Chapter 4 Electrolytes and Aqueous Reactions. Dr. Sapna Gupta

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Chapter 4 Electrolytes and Aqueous Reactions Dr. Sapna Gupta

Aqueous Solutions Solution - a homogeneous mixture of solute + solvent Solute: the component that is dissolved Solvent: the component that does the dissolving (the larger quantity) Aqueous solutions are those in which water is the solvent. Dissociation - ionic compounds separate into constituent ions when dissolved in solution Ionization - formation of ions by molecular compounds when dissolved Dr. Sapna Gupta/Electrolytes 2

Electrolytes Electrolyte: substance that dissolved in water produces a solution that conducts electricity. Will contain ions. Strong Electrolyte: substances that dissolve completely in water; 100% dissociation All water soluble ionic compounds, strong acids and strong bases Weak Electrolytes: substances that dissolve partially or dissociate partially in water. This solution does not contain many ions. Exist mostly as the molecular form in solution Weak acids and weak bases Nonelectrolyte: substance that dissolved in water produces a solution that does not conduct electricity and does not contain ions. Dr. Sapna Gupta/Electrolytes 3

Electrolytes Method to Distinguish Types of Electrolytes nonelectrolyte weak electrolyte strong electrolyte Dr. Sapna Gupta/Electrolytes 4

Strong Acids These acids dissociate completely Dr. Sapna Gupta/Electrolytes 5

Electrolytes Practical Application Our body is about 70% water and we have a number of ionic salts in our body. Some common ions are Na +, Ca 2+, K +, Cl -, CO 3 2-. Electrolytes maintain voltages in our cells; they help with nerve impulses in our nervous system and help with muscle contractions. We get electrolytes through our diet and the kidneys are responsible for maintaining an electrolytic balance in the body. If the ions are not in the correct concentration then the above mentioned functions cannot occur. One way we lose electrolytes is during sweating. This is two fold one: we lose water in the body so the concentration of ions change and two: we lose ions also during sweating. These ions have to replenished or we can lose muscle control. Electrolytes (sports drinks) are commonly used to replace these ions. One has to be careful though they also have a lot of sugar in them! The first electrolyte beverage was invented in University of Florida Dr. Sapna Gupta/Electrolytes 6

Types of Reactions Two classifications: one how atoms are rearrangement and the other is chemical reaction 1) Atomic Rearrangement Synthesis (combination): two substances combine to form one. 2Na(s) + Cl 2 (g) 2NaCl(s) Double Displacement: A reaction in which two elements displaces two elements. AgNO 3 (aq) + NaCl(aq) AgCl(s) + NaNO 3 (aq) Single displacement: A reaction where one element displaces one other element. Zn(s) + CuSO 4 (aq) ZnSO 4 (aq) + Cu(s) Decomposition: A reaction in which a single compound reacts to give two or more substances. 2HgO(s) 2Hg(l) + O 2 (g) 2) Chemical Classification: Types of Chemical Reactions Precipitation Reactions: where a solid is formed when two solutions are mixed. Neutralization Reactions: when an acid and base react to from salt and water. Oxidation Reduction Reactions: addition or removal of oxygen and/or transfer of electrons. Dr. Sapna Gupta/Electrolytes 7

Precipitation Reactions Precipitation (formation of a solid from two aqueous solutions) occurs when product is insoluble in water. Reaction type: Double displacement What is solubility? Solubility is defined as the maximum amount of a solid that can dissolve in a given amount of solvent at a specified temperature Prediction of precipitate is based on solubility rules Dr. Sapna Gupta/Electrolytes 8

Solubility Guidelines Dr. Sapna Gupta/Electrolytes 9

Solved Problems 1) Identify the Precipitate Pb(NO 3 ) 2 (aq) + 2NaI(aq) 2NaNO 3 + PbI 2 PbI 2 according to solubility rules 2) Classify the following as soluble or insoluble in water Ba(NO 3 ) 2 soluble AgI insoluble Mg(OH) 2 insoluble Dr. Sapna Gupta/Electrolytes 10

