Chemistry: A Molecular Approach, 1st Ed. Nivaldo Tro Chapter 12 Solutions Roy Kennedy Massachusetts Bay Community College Wellesley Hills, MA 2008, Prentice Hall Solution • homogeneous mixtures composition may vary from one sample to another appears to be one substance, though really contains multiple materials • most homogeneous materials we encounter are actually solutions e.g., air and sea water • nature has a tendency toward spontaneous mixing generally, uniform mixing is more energetically favorable Tro, Chemistry: A Molecular Approach 2 Solutions • solute is the dissolved substance • • • seems to “disappear” “takes on the state” of the solvent solvent is the substance solute dissolves in does not appear to change state when both solute and solvent have the same state, the solvent is the component present in the highest percentage solutions in which the solvent is water are called aqueous solutions Tro, Chemistry: A Molecular Approach 3 Common Types of Solution Solution Phase gaseous solutions liquid solutions solid solutions Solute Phase gas gas liquid solid solid Solvent Phase gas liquid liquid liquid solid Example air (mostly N2 & O2) soda (CO2 in H2O) vodka (C2H5OH in H2O) seawater (NaCl in H2O) brass (Zn in Cu) • solutions that contain Hg and some other metal are • called amalgams solutions that contain metal solutes and a metal solvent are called alloys Tro, Chemistry: A Molecular Approach 4 Brass Type Color % Cu % Zn Density g/cm3 MP °C Tensile Strength psi Uses Gilding redish 95 5 8.86 1066 50K pre-83 pennies, munitions, plaques Commercial bronze 90 10 8.80 1043 61K door knobs, grillwork Jewelry bronze 87.5 12.5 8.78 1035 66K costume jewelry Red golden 85 15 8.75 1027 70K electrical sockets, fasteners & eyelets Low deep yellow 80 20 8.67 999 74K musical instruments, clock dials Cartridge yellow 70 30 8.47 954 76K car radiator cores Common yellow 67 33 8.42 940 70K lamp fixtures, bead chain Muntz metal yellow 60 40 8.39 904 70K nuts & bolts, brazing rods 5 Solubility • when one substance (solute) dissolves in another • (solvent) it is said to be soluble salt is soluble in water bromine is soluble in methylene chloride when one substance does not dissolve in another it is said to be insoluble oil is insoluble in water • the solubility of one substance in another depends on two factors – nature’s tendency towards mixing, and the types of intermolecular attractive forces Tro, Chemistry: A Molecular Approach 6 Spontaneous Mixing Tro, Chemistry: A Molecular Approach 7 Solubility • there is usually a limit to the solubility of one substance in another gases are always soluble in each other two liquids that are mutually soluble are said to be miscible alcohol and water are miscible oil and water are immiscible • the maximum amount of solute that can be dissolved • in a given amount of solvent is called the solubility the solubility of one substance in another varies with temperature and pressure Tro, Chemistry: A Molecular Approach 8 Mixing and the Solution Process Entropy • formation of a solution does not necessarily lower the potential energy of the system the difference in attractive forces between atoms of two separate ideal gases vs. two mixed ideal gases is negligible yet the gases mix spontaneously • the gases mix because the energy of the • • system is lowered through the release of entropy entropy is the measure of energy dispersal throughout the system energy has a spontaneous drive to spread out over as large a volume as it is allowed Tro, Chemistry: A Molecular Approach 9 Intermolecular Forces and the Solution Process Enthalpy of Solution • energy changes in the formation of most solutions also • involve differences in attractive forces between particles must overcome solute-solute attractive forces endothermic • must overcome