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33 Chapter 4: Chemical Quantities & Aqueous Reactions I) Interpreting a Balanced Chemical Reaction 1) Reactions can be viewed from the microscopic level as well as the macroscopic level. 2) The coefficients in a chemical reaction specify the relative amounts in moles of each substance involved in the reaction. II) Stoichiometry 1) Stoichiometry deals with the quantity of materials consumed and or produced in chemical reactions. 2) Stoichiometry deals specifically with mass-mole relationships between reactants and products found in a chemical equation. 3) Fundamental Principles i) ALWAYS have the balanced chemical equation ii) MOLES are the vehicle that carry us everywhere we want to go in chemistry. [AXIOM #3] 4) Handy Dandy 5 Step Method for Solving Stoichiometry Problems: Step 1: Write out the balanced chemical equation. Write givens and unknowns above items in the equation. Step 2: Calculate Molar Masses for items needed in reaction. Step 3: Convert given quantities into moles. Remember axiom #3. Step 4: Use balanced equation to set up mole ratios between given and unknown. Convert given mole quantity into moles of what we are after. Step 5: Convert final quantity moles to units desired in answer. 5) Some Examples How many grams of oxygen are required for the combustion of 96.1 g of propane (C3H8)? Step 1: 96.1 g ? g ?g ?g C3H8 + 5O2 --------> 3 CO2 + 4 H2O Step 2: MM (g/mol) 44.094 32.00 44.01 18.016 34 Note: The calculation of molar mass values are shown below. C3H8 (3 x 12.01 amu) + (8 x 1.008 amu) = 44.094 amu 44.094 g C3H8 = 1 mole C3H8 O2 32.00 g O2 = 1 mole O2 (2 x 16.00 amu) = 32.00 amu Step 3:96.1 g C3H8 x (1 mol C3H8 /44.094 g C3H8) = 2.179 mole C3H8 Note: The underlined digit (2.179 mole C3H8) represents the first uncertain digit and is used to remind us of the proper number of significant figures to that point in the calculation. Step 4:2.179 mole C3H8 x (5 mol O2 /1 mol C3H8 ) = 10.89 mole O2 Step 5:10.89 mole O2 x (32.000 g O2 / 1 mol O2) = 348.7 g O2 = 349 g O2 Check: Answer has correct units and seems reasonable. (For Homework find # g of two products produced). Answers: 288 g CO2 157 g H2O ____________________________________________________________________ III) Yields of Chemical Reactions 1) Most reactions do not go to completion (100% conversion of reactants into products). 2) In addition to the specified reaction, side reactions may also occur. 3) Instead we normally speak of the yield of a reaction (the amount of product actually formed). 4) Percent Yield Calculations % yield = (actual yield / theoretical yield) * 100 % actual yield – amount obtained by investigator during analysis theoretical yield – amount obtained assuming 100 % complete reaction Example Problem Rodney J. Smith is in the laboratory synthesizing aspirin C9H8O4. Aspirin is prepared by the following chemical reaction. Rodney starts out by reacting 11.56 g of salicylic acid (C7H6O3) with an excess of acetic anhydride (C4H6O2). If Rodney isolated 10.92 g of aspirin (C9H8O4), what is the percent yield for his experiment? 