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Acid and Base Anhydrides These are compounds that themselves are not acids or base, but when dissolved in water produce an acid or base by reacting with water. Example: SO3(g) can dissolve in water and react with water. SO3(g) + H2O(l) --> H2SO4(aq) Reaction of compounds with water are called HYDRATION reactions. SO2(g), a pollutant in the atmosphere produced as a byproduct of the burning of coal, reacts with O2(g) to form SO3(g) 2SO2(g) + O2 --> 2SO3 (g) The SO3 formed then react with water in the atmosphere to form H2SO4. SO3(g) + H2O(l) --> H2SO4(l) The consequence of the reaction of SO3 and H2O is ACID RAIN. Oxides of alkali and alkaline earth metals (Gr IA and IIA) react with water to form a base and hence are base anhydrides. Na2O(s) + H2O(l) --> 2 NaOH(aq) Oxides of non-metals react with water to form acids and hence are acid anhydrides. Cl2O(g) + H2O(l) --> 2 HOCl(aq) ionic oxides --> base anhydrides covalent oxides --> acid anhydrides Other reactions of acids and bases 1) Acids react with carbonates and hydrogen carbonates (bicarbonates) producing CO2(g), salt and water NaHCO3(s) + HCl(aq) --> NaCl(aq) + H2O(l) + CO2(g) Net ionic equation NaHCO3(s) + H+(aq) + Cl-(aq) --> Na+(aq) + H2O(l) + CO2(g) 2) Acids react with oxides of metals to form salt and water CuO(s) + H2SO4(aq) --> CuSO4(aq) + H2O(l) Net ionic equation CuO(s) + 2H+(aq) --> Cu2+(aq) + H2O(l) 3) Acids react with many metallic elements to form H2(g) and a salt. Zn(s) + 2 HCl(aq) --> ZnCl2(aq) + H2(g) Net ionic equation Zn(s) + 2 H+(aq) --> Zn2+(aq) + H2(g) One of the constituents of acid rain is nitric acid. Marble has the chemical composition of calcium carbonate. Write balanced chemical equations representing how acid rain containing nitric acid dissolves marble statues. Net ionic equation CaCO3(s) + 2H+ --> Ca2+(aq) + CO2(g) + H2O(l) Naming Acids & Bases There are three classes of acids 1) Binary acids - e.g. HCl, HF replace “ide” with “ic” 2) Oxoacids - contain H, O and a 3rd element Replace “-ate” with “ic”. e.g. HNO3 - nitric acid, H2SO4 - sulfuric acid or replace “-ite” with “-ous”. e.g. HNO2 - nitrous acid 3) Organic acids - CH3COOH acetic acid Bases NaOH - sodium hydroxide Mg(OH)2 - magnesium hydroxide CH3 C OH O Oxidation-Reduction Reaction Oxidation-Reduction reactions, or REDOX reactions involve transfer of electrons between reactants Examples of reactions that fall under the class of redox reactions are the reactions that take place when a battery operates, reactions responsible for corrosion of metals, metabolic reactions Fe(s) + 2H+(aq) --> Fe2+(aq) + H2(g) Fe(s) is OXIDIZED to Fe2+ H+ is REDUCED to H2 Charges on Atoms and Molecules A charged ion forms when the neutral atom or molecule gives up or accepts electrons. Ionic compounds are made up of oppositely charged ions. Solid NaCl exists as a lattice of Na+ and Cl- interacting with each other; a crystal of potassium permanganate, KMnO4, is made up of K+ ions and MnO4- ions. The charge on these ions is real; the atom or molecule is charged. Formal Charges Formal charges are hypothetical charges calculated assuming that the electrons in a covalent bond are equally shared by both atoms. So in HCl, the formal charge on both H and Cl is zero 0 0 H Cl Formal charges do not account for electronegativities Oxidation Number or Oxidation State The oxidation number of an atom in a compound is the charge the atom would have if the compound was completely ionic. For an ionic compound, an atom’s oxidation number is the same as the charge on the atom. For example, in NaCl, the oxidation number of Na+ is +1 and that of Cl- is -1. Oxidation numbers