some of the solvent-solvent attractive forces endothermic • at least some of the energy to do this comes from making new solute-solvent attractions exothermic Tro, Chemistry: A Molecular Approach 10 Intermolecular Attractions Tro, Chemistry: A Molecular Approach 11 Relative Interactions and Solution Formation Solute-to-Solvent Solute-to-Solvent Solute-to-Solvent Solute-to-Solute + > Solution Forms Solvent-to-Solvent Solute-to-Solute + = Solution Forms Solvent-to-Solvent Solute-to-Solute + Solution May or < Solvent-to-Solvent May Not Form • when the solute-to-solvent attractions are weaker than the sum of the solute-to-solute and solvent-to-solvent attractions, the solution will only form if the energy difference is small enough to be overcome by the entropy Tro, Chemistry: A Molecular Approach 12 Solution Interactions Tro, Chemistry: A Molecular Approach 13 Will It Dissolve? • Chemist’s Rule of Thumb – Like Dissolves Like • a chemical will dissolve in a solvent if it has a similar • structure to the solvent when the solvent and solute structures are similar, the solvent molecules will attract the solute particles at least as well as the solute particles to each other Tro, Chemistry: A Molecular Approach 14 Classifying Solvents Solvent Class Structural Feature Water, H2O polar O-H Methyl Alcohol, CH3OH Ethyl Alcohol, C2H5OH Acetone, C3H6O polar polar polar O-H O-H C=O Toluene, C7H8 Hexane, C6H14 Diethyl Ether, C4H10O nonpolar nonpolar nonpolar C-C & C-H C-C & C-H C-C, C-H & C-O, (nonpolar > polar) Carbon Tetrachloride nonpolar C-Cl, but symmetrical Tro, Chemistry: A Molecular Approach 15 Example 12.1a predict whether the following vitamin is soluble in fat or water OH The 4 OH groups make the molecule highly polar and it will also H-bond to water. Vitamin C is water soluble OH H2C C H H C O C C O C HO OH Vitamin C Tro, Chemistry: A Molecular Approach 16 Example 12.1b predict whether the following vitamin is soluble in fat or water The 2 C=O groups are polar, but their geometric symmetry suggests their pulls will cancel and the molecule will be nonpolar. O H C C CH3 HC C C HC C CH C H C O Vitamin K3 is fat soluble Tro, Chemistry: A Molecular Approach Vitamin K3 17 Energetics of Solution Formation • overcome attractions between the solute particles – • • • endothermic overcome some attractions between solvent molecules – endothermic for new attractions between solute particles and solvent molecules – exothermic the overall DH depends on the relative sizes of the DH for these 3 processes DHsol’n = DHsolute +DHsolvent + DHmix Tro, Chemistry: A Molecular Approach 18 Solution Process 1. add energy in to overcome solute-solute attractions 3. form new solute-solvent attractions, releasing energy 2. add energy in to overcome some solvent-solvent attractions Tro, Chemistry: A Molecular Approach 19 Energetics of Solution Formation if the total energy cost for breaking attractions between particles in the pure solute and pure solvent is greater less thanthan the the energy released in making the new attractions between the solute and solvent, the overall process will be endothermic exothermic Tro, Chemistry: A Molecular Approach 20 Heats of Hydration • for aqueous ionic solutions, the energy added to overcome the attractions between water molecules and the energy released in forming attractions between the water molecules and ions is combined into a term called the heat of hydration attractive forces in water = H-bonds attractive forces between ion and water = ion-dipole DHhydration = heat released when 1 mole of gaseous ions dissolves in water Tro, Chemistry: A Molecular Approach 21 Heat of Hydration Tro, Chemistry: A Molecular Approach 22 Ion-Dipole Interactions • when ions dissolve in water they become hydrated • each ion is surrounded by water molecules