35 Apply the Handy Dandy Five Step Method to find theoretical yield. Step 1: Step 2: MM in g/mole Step 3: 11.56 g excess 10.92 g = actual yield C7H6O3 + C4H6O2 C9H8O4 + C2H4O 138.12 180.15 The acetic anhydride is in excess; that means there is more than enough acetic anhydride present to consume ALL of the salicylic acid. 11.56 g C7H6O3 x ( 1 mole C7H6O3 / 138.12 g C7H6O3) = 0.083695 moles C7H6O3 Step 4: 0.083695 moles C7H6O3 x ( 1 mole C9H8O4 / 1 mole C7H6O3 ) = 0.083695 moles C9H8O4 Step 5: 0.083695 moles C9H8O4 x ( 180.15 g C9H8O4 / 1 mole C9H8O4 ) = 15.077 g C9H8O4 % yield = (10.92 g / 15.077 g) * 100 % = 72.42 % yield = Answer _______________________________________________________________________ IV) Calculations Involving Limiting Reactants 1) Limiting Reactant (reagent): reactant that is consumed FIRST in a chemical reaction and, therefore, limits amount of products that form. 2) Examples: A) What happens if ratio of reactants is 1:1 ? - the reactant with the smallest # of moles is limiting reactant B) Suppose ratio of reactants is NOT 1:1 ? - must calculate number of moles product that forms from each reactant. Results establish which reactant is limiting (it produces the least amount of product). CH4 (g) + 2 O2 (g) ------> CO2 (g) + 2 H2O (g) 0.500 mol 2.50 mol ? mol 0.500 mol CH4 x ( 1 mol CO2 / 1 mole CH4) = 0.500 mol CO2 2.50 mol O2 x (1 mol CO2 / 2 mol O2) = 1.25 mol CO2 CH4 is limiting reactant; it produces the fewest moles of product. 36 - Another example N2 (g) + 3 H2 (g) ------> 2 NH3 (g) 5 mol 9 mol ? mol Ans. = 6 mol Let us construct a table to visualize what is going on here. N2 (g) + 3 H2 (g) ------> 2 NH3 (g) initial 1st 2nd 3rd 5 mol 4 mol 3 mol 2 mol 9 mol 6 mol 3 mol 0 mol 0 mol 2 mol 4 mol 6 mol = Answer H2 is limiting reactant so when it is used up the reaction STOPS !!! ____________________________________________________________________ 3) Production Problem Step 1: Step 2: MM (g/mole) (Real Life Situation) 25.0 kg 5.00 kg ? kg N2 (g) + 3 H2 (g) ------> 2 NH3 (g) 28.02 2.016 17.03 Step 3: Convert starting material quantities into moles and determine limiting reactant. 25.0 kg N2 x (1000 g / 1 kg) x ( 1 mol N2 / 28.02 g N2 ) = 8.922 x 102 mol N2 5.00 kg H2 x (1000 g / 1 kg) x ( 1 mol H2 / 2.016 g H2 ) = 2.480 x 103 mol H2 Note: Since reaction is NOT 1:1, we must make a comparison assuming a 1:1 ratio in order to find limiting reactant. We see from the balanced chemical equation that 1 mol nitrogen reacts with 3 mol hydrogen, so we now find the EXACT # moles hydrogen needed for a complete reaction (stoichiometric reaction). 8.922 x 102 mol N2 x ( 3 mol H2 / 1 mol N2 ) = 2.676 x 103 mol H2 Find the limiting reactant Since 2.676 x 103 mol H2 (exact quantity needed) is >> 2.480 x 103 mol H2 (calculated quantity), H2 is limiting reactant . 37 Steps 4 & 5: Solve the problem in the usual "handy dandy" fashion ! 2.480 x 103 mol H2 x (2 mol NH3 / 3 mol H2 ) = 1.653 x 103 mol NH3 1.653 x 103 mol NH3 x (17.03 g NH3 / 1 mol NH3) = 28,158 g NH3 Simply converting to kg gives final answer 28,158 g NH3 x (1 kg / 1000 g) = 28.1 kg NH3 (Value is reasonable). ______________________________________________________________________ V) Introduction to Solutions 1) A solution is a homogeneous mixture consisting of two components. A) Solute – substance being dissolved in the solution. B) Solvent – dissolving medium. This component is always in greatest amount. C) Most chemical reactions are carried out in the liquid state or in solution. This is due to the requirement that reactant molecules or ions be highly mobile so they can interact with each other. 2) Although solutions can be described as being concentrated or dilute; it is often necessary to quantify a solution’s concentration. A) There are many ways of expressing solution concentration, but for the moment we will only focus on molarity. B) Molarity = M = moles solute / Volume of solution in liters C) To find the number of moles of solute one uses the following relationship Volume of solution in liters x Molarity = moles of solute D) To find the volume of solution one need only manipulate the above equation Volume of solution in liters = moles of solute / Molarity 3) Solutions are often prepared by adding a weighed quantity of solute to a volumetric flask and dissolving the contents in solvent. When the flask is filled to the mark with solvent, the concentration of the solution is accurately known. 