Writing Equations in Aqueous Solutions A chemical equation in which the reactants and products are written as if they were molecular substances, even though they may actually exist in solution as ions. Symbols indicating the states are include: (s), (l), (g), (aq). For example: Molecular Equation: AgNO 3 (aq) + NaCl(aq) AgCl(s) + NaNO 3 (aq) Although AgNO 3, NaCl, and NaNO 3 exist as ions in aqueous solutions, they are written as compounds in the molecular equation. Ionic Equation: Ag + (aq) + NO 3 (aq) + Na + (aq) + Cl (aq) AgCl(s) + Na + (aq) + NO 3 (aq) All compounds that dissociate are shown as ions. Net Ionic Equation: In this the spectator ions (ions on both sides of the equation) are eliminated. Ag + (aq) + NO 3 (aq) + Na + (aq) + Cl (aq) AgCl(s) + Na + (aq) + NO 3 (aq) Net ionic equation represents the ions reacting. Those will be (g), (l) and (s) products formed. Ag + (aq) + Cl (aq) AgCl(s) Dr. Sapna Gupta/Electrolytes 11

Solved Problems Decide whether the following reaction occurs. If it does, write the molecular, ionic, and net ionic equations. KBr + MgSO 4 Determine the product formulas by double displacement method K + and SO 4 2 make K 2 SO 4 Mg 2+ and Br make MgBr 2 Determine whether the products are soluble: K 2 SO 4 is soluble and MgBr 2 is soluble KBr + MgSO 4 no reaction Dr. Sapna Gupta/Electrolytes 12

Solved Problems Decide whether the following reaction occurs. If it does, write the molecular, ionic, and net ionic equations. NaOH + MgCl 2 Determine the product formulas by double displacement method Na + and Cl make NaCl Mg 2+ and OH make Mg(OH) 2 Determine whether the products are soluble NaCl is soluble and Mg(OH) 2 is insoluble Molecular Equation Balance the reaction and include state symbols 2NaOH(aq) + MgCl 2 (aq) 2NaCl(aq) + Mg(OH) 2 (s) Ionic Equation 2Na + (aq) + 2OH (aq) + Mg 2+ (aq) + 2Cl (aq) 2Na + (aq) + 2Cl (aq) + Mg(OH) 2 (s) Net Ionic Equation 2OH (aq) + Mg 2+ (aq) Mg(OH) 2 (s) Dr. Sapna Gupta/Electrolytes 13

One more. Decide whether the following reaction occurs. If it does, write the molecular, ionic, and net ionic equations. K 3 PO 4 + CaCl 2 Determine the product formulas: K + and Cl make KCl; Ca 2+ and PO 4 3 make Ca 3 (PO 4 ) 2 Determine whether the products are soluble: KCl is soluble and Ca 3 (PO 4 ) 2 is insoluble Molecular Equation (Balance the reaction and include state symbols) 2K 3 PO 4 (aq) + 3CaCl 2 (aq) 6KCl(aq) + Ca 3 (PO 4 ) 2 (s) Ionic Equation 6K + (aq) + 2PO 4 3 (aq) + 3Ca 2+ (aq) + 6Cl (aq) 6K + (aq) + 6Cl (aq) + Ca 3 (PO 4 ) 2 (s) Net Ionic Equation 2PO 4 3 (aq) + 3Ca 2+ (aq) Ca 3 (PO 4 ) 2 (s) Dr. Sapna Gupta/Electrolytes 14