Tro, Chemistry: A Molecular Approach 23 Solution Equilibrium • the dissolution of a solute in a solvent is an equilibrium • • • process initially, when there is no dissolved solute, the only process possible is dissolution shortly, solute particles can start to recombine to reform solute molecules – but the rate of dissolution >> rate of deposition and the solute continues to dissolve eventually, the rate of dissolution = the rate of deposition – the solution is saturated with solute and no more solute will dissolve Tro, Chemistry: A Molecular Approach 24 Solution Equilibrium Tro, Chemistry: A Molecular Approach 25 Solubility Limit • a solution that has the maximum amount of solute dissolved in it is said to be saturated depends on the amount of solvent depends on the temperature and pressure of gases • a solution that has less solute than saturation is said to • be unsaturated a solution that has more solute than saturation is said to be supersaturated Tro, Chemistry: A Molecular Approach 26 How Can You Make a Solvent Hold More Solute Than It Is Able To? • solutions can be made saturated at non-room conditions • • – then allowed to come to room conditions slowly for some solutes, instead of coming out of solution when the conditions change, they get stuck in-between the solvent molecules and the solution becomes supersaturated supersaturated solutions are unstable and lose all the solute above saturation when disturbed e.g., shaking a carbonated beverage Tro, Chemistry: A Molecular Approach 27 Adding Solute to a Supersaturated Solution of NaC2H3O2 Tro, Chemistry: A Molecular Approach 28 Temperature Dependence of Solubility of Solids in Water • solubility is generally given in grams of solute that will • dissolve in 100 g of water for most solids, the solubility of the solid increases as the temperature increases when DHsolution is endothermic • solubility curves can be used to predict whether a solution with a particular amount of solute dissolved in water is saturated (on the line), unsaturated (below the line), or supersaturated (above the line) Tro, Chemistry: A Molecular Approach 29 Solubility Curves Tro, Chemistry: A Molecular Approach 30 Solubility of Some Salts in Water 120 110 Solubility, g salt in 100 g water 100 90 80 KCl 70 NaCl 60 NH4Cl 50 Li2SO4 40 Ce2(SO4)3•9H2O 30 KNO3 20 10 0 0 10 20 30 Tro, Chemistry: A Molecular Approach 40 50 60 70 Temperature, °C 80 90 100 110 31 Temperature Dependence of Solubility of Gases in Water • solubility is generally given in moles of solute that will dissolve in 1 Liter of solution • for all gases, the solubility of the gas decreases as the temperature increases the DHsolution is exothermic because you do not need to overcome solute-solute attractions Tro, Chemistry: A Molecular Approach 32 Solubility of Gases in Water at Various Temperatures 0.4 Solubility, g in 100 g water 0.35 0.3 0.25 CO2 acetylene 0.2 0.15 0.1 0.05 0 0 10 20 30 40 50 60 70 80 90 100 110 Temperature, °C Tro, Chemistry: A Molecular Approach 33 Solubility of Gases in Water at Various Temperatures Solubility, g in 100 g water 0.008 0.007 0.006 0.005 N2 O2 0.004 0.003 0.002 0.001 0 0 10 20 30 40 50 60 70 80 90 100 110 Temperature, °C Tro, Chemistry: A Molecular Approach 34 Pressure Dependence of Solubility of Gases in Water • the larger the partial pressure of a gas in contact with a liquid, the more soluble the gas is in the liquid 35 Henry’s Law • the solubility of a gas (Sgas) is directly proportional to its partial pressure, (Pgas) Sgas = kHPgas • kH is called Henry’s Law Constant Tro, Chemistry: A Molecular Approach 36 Relationship between Partial Pressure and Solubility of a Gas Partial Pressure 100 200 300 400 500 600 700 800 900 1000 Tro, Chemistry: A Molecular Approach O2 CO2 0.000571 0.001142 0.001713 0.002284 0.002855 