38 4) Example Molarity Calculation What is the molarity of a solution prepared by adding 11.5 g of NaOH to 1.50 L of water? (Note: The molar mass of NaOH is 40.00 g/mole) Unknown: Given: ? M (NaOH) 11.5 g NaOH + 1.50 L water Rel. Info: M = # moles solute / Vol. soln. (L) Solution: # moles NaOH = 11.5 g NaOH x (1 mole / 40.00 g NaOH) Water is solvent! # moles NaOH = 0.288 moles NaOH Therefore, M = 0.288 mol NaOH / 1.50 L = 0.192 M (Reasonable) ________________________________________________________________ 5) Diluting Concentrated Solutions A) Dilution - process by which water (or another solvent) is added to a solution of known concentration to achieve a new solution of lower concentration. B) Dilution does not alter the number of moles of solute. # MOLES SOLUTE AFTER = # MOLES SOLUTE BEFORE DILUTION DILUTION C) Dilution Equation M1V1 = M2V2 VI) Solution Stoichiometry 1) Solving stoichiometry problems with one or both reactants in solution involves applying the same 5 step method. The only “change” usually involves getting the number of moles of reactant(s) that are in solution. 2) To obtain the number of moles of reactant, one need only apply the equation Volume of solution in liters x Molarity = moles of solute 39 VII) Introduction to Titrations 1) A titration is a technique that allows one to determine the concentration of a solution by allowing a carefully measured volume to react with another substance whose concentration is accurately known. 2) The solution of known concentration, called the titrant, is dispensed from a buret. 3) An indicator is used as a visual means of determining when the titration is finished. The end of a titration is usually observed when the indicator undergoes a dramatic color change VIII) Water, The Universal Solvent 1) Water is a very common solvent due to its wide availability and low cost (most of our world is water). 2) Many reactions take place in aqueous solution. The term aqueous means dissolved in water. 3) Hydration of solids in Water A) Solid dissolves (falls apart) through interaction of ions with water. B) Newly formed ions are now “FREE TO MOVE”. C) “Like Dissolves Like” i) polar materials dissolve in polar solvents ii) nonpolar materials dissolve in nonpolar solvents. 4) For now, consider that chemical reactions involve a “driving force” that account for reactants being converted into products. 5) Three general categories of aqueous solutions. A) Precipitation reactions B) Acid-Base Neutralization reactions C) Oxidation-Reduction (Redox) reactions IX) Electrolytes in Aqueous Solutions 1) Electrical conductivity is a property associated with solutions. 2) Substances (e.g. NaCl, KBr, etc.) that produce ions when dissolved in water are called electrolytes. 3) The concept of electrolytes was first proposed by Arrhenius. 4) An electrolyte solution conducts electricity because the ions are free to when dissolved in water. 