O3 (alumina) Metabolic processes 38 Rules for Assigning Oxidation States 1. Oxidation state of an atom in an element = 0 2. Oxidation state of monatomic element = charge 3. Oxygen = 2 in covalent compounds (except in peroxides where it = 1) 4. H = +1 in covalent compounds 5. Fluorine = 1 in compounds 6. Sum of oxidation states = 0 in compounds Sum of oxidation states = charge of the ion 39 40 Zn (s) + CuSO4 (aq) Zn ZnSO4 (aq) + Cu (s) Zn2+ + 2e- Zn is oxidized Cu2+ + 2e- Zn is the reducing agent Cu Cu2+ is reduced Cu2+ is the oxidizing agent Copper wire reacts with silver nitrate to form silver metal. What is the oxidizing agent in the reaction? Cu (s) + 2AgNO3 (aq) Cu Ag+ + 1e- Cu(NO3)2 (aq) + 2Ag (s) Cu2+ + 2eAg Ag+ is reduced Ag+ is the oxidizing agent 41 IF7 Oxidation numbers of all the elements in the following ? F = -1 7x(-1) + ? = 0 I = +7 NaIO3 Na = +1 O = -2 3x(-2) + 1 + ? = 0 I = +5 K2Cr2O7 O = -2 K = +1 7x(-2) + 2x(+1) + 2x(?) = 0 Cr = +6 42 Balancing by Half-Reaction Method 1. Write separate reduction, oxidation reactions. 2. For each half-reaction: Balance elements (except H, O) Balance O using H2O Balance H using H+ Balance charge using electrons 43 Balancing by Half-Reaction Method (continued) 3. If necessary, multiply by integer to equalize electron count. 4. Add half-reactions. 5. Check that elements and charges are balanced. 44 Half-Reaction Method Balancing in Base 1. Balance as in acid. 2. Add OH that equals H+ ions (both sides!) 3. Form water by combining H+, OH. 4. Check elements and charges for balance. 45 Balancing Redox Equations •Example: Balance the following redox reaction: •Cr2O72- + Fe2+ Cr3+ + Fe3+ (acidic soln) 1) Break into half reactions: Cr2O72Cr3+ Fe2+ Fe3+ 46 Balancing Redox Equations 2) Balance each half reaction: Cr2O72Cr3+ Cr2O72Cr2O72- 2 Cr3+ 2 Cr3+ + 7 H2O Cr2O72- + 14 H+ 6 e- + Cr2O72- + 14 H+ 2 Cr3+ + 7 H2O 2 Cr3+ + 7 H2O 47 Balancing Redox Equations 2) Balance each half reaction (cont) Fe2+ Fe2+ Fe3+ Fe3+ + 1 e- 48 Balancing Redox Reactions 3) Multiply by integer so e- lost = e- gained 6 e- + Cr2O72- + 14 H+ Fe2+ 2 Cr3+ + 7 H2O Fe3+ + 1 e- x6 49 Balancing Redox Reactions 3) Multiply by integer so e- lost = e- gained 6 e- + Cr2O72- + 14 H+ 6 Fe2+ 2 Cr3+ + 7 H2O 6 Fe3+ + 6 e- 4) Add both half reactions Cr2O72- + 6 Fe2+ + 14 H+ 2 Cr3+ + 6 Fe3+ + 7 H2O 50 Balancing Redox Reactions 5) Check the equation Cr2O72- + 6 Fe2+ + 14 H+ 2 Cr 7O 6 Fe 14 H +24 2 Cr3+ + 6 Fe3+ + 7 H2O 2 Cr 7O 6 Fe 14 H + 24 51 Balancing Redox Reactions • Procedure for Basic Solutions: – Divide the equation into 2 incomplete half reactions • one for oxidation • one for reduction 52 Balancing Redox Reactions – Balance each half-reaction: different • • • • • • • balance elements except H and O balance O atoms by adding H2O balance H atoms by adding H+ add 1 OH- to both sides for every H+ added combine H+ and OH- on same side to make H2O cancel the same # of H2O from each side balance charge by adding e- to side with greater overall + charge 53 Balancing Redox Equations – Multiply each half reaction by an integer so that • # e- lost = # e- gained – Add the half reactions together. • Simply where possible by canceling species appearing on both sides of equation – Check the equation • # of atoms • total charge on each side 54 Balancing Redox Reactions Example: Balance the following redox reaction. NH3 + ClOCl2 + N2H4 (basic soln) 1) Break into half reactions: NH3 ClO- N2H4 Cl2 55 Balancing Redox Reactions 2) Balance each half reaction: NH3 N2H4 2 NH3 N2H4 2 NH3 N2H4 + 2 H+ + 2 OH+ 2 OH2 NH3 + 2 OH 2 NH3 + 2 OH - 2 H2O N2H4 + 2 H2O N 2 H 4 + 2 H 2O + 2 e 56 Balancing Redox Reactions 2) Balance each half reaction: ClOCl2 2 ClOCl2 2 ClOCl2 + 2 H2O 2 ClO- + 4 H+ Cl2 + 2 H2O + 4 OH+ 4 OH2 ClO- + 4 H2O Cl2 + 2 H2O + 4 OH2 ClO- + 2 H2O Cl2 + 4 OH2 e- + 2 ClO- + 2 H2O Cl2 + 4 OH57 Balancing Redox Reactions 3) Multiply