Another one. Aqueous solutions of silver nitrate and sodium sulfate are mixed. Write the net ionic reaction. 2AgNO 3 (aq)+na 2 SO 4 (aq) 2NaNO 3 (?)+Ag 2 SO 4 (?) Determine solubility of salts. All nitrates are soluble but silver sulfate is insoluble Molecular Equation 2AgNO 3 (aq)+na 2 SO 4 (aq) 2NaNO 3 (aq)+ag 2 SO 4 (s) Ionic equation 2Ag + (aq) + 2NO 3 (aq) + 2Na + (aq) + SO 4 2 (aq) 2Na + (aq) + 2NO 3 (aq) + Ag 2 SO 4 (s) Cancel spectators 2Ag + (aq) + 2NO 3 (aq) + 2Na + (aq) + SO 4 2 (aq) 2Na + (aq) + 2NO 3 (aq) + Ag 2 SO 4 (s) Net ionic equation 2Ag + (aq) + SO 4 2 (aq) Ag 2 SO 4 (s) Dr. Sapna Gupta/Electrolytes 15

Neutralization Reactions (acid-base) Acids Arrhenius Acid A substance that produces hydrogen ions, H +, when dissolved in water. Brønsted Lowry Acid The species (molecule or ion) that donates a proton, H +, to another species in a proton transfer reaction. Sour Corrosive Bases Arrhenius Base A substance that produces hydroxide ions, OH, when dissolved in water. Brønsted Lowry Base The species (molecule or ion) that accepts a proton, H +, from another species in a proton transfer reaction. Bitter Caustic, slippery ph value 1-7 ph value 7-14 Strong acids (inorganic acids) ionize completely in water, e.g.: HNO 3, H 2 SO 4, HClO 4, HCl, HBr, HI Strong bases (inorganic bases) ionize completely in water; most are hydroxides, e.g.: NaOH, KOH, Ca(OH) 2 Weak acids ionize partially in water, Weak bases ionize partially in water, e.g. HF e.g.: NH 4 OH, Na 2 CO 3, NaHCO 3 Organic acid: HC 2 H 3 O 2 (CH 3 COOH) organic bases: CH 3 NH 2 Dr. Sapna Gupta/Electrolytes 16

Common Acids and Bases Dr. Sapna Gupta/Electrolytes 17

More on Acids-Bases Indicators: these are chemicals used to determine if an acid or base is strong or weak by changing colors. Polyprotic Acid: An acid that results in two or more acidic hydrogens per molecule. For example: H 2 SO 4, sulfuric acid Neutralization Reaction: Almost all acid base reactions are double displacement reactions. Most will produce a salt and water as product. Carbonates and sulfites give CO 2 and SO 2 gases in product. Dr. Sapna Gupta/Electrolytes 18

Acid-Base Neutralization Reactions Neutralization: Reaction between an acid and a base Acid + Base Salt + Water Molecular equation: HCl(aq) + NaOH(aq) NaCl(aq) + H 2 O(l) Ionic equation: H + (aq)+ Cl (aq) + Na + (aq) + OH (aq) Na + (aq) + Cl (aq) + H 2 O(l) Net ionic equation: H + (aq) + OH (aq) H 2 O(l) Dr. Sapna Gupta/Electrolytes 19

Neutralization Reactions Write the molecular, ionic, and net ionic equations for the neutralization of sulfurous acid, H 2 SO 3, by potassium hydroxide, KOH The reaction is a double displacement reaction. Molecular Equation (Balance the reaction and include state symbols) H 2 SO 3 (aq) + 2KOH(aq) 2H 2 O(l) + K 2 SO 3 (aq) Ionic Equation H 2 SO 3 (aq) + 2K + (aq) + 2OH (aq) 2H 2 O(l) + 2K + (aq) + SO 3 2 (aq) Net Ionic Equation H 2 SO 3 (aq) + 2OH (aq) 2H 2 O(l) + SO 3 2 (aq) Dr. Sapna Gupta/Electrolytes 20

Neutralization Reactions Producing Gases Sulfides, carbonates, sulfites react with acid to form a gas. Na 2 S(aq) + 2HCl(aq) 2NaCl(aq) + H 2 S(g) Na 2 CO 3 (aq) + 2HCl(aq) 2NaCl(aq) + H 2 O(l) + CO 2 (g) Na 2 SO 3 (aq) + 2HCl(aq) 2NaCl(aq) + H 2 O(l) + SO 2 (g) The photo below shows baking soda (sodium hydrogen carbonate) reacting with acetic acid in vinegar to give bubbles of carbon dioxide. + Dr. Sapna Gupta/Electrolytes 21