40 5) Types of Electrolytes A) strong electrolytes: completely ionize in solution Examples: SA (HCl, HNO3, HClO4, H2SO4) SB (NaOH, LiOH, KOH) soluble salts (NaCl, KF, BaCl2) Arrhenius: acids- source of H+ ions bases - source of OH- ions HCl NaOH sour taste feel slippery H+ (aq) + Cl- (aq) Na+ (aq) + OH- (aq) B) weak electrolytes: incompletely ionize in solution Examples WA WB C) nonelectrolytes: Examples acetic acid ammonia HoAc <-----> H+ + oAcNH3 <--------> NH4+ + OH- do not produce ions when dissolved in water. EtOH and sucrose dissolved in water EtOH (l) -------> EtOH (l) sucrose (s) ---------> sucrose (l) X) Precipitation Reactions & Solubility Rules 1) A precipitate is an insoluble solid formed by mixing two or more solutions together. 2) Precipitates are NEUTRAL in charge. 3) Precipitate formation is possible since dissolved ions move freely in solution. 4) Beaker Analogy – used to determine identity of products in solution. Example 1: Ba(NO3)2 (aq) + K2CrO4 (aq) ---------> products colorless yellow soln yellow ppt observed Ba2+ (aq) + 2 NO3 - (aq) + 2 K+ (aq) + CrO4 2- (aq) ---------> products Check solubility (Review Table 4.1). Know the general trends for solubility. From picture, KNO3 and BaCrO4 are products that are possible. Other two are reactants !! 41 - Also yellow soln in reactants leads us to believe yellow ppt. in product contains ion from that reactant... KNO3 is soluble salt and BaCrO4 is an insoluble salt (must be identity of yellow solid)... Describing Precipitation Reactions 1) Molecular Equation - gives overall solution stoichiometry... Ba(NO3)2 (aq) + K2CrO4 (aq) ---------> 2 KNO3 (aq) + BaCrO4 (s) 2) Complete Ionic Equation - strong electrolytes represented as free moving ions... Ba2+ (aq) + 2 NO3- (aq) + 2 K+ (aq) + CrO42- (aq) -----> 2 K+ (aq) + 2 NO3- (aq) + BaCrO4 (s) 3) Net Ionic Equation - gets rid of spectator ions (ions that do not DIRECTLY participate in the reaction). ONLY include species which directly take part in the reaction. Ba2+ (aq) + CrO4 2- (aq) ---------> BaCrO4 (s) Example 2: (yellow solid) AgNO3 (aq) + KCl (aq) ---------> products colorless colorless (white solid observed) AgNO3 (aq) + KCl (aq) ---------> AgCl (s) + KNO3 (aq) Ag+ (aq) + NO3- (aq) + K+ (aq) + Cl- (aq) ---------> AgCl (s) + K+ (aq) + NO3 - (aq) Ag+ (aq) + Cl- (aq) ---------> AgCl (s) KEY TO SUCCESS: DRAW PICTURE. DETERMINE LIKELY PRODUCTS & KNOW TRENDS. (Review Table 4.1) Slightly soluble means same thing as insoluble (Why the distinction?) Slightly soluble means a tiny portion of solid dissolves but is not noticeable to observer 42 XI) Acid/Base Reactions 1) There are three systems for defining acids & bases. A) Arrhenius i) Acids contain H+ in chemical formula. ii) Bases contain OH- in chemical formula. H+ proton B) Bronsted-Lowry i) Acids are proton donors. ii) Bases are proton acceptors. C) Lewis (CHE 124) 2) Mixing Acids and Bases [Neutralization Reaction] Acid + Base salt + water KEY: Write down species present and figure out reaction being studied... (always) [SA + SB -------> Neutral Salt + Water] [WA + SB ------> Basic Salt + Water] [WB + SA ------> Acidic Salt + Water] XII) Oxidation/Reduction Reactions (Redox Rxns) 1) Redox reactions are characterized by electrons being transferred between species. 2) Number line pneumonic 3) Fundamental Definitions KNOW THESE A) oxidation - loss of electrons (moving to right on number line) B) reduction - gain of electrons (moving to left on number line) C) oxidizing agent - species being reduced (electron acceptor) D) reducing agent - species being oxidized (electron donor) 4) Oxidation States (Oxidation Numbers) A) Electron Accounting B) Learn rules for assigning oxidation numbers (see page ). Designate charged ions as n+ or m- 43 Designate oxidation states as +n or -m 5) Oxidation and reduction reactions always occur together.