can also be assigned to atoms in a covalent compound. In assigning oxidation number to atoms in a covalent bond, the relative electronegativity of the two bonded atoms is taken into account For example, in HCl, since Cl is more electronegative than H, Cl is assigned an oxidation state of -1 and H a +1 oxidation number. +1 -1 H Cl Assignment of oxidation numbers assumes no sharing of the electron pair in the covalent bond. Rules to assign oxidation numbers 1) The oxidation state on any atom in its elemental form is zero (H2, O2, Na(s)) 2) The sum of the oxidation states of all atoms in a neutral compound is zero (CH4, NH3) 3) The sum of the oxidation states of all atoms in an ion is equal to the charge on the ion (NO3-, SO42-) 4) The oxidation state of all Group IA elements on compounds is +1, Group IIA elements is +2 5) The oxidation state of H in compounds is +1, except in metal hydrides of very electropositive elements where it is -1 6) The oxidation state of F is always -1 7) The oxidation state of O in a compound is always -2, except where two O atoms are bonded together, as in H2O2, (each O is -1), or O is bonded to F as in OF2 (O is +2). Problem: Determine the oxidation number of S in each of the following compounds a) H2S; b) S8; c) SCl2; d) Na2SO3, e) SO42a) H : +1; S : -2 b) S8 - elemental form of S, oxidation number of S is zero c) SCl2 - Cl has an oxidation number of -1; S is +2 d) Na2SO3 - Na is +1; O is -2 2(1) + y + 3(-2) = 0 2 + y - 6 = 0; hence y = 4 Na2SO3 S is +4 e) y + (4(-2)) = -2 => y = +6. Hence in SO42- S is +6 Oxidizing and Reducing Agents An atom is oxidized (loses electrons) if its oxidation number increases, and is reduced (gains electrons) if its oxidation number decreases An oxidizing agent causes the oxidation of another species by accepting an electron from it; in the process it is reduced. A reducing agent causes the reduction of another species by giving up an electron to it; in the process it is oxidized. A strong oxidizing agent can remove electrons from a weak reducing agent and a strong reducing agent can force electrons onto a poor oxidizing agent. Animation ClO-(aq) + 2H+(aq) + Cu(s) --> Cl-(aq) + H2O(l) + Cu2+(aq) +1 -2 +1 0 -1 +1 -2 +2 ClO-(aq) + 2H+(aq) + Cu(s) --> Cl-(aq) + H2O(l) + Cu2+(aq) Types of Redox Reactions 1) Combination Reactions Most metals react with non-metals to give ionic compounds. The metals are oxidized and the non-metals reduced. Example: 2 Na(s) + Cl2(g) --> 2 NaCl(s) When the metal can form ions of different charges, different products are possible depending on the experimental conditions. Example: 2 Fe(s) + O2(g) --> FeO(s) Oxidation Number of Fe is +2 4 Fe(s) + 3O2 (g) -->2 Fe2O3(s) Oxidation Number of Fe is +3 Non-metallic compounds can combine with other nonmetallic compounds. For example, if P4(s) reacts with Cl2(g), the product depends on the amount of Cl2(g) present. If the amount of Cl2(g) is low: 0 +3 0 -1 P4(s) + 6Cl2(g) --> 4PCl3(l) At higher levels of Cl2(g) 0 0 +5 -1 P4(s) + 10Cl2(g) --> 4PCl5(l) 2) Decomposition Reactions: reverse of combination reactions For example, strong heating can result in a decomposition reaction. +1 -2 0 0 2Ag2O(s) --> 4Ag(s) + O2(g) Products of decomposition reactions can sometimes be determined by looking for chemical formulas of stable molecules (e.g. H2O, HCl, CO2, SO2, NaCl) embedded in the compound being heated. +1 +5 -2 +1 -1 0 2 KClO3-->2 KCl + 3O2 Note: Check that oxidation-reduction occurs in the reaction. +1 +3 -2 +3 -2 +1 -2 2HNO2 --> N2O3 + H2O Is this a redox reaction? 3) Oxygenation Reactions O2 is a powerful oxidizing agent and combines with most elements forming oxides. 