by integer so # e- lost = # e- gained 2 NH3 + 2 OHN2H4 + 2 H2O + 2 e2 e- + 2 ClO- + 2 H2O Cl2 + 4 OH4) Add both half reactions 2 NH3 + 2 OH- + 2ClO- + 2 H2O N2H4 + 2 H2O + Cl2 + 4 OH- 58 Balancing Redox Reactions 5) Cancel out common species 2 NH3 + 2 OH- + 2 ClO- + 2 H2O 6) Check final equation: 2 NH3 + 2 ClO2N 6H 2 Cl 2O -2 N2H4 + 2 H2O + Cl2 + 4 OH- 2 N2H4 + Cl2 + 2 OH2N 6H 2 Cl 2O -2 59 60 61 Practice Example In the following the oxidizing agent is: 5H2O2 + 2MnO4- + 6H+ 2Mn2+ + 8H2O + 5O2 a. MnO4b. H2O2 c. H+ d. Mn2+ e. O2 62 Practice Example Determine the coefficient of Sn in acidic solution Sn + HNO3 SnO2 + NO2 + H2O 1 63 Practice Example The sum of the coefficients when they are whole numbers in basic solution: Bi(OH)3 + SnO22- Bi + SnO32- 13 64 http://www.chemistrycoach.com/balancing_redox_in_acid.htm#Bal ancingRedoxEquationsinAcidicorBasicMedium 65 http://www.chemistrycoach.com/tutorials-5.htm#Oxidation-Reduction 66 • http://www.sstdt.org.sa/arc-e.htm 67 QUESTION An unknown substance dissolves readily in water but not in benzene (a nonpolar solvent). Molecules of what type are present in the substance? 1) Neither polar nor nonpolar 2) Polar 3) Either polar or nonpolar 4) Nonpolar 5) none of these 68 ANSWER 2) Polar Section 4.1 Water, the Common Solvent (p. 134) The solubility rule for molecular compounds is “like dissolves like”, that is, polar molecules dissolve in polar solvents and nonpolar molecules dissolve in nonpolar solvents. 69 QUESTION How many grams of NaCl are contained in 350. mL of a 0.250 M solution of sodium chloride? 1) 41.7 g 2) 5.11 g 3) 14.6 g 4) 87.5 g 5) None of these 70 ANSWER 2) 5.11 g Section 4.3 The Composition of Solutions (p. 140) Volume (L) times concentration (mol/L) gives moles. Moles are then converted to grams. 71 QUESTION What volume of 18.0 M sulfuric acid must be used to prepare 15.5 L of 0.195 M H2SO4? 1) 168 mL 2) 0.336 L 3) 92.3 mL 4) 226 mL 5) None of these 72 ANSWER 1) 168 mL Section 4.3 The Composition of Solutions (p. 140) Use the dilution formula, M1 V1 = M2 V2, M is in mol/L and V is in L. 73 QUESTION The net ionic equation for the reaction of aluminum sulfate and sodium hydroxide contains which of the following species? 3+ 1) 3Al (aq) – 2) OH (aq) – 3) 3OH (aq) 3+ 4) 2Al (aq) 5) 2Al(OH)3(s) 74 ANSWER 3) – 3OH (aq) Section 4.6 Describing Reactions in Solution (p. 154) The net ionic equation is found by canceling the spectator ions from the total ionic equation. 75 QUESTION Which of the following is a strong acid? 1) HF 2) KOH 3) HClO4 4) HClO 5) HBrO 76 ANSWER 3) HClO4 Section 4.2 The Nature of Aqueous Solutions: Strong and Weak Electrolytes (p. 136) Memorization of the list of strong acids will allow one to determine the difference between strong acids and weak acids. 77 QUESTION All of the following are weak acids except: 1) HCNO. 2) HBr. 3) HF. 4) HNO2. 5) HCN. 78 ANSWER 2) HBr. Section 4.2 The Nature of Aqueous Solutions: Strong and Weak Electrolytes (p. 136) Knowing the list of strong acids will allow one to determine which acids are strong and which are weak. 79 QUESTION Which of the following is not a strong base? 1) Ca(OH)2 2) KOH 3) NH3 4) LiOH 5) Sr(OH)2 80 ANSWER 3) NH3 Section 4.2 The Nature of Aqueous Solutions: Strong and Weak Electrolytes (p. 136) Knowing the list of strong bases will allow one to determine which bases are strong and which are weak. 81 QUESTION The interaction between solute particles and water molecules, which tends to cause a salt to fall apart in water, is called: 1) hydration. 2) polarization. 3) dispersion. 4) coagulation. 5) conductivity. 82 ANSWER 1) hydration. Section 4.1 Water, the Common Solvent (p. 134) Hydration is the process of water molecules surrounding and stabilizing ions so that they can be pulled into solution. 