Neutralization Reaction another one Molecular Equation (Balance the reaction and include state symbols) CuCO 3 (s) + 2HCl(aq) CuCl 2 (aq) + H 2 O(l) + CO 2 (g) Ionic Equation CuCO 3 (s) + 2H + (aq) + 2Cl (aq) Cu 2+ (aq) + 2Cl (aq) + H 2 O(l) + CO 2 (g) Net Ionic Equation CuCO 3 (s) + 2H + (aq) Cu 2+ (aq) + H 2 O(l) + CO 2 (g) Dr. Sapna Gupta/Electrolytes 22

Redox Reactions Oxidation Addition of oxygen Removal of hydrogen Loss of electrons (LEO) Metals lose electrons hence undergo oxidation Reducing agents something that causes reduction of another element and gets oxidized (loses electrons) itself Reduction Removal of oxygen Addition of hydrogen Gain of electrons (GER) Non metals gain electrons hence undergo reduction Oxidizing agent an element that causes oxidation of another element and gets reduced (gains electrons) itself Dr. Sapna Gupta/Electrolytes 23

Writing Redox Reactions Example Zn(s) + CuSO 4 (aq) ZnSO 4 (aq) + Cu(s) gaining 2 electrons, reduction Zn(s) + Cu 2+ (aq) Zn 2+ (aq) + Cu(s) loses 2 electrons, oxidation Half Reactions: Zinc is losing 2 electrons and oxidized. It is the reducing agent Zn(s) Zn 2+ (aq) + 2e Copper ions are gaining the 2 electrons. It is the oxidizing agent Cu 2+ (aq) + 2e Cu(s) Dr. Sapna Gupta/Electrolytes 24

Rules for Assigning Oxidation Numbers 1. Elements: The oxidation number of an element is zero. 2. Monatomic ions: The oxidation number of a monatomic ion equals the charge on the ion. 3. Oxygen: The oxidation number of oxygen is 2 in most compounds. (An exception is O in H 2 O 2 and other peroxides, where the oxidation number is 1.) 4. Hydrogen: The oxidation number of hydrogen is +1 in most of its compounds. (The oxidation number of hydrogen is 1 in binary compounds with a metal such as CaH 2.) 5. Halogens: The oxidation number of fluorine is 1. Each of the other halogens (Cl, Br, I) has an oxidation number of 1 in binary compounds, except when the other element is another halogen above it in the periodic table or the other element is oxygen. 6. Compounds and ions: The sum of the oxidation numbers of a compound is zero. The sum of the oxidation numbers of the atoms in a polyatomic ion equals the charge on the ion. Dr. Sapna Gupta/Electrolytes 25

Oxidation Numbers on the Periodic Table (most common in red) Dr. Sapna Gupta/Electrolytes 26

Activity Series Loses electrons easily Does not lose electrons easily Dr. Sapna Gupta/Electrolytes 27

Assigning Oxidation States Assign oxidation numbers for all elements in each species 1) MgBr 2 : Mg +2, Br 1 x 2= -2; +2 +(-2) = total charge of 0 2) ClO 2 : O 2 x 2 = -4; Cl +3; (-4) + (+3) = -1 (charge left over on ion) 3) Assign oxidation number of Mn in KMnO 4 K Mn O 1(+1) + 1(oxidation number of Mn) + 4( 2) = 0 1 + 1(oxidation number of Mn) + ( 8) = 0 ( 7) + (oxidation number of Mn) = 0 Oxidation number of Mn = +7 4) What is the oxidation number of Cr in dichromate, Cr 2 O 7 2? Cr 2(oxidation number of Cr) + 7( 2) = 2 2(oxidation number of Cr) + ( 14) = 2 2(oxidation number of Cr) = +12 Oxidation number of Cr = +6 Dr. Sapna Gupta/Electrolytes 28 O