0 0 +1 -2 4Li(s) + O2(g) -->2 Li2O(s) In the presence of excess O2, electropositive elements can also form peroxides (the peroxide ion is O2-) 0 0 +1 -1 K(s) + O2(g) --> KO2(s) Many binary compounds containing hydrogen can be oxidized by O2 to form water and an oxide. -3 +1 0 +5 -2 +1 -2 4PH3(g) + 8O2(g) --> P4O10(s) + 6H2O(g) A class of oxygenation reactions is combustion reactions where C and H containing compounds are burnt in O2 to form CO2 and H2O -4 +1 0 +4 -2 +1 -2 CH4(g) + 2O2(g) --> CO2(g) +2 H2O(g) Metabolism of glucose, C6H12O6(s), to form CO2(g) and H2O(g) 4) Hydrogenation reactions H2 is a good reducing agent. i) Nonmetallic elements are reduced by H2 0 0 -3 +1 P4(s) + H2(g) --> PH3(g) ii) However, when reacting with very electropositive elements H2 acts as an oxidizing agent, being reduced itself 0 0 +1 -1 Na(l) + H2(g) --> NaH(s) iii) H2 reacts with metal oxides to yield the metal and water +1 -2 0 0 +1 -2 Ag2O(s) + H2(g) --> 2Ag(s) + H2O (g) iv) H2 reacts with non-metal oxides to form water and the non-metal bonded to H +2 -2 0 -4 +1 +1 -2 CO(s) + 3H2(g) --> CH4(s) + H2O (g) 5) Displacement Reactions Reactions when one element displaces another from a compound. +1 +5 -2 0 +2 +5 -2 0 2AgNO3(aq) + Cu(s) --> Cu(NO3)2(aq) + Ag(s) Net ionic reaction +1 0 +2 0 2Ag+(aq) + Cu(s) --> Cu+2(aq) + Ag(s) Can we predict which element will displace another? Cu is a more electropositive element that Ag In general, the more electropositive element displaces the less electropositive element. The ACTIVITY series is a list of metals (and hydrogen) arranged in decreasing ease of oxidation Elements higher in the activity series can displace elements lower in the series. Predict what happens when i) Fe(s) is added to a solution of Cu(NO3)2 ii) Cu(s) is added to a solution of Fe(NO3)3 Why should you not cook tomatoes in an aluminum pan? Why does iron rust in an acidic solution? Displacement reactions with electronegative elements The more electronegative element displaces the less electronegative element, acting as an oxidizing agent. 0 +1 -1 0 +1 -1 Cl2 (g) + 2 KI(aq) --> I2(s) + KCl(aq) 0 -1 0 -1 Cl2 (g) + 2 I- (aq) --> I2(s) + Cl-(aq) Cl is reduced from 0 in Cl2 to -1 in KCl and I is oxidized from -1 in KI to 0 in I2 I2 (s) + 2 KCl(aq) --> ???? 6) Disproportionation Reactions A reaction in which the same compound undergoes both oxidation and reduction. +1 -1 +1 -2 0 2 H2O2(l) --> 2 H2O(l) + O2(g) A final note on redox reaction: To determine if a reaction is a redox reaction calculate the oxidation numbers of elements in the reactants and products. If the oxidation numbers of elements change during the reaction indicating that both oxidation and reduction occurs then the reaction is a redox reaction. Determining Concentrations of Solutions We can use our knowledge of the type of chemical reactions and stoichiometry to determine concentrations of solutions. Determine the volume of the solution of known concentration that is required to completely react with a given volume of the solution of unknown concentration. Method of determining the concentration of solutions is called TITRATION. Can be an acid-base reaction, precipitation reaction, redox reaction Prepare a STANDARD solution, of known concentration. Measure a known volume of the solution whose concentration is to be determined Add sufficient amount of the standard solution to completely react with the volume measured of the solution of unknown concentration. The most commonly used unit for concentration of solutions is MOLARITY which is defined as the number of moles of solute in a liter of solution. Molarity = moles of solute = mol L-1 (M) Volume of solution in liters Molarity of a solution made by dissolving 23.4 g of sodium sulfate, Na2SO4, in enough water to form 125 mL of solution. 