83 QUESTION The concentration of a salt water solution that sits in an open beaker decreases over time. 1) True 2) False 84 ANSWER 2) False Section 4.3 The Composition of Solutions (p. 140) The amount of water decreases over time so the concentration (mol NaCl/volume of water) increases over time. 85 QUESTION The following reactions: – Pb + 2I PbI2 4+ – 3+ 2Ce + 2I I2 + 2Ce + – HOAc + NH3 NH4 + OAc 2+ are examples of 86 QUESTION (continued) 1) 2) 3) 4) 5) acid-base reactions. unbalanced reactions. precipitation, acid-base, and redox reactions, respectively. redox, acid-base, and precipitation reactions, respectively. precipitation, redox, and acid-base reactions, respectively. 87 ANSWER 5) precipitation, redox, and acid-base reactions, respectively. Section 4.5 Precipitation Reactions (p. 151) 4+ PbI2 is insoluble, Ce changes to Ce HOAc is an acid while NH3 is a base. 3+ and 88 QUESTION Which of the following salts is insoluble in water? 1) Na2S 2) K3PO4 3) Pb(NO3)2 4) CaCl2 5) All of these are soluble in water. 89 ANSWER 5) All of these are soluble in water. Section 4.5 Precipitation Reactions (p. 153) According to the solubility rules for ionic compounds, compounds containing Group IA ions or nitrate ions will always be soluble. Compounds containing halides are generally soluble, aside from silver, lead and mercury(I) halides. 90 QUESTION 2+ When NH3(aq) is added to Cu (aq), a precipitate initially forms. Its formula is: 2+ 1) Cu(NH3)4 2) Cu(NO3)2 3) Cu(OH)2 2+ 4) Cu(NH3)4 5) CuO 91 ANSWER 3) Cu(OH)2 Section 4.4 Types of Chemical Reactions (p. 148) Ammonia produces hydroxide ion in water: + – NH3 + H2O NH4 + OH 92 QUESTION In the balanced molecular equation for the neutralization of sodium hydroxide with sulfuric acid, the products are: 1) NaSO4 + H2O 2) NaSO3 + 2H2O 3) 2NaSO4 + H2O 4) Na2S + 2H2O 5) Na2SO4 + 2H2O 93 ANSWER 5) Na2SO4 + 2H2O Section 4.8 Acid-Base Reactions (p. 158) The salt is made from the anion of the acid and the cation of the base. 94 QUESTION What mass of NaOH is required to react exactly with 25.0 mL of 1.2 M H2SO4? 1) 1.2 g 2) 1.8 g 3) 2.4 g 4) 3.5 g 5) None of these 95 ANSWER 3) 2.4 g Section 4.8 Acid-Base Reactions (p. 158) Remember that the reaction is 2NaOH + H2SO4 Na2SO4 + 2H2O, so there are two moles of NaOH used per one mole of H2SO4. 96 QUESTION In which of the following does nitrogen have an oxidation state of +4? 1) HNO3 2) NO2 3) N2O 4) NH4Cl 5) NaNO2 97 ANSWER 2) NO2 Section 4.9 Oxidation-Reduction Reactions (p. 164) Oxygen almost always has an oxidation state of –2 when part of a compound. The exception is when it is part of a peroxide. For example, hydrogen peroxide H2O2. Then it has an oxidation state of –1. 98 QUESTION In the reaction 2Cs(s) + Cl2(g) 2CsCl(s), Cl2 is 1) the reducing agent. 2) the oxidizing agent. 3) oxidized. 4) the electron donor. 5) two of these 99 ANSWER 2) the oxidizing agent. Section 4.9 Oxidation-Reduction Reactions (p. 164) Metals lose electrons, so they are oxidized, making the other reactant an oxidizing agent. 100 QUESTION Which of the following statements is(are) true? Oxidation and reduction: 1) cannot occur independently of each other. 2) accompany all chemical changes. 3) describe the loss and gain of electron(s), respectively. 4) result in a change in the oxidation states of the species involved. 5) 1, 3, and 4 are true 101 ANSWER 5) 1, 3, and 4 are true. Section 4.9 Oxidation-Reduction Reactions (p. 167) (2) is false because certain reactions, such as double displacement reactions, are not redox reactions. 102 QUESTION How many of the following are oxidationreduction reactions? NaOH + HCl NaCl + H2O Cu + 2AgNO3 2Ag + Cu(NO3)2 Mg(OH)2 MgO + H2O N2 + 3H2 2NH3 103 QUESTION (continued) 1) 2) 3) 4) 5) 0 1 2 3 4 104 ANSWER 3) 2 Section 4.9 Oxidation-Reduction Reactions (p. 164) If an element is found on the reactant’s side, this is almost always a redox reaction, since an element usually becomes part of a compound during a chemical reaction. 105