Balancing Redox Equations (electronically) Balance the following reaction. Zn(s) + Ag + (aq) Zn 2+ (aq) + Ag(s) Oxidation Numbers 0 + +2 0 Next, write the unbalanced half reactions. Zn(s) Zn 2+ (aq) Ag + (aq) Ag(s) (oxidation) (reduction) Now, balance the charge in each half reaction by adding electrons. Zn(s) Zn 2+ (aq) + 2e e + Ag + (aq) Ag(s) (oxidation) (reduction) Each half reaction should have the same number of electrons. To do this, multiply each half reaction by a factor so that when the half reactions are added, the electrons cancel. Zn(s) Zn 2+ (aq) + 2e 2e + 2Ag + (aq) 2Ag(s) (oxidation) (reduction) Lastly, add the two half reactions together. Zn(s) + 2Ag + (aq) Zn 2+ (aq) + 2Ag(s) Dr. Sapna Gupta/Electrolytes 29

One more Balancing Redox Equation FeI 3 (aq) + Mg(s) Fe(s) + MgI 2 (aq) The oxidation numbers are given below the reaction. FeI 3 (aq) + Mg(s) Fe(s) + MgI 2 (s) +3 1 0 0 +2 1 Now, write the half reactions. Since Iodide is a spectator ion it is omitted at this point. Mg(s) Mg 2+ (aq) Fe 3+ (aq) Fe(s) Balancing the half reactions: Mg(s) Mg 2+ (aq) + 2e (oxidation) (reduction) Fe 3+ (aq) + 3e Fe(s) (reduction) (oxidation) Multiply the oxidation half reaction by 3 and the reduction half reaction by 2. 3Mg(s) 3Mg 2+ (aq) + 6e 2Fe 3+ (aq) + 6e 2Fe(s) Add the half reactions together. (oxidation) (reduction) 2Fe 3+ (aq) + 3Mg(s) 2Fe(s) + 3Mg 2+ (aq) Now, return the spectator ion, I. 2FeI 3 (aq) + 3Mg(s) 2Fe(s) + 3MgI Dr. Sapna 2 (aq) Gupta/Electrolytes 30

Types of Redox Reactions Displacement reactions A common reaction: active metal replaces (displaces) a metal ion from a solution (use the activity series to predict if reaction will take place) Mg(s) + CuCl 2 (aq) Cu(s) + MgCl 2 (aq) Decomposition reactions 2KClO 3 (s) 2KCl(s) + 3O 2 (g) Combination Reactions 2H 2 (g) + O 2 (g) 2H 2 O(l) Combustion reactions Common example, hydrocarbon fuel reacts with oxygen to produce carbon dioxide and water CH 4 (g) + O 2 (g) H 2 O(l) + CO 2 (g) Dr. Sapna Gupta/Electrolytes 31

Solved Example Classify the following reactions as precipitation; acid-base; or redox reaction and any other classification that can describe the reaction. 2H 2 + O 2 2H 2 O Redox (combustion, combination) Zn + H 2 SO 4 ZnSO 4 + H 2 Redox (single displacement) H 2 O + NH 3 NH 4+ + OH - Acid-base (double displacement) 6FeSO 4 + K 2 Cr 2 O 7 + 7H 2 SO 4 Cr 2 (SO 4 ) 3 + 3Fe 2 (SO 4 ) 3 + K 2 SO 4 + 7H 2 O Redox 2NaCl + Pb(NO 3 ) 2 PbCl 2 + 3NaNO 3 Precipitation (double displacement) Dr. Sapna Gupta/Electrolytes 32

Key Words and Concepts Ions in Aqueous Solution Electrolytes Solubility Rules Molecular, Ionic and Net Ionic Equations Types of Chemical Reactions Precipitation Reactions Acid Base Reactions Oxidation Reduction Reactions Oxidation Reduction Reducing agent Oxidizing agent Half reactions Dr. Sapna Gupta/Electrolytes 33