23.4 g x 1 mol Na2SO4 142 g Na2SO4 = 0.165 mol Na2SO4 Molarity of solution = 0.165 mol Na2SO4 = 1.32 M 0.125 L solution In solution Na2SO4 completely dissociates to Na+ and SO42Na2SO4(s) --> 2 Na+(aq) + SO42-(aq) Molarity of Na+(aq) (1.32 M x 2) = 2.64 M Molarity of SO42-(aq) = 1.32 M Preparing solutions of known concentrations How many grams of Na2SO4 are required to make 350 mL of 0.500 M Na2SO4? First determine how many moles of Na2SO4 are contained in 350 mL of a 0.500 M solution. Moles of Na2SO4 = 0.500 mole Na2SO4 x 0.350 L solution 1 L solution = 0.175 moles Na2SO4 Grams of Na2SO4 = 0.175 moles Na2SO4 x 142 g Na2SO4 1 mole Na2SO4 = 24.9 g Na2SO4 Dilutions A more dilute solution of a specific concentration can be prepared from solution of higher and known concentration. Number of moles before dilution = Number of moles after dilution Since, moles = molarity (mol/L) x volume (L) For the dilution Initial molarity x initial volume = final molarity x final volume Mi x Vi = Mf x Vf How many milliliters of 3.0M H2SO4 are required to make 450 mL of 0.10 M H2SO4? Mi x Vi = Mf x Vf Vi = Mf x Vf Mi = 0.10 M x 450 mL = 15 mL 3.0 M To prepare the 0.10 M solution, measure out 15 mL of the 3.0M H2SO4 (also known as the stock solution) and add water till the total volume is 450 mL. Determining the concentation of an HCl solution via an acid-base titration HCl(aq) + NaOH(aq) --> NaCl(aq) + H2O(l) H+(aq) + OH-(aq) --> H2O(l) Net ionic equation As more NaOH is added, more of the HCl is consumed. The point at which just enough NaOH has been added so that all the HCl has been consumed is called the EQUIVALENCE point. Knowing the equivalence point, the stoichiometry of the reaction, the concentration of the NaOH solution, we can determine the concentration of the HCl solution. To indicate when the equivalence point has been reached, a very small amount of a chemical compound called an INDICATOR is added to the HCl solution, before the NaOH is added. At the equivalence point, all the HCl has reacted. Addition of a very small amount of NaOH results in a dramatic color change of the indicator. This is called the END POINT of the titration. Based on the volume of NaOH that must be added to reach the end point we can determine the concentration of the HCl. In an acid-base titration 45.7 mL of 0.500M H2SO4 is required to neutralize 20.0mL of a NaOH solution. Determine the concentration of the NaOH solution We know that at the equivalence point of the titration enough H2SO4 has been added so that all the NaOH has reacted. This means that the number of moles in 45.7 mL of 0.500M H2SO4 is enough to react with all the NaOH. We do need to know the stoichiometry of the reaction between H2SO4 and NaOH. H2SO4 + 2 NaOH --> Na2SO4 + 2 H2O This means that 1 mole of H2SO4 reacts with 2 moles of NaOH. Moles of H2SO4 added = 0.0457 L x 0.500M = 0.00228 mol Hence the number of moles of NaOH = 2 x 0.00228 = 0.00456 mol Hence, molarity of NaOH solution 0.00456 mol NaOH 0.0200 L NaOH = 2.28 M The quantity of Cl- in a water supply is determined by titrating the sample with Ag+. a) How many grams of chloride ion are in a sample of the water, if 20.2 mL of 0.100M Ag+ is required to react with all the chloride ions in the sample? b) If the sample has a mass of 10.0g,what percent chloride does it contain? Ag+(aq) + Cl-(aq) --> AgCl(s) Moles of Ag+ added = 0.100 M x 0.00202 L = 2.02 x 10-3 mol Hence, moles of Cl- in sample = 2.02 x 10-3 grams of Cl- in sample = 2.02 x 10-3 mol x 35.5g/mol Cl= 7.17 x 10-2 g Clb) % Cl- in sample = 7.17 x 10-2 g Cl10.0 g solution x 100% = 0.717 % Cl-