0.003426 0.003997 0.004568 0.005139 0.005711 0.022237 0.044474 0.066711 0.088947 0.111184 0.133421 0.155658 0.177895 0.200132 0.222368 37 Solubility of Gases in Water at Various Pressures (temp = 20°C) Solubility, g in 100 g water 0.25 0.2 0.15 O2 CO2 0.1 0.05 0 0 200 400 600 800 1000 1200 Partial Pressure Tro, Chemistry: A Molecular Approach 38 persrst Tro, Chemistry: A Molecular Approach 39 Ex 12.2 – What pressure of CO2 is required to keep the [CO2] = 0.12 M at 25°C? Given: S = [CO2] = 0.12 M, Find: P of CO2, atm Concept Plan: [CO2] S P kH P Relationships: S = kHP, kH = 3.4 x 10-2 M/atm Solve: S 0.12 M P 3.5 atm 2 -1 k H 3.14 10 M atm Check: the unit is correct, the pressure higher than 1 atm meets our expectation from general experience Tro, Chemistry: A Molecular Approach 40 Concentrations • solutions have variable composition • to describe a solution, need to describe components • • and relative amounts the terms dilute and concentrated can be used as qualitative descriptions of the amount of solute in solution concentration = amount of solute in a given amount of solution occasionally amount of solvent Tro, Chemistry: A Molecular Approach 41 Solution Concentration Molarity • moles of solute per 1 liter of solution • used because it describes how many molecules of solute in each liter of solution • if a sugar solution concentration is 2.0 M, 1 liter of solution contains 2.0 moles of sugar, 2 liters = 4.0 moles sugar, 0.5 liters = 1.0 mole sugar moles of solute molarity = liters of solution Tro, Chemistry: A Molecular Approach 42 Molarity and Dissociation • the molarity of the ionic compound allows you to • • • • determine the molarity of the dissolved ions CaCl2(aq) = Ca+2(aq) + 2 Cl-1(aq) A 1.0 M CaCl2(aq) solution contains 1.0 moles of CaCl2 in each liter of solution 1 L = 1.0 moles CaCl2, 2 L = 2.0 moles CaCl2 Because each CaCl2 dissociates to give one Ca+2 = 1.0 M Ca+2 1 L = 1.0 moles Ca+2, 2 L = 2.0 moles Ca+2 Because each CaCl2 dissociates to give 2 Cl-1 = 2.0 M Cl-1 1 L = 2.0 moles Cl-1, 2 L = 4.0 moles Cl-1 Tro, Chemistry: A Molecular Approach 43 Solution Concentration Molality, m • moles of solute per 1 kilogram of solvent defined in terms of amount of solvent, not solution like the others • does not vary with temperature because based on masses, not volumes moles of solute molality, m kg of solvent Tro, Chemistry: A Molecular Approach 44 Percent • parts of solute in every 100 parts solution • mass percent = mass of solute in 100 parts solution by mass if a solution is 0.9% by mass, then there are 0.9 grams of solute in every 100 grams of solution or 0.9 kg solute in every 100 kg solution Mass of Solute, g Mass Percent 100% Mass of Solution, g Mass of Solute Mass of Solvent Mass of Solution Tro, Chemistry: A Molecular Approach 45 Using Concentrations as Conversion Factors • concentrations show the relationship between the amount of solute and the amount of solvent 12%(m/m) sugar(aq) means 12 g sugar 100 g solution or 12 kg sugar 100 kg solution; or 12 lbs. 100 lbs. solution 5.5%(m/v) Ag in Hg means 5.5 g Ag 100 mL solution 22%(v/v) alcohol(aq) means 22 mL EtOH 100 mL solution • The concentration can then be used to convert the amount of solute into the amount of solution, or vice versa Tro, Chemistry: A Molecular Approach 46 Preparing a Solution • need to know amount of solution and concentration of solution • calculate the mass of solute needed start with amount of solution use concentration as a conversion factor 5% by mass 5 g solute 100 g solution “Dissolve the grams of solute in enough solvent to total the total amount of solution.” Tro, Chemistry: A Molecular Approach 47 Example - How would you prepare 250.0 g of 5.00% by mass glucose solution (normal glucose)? Given: Find: Equivalence: Solution Map: 250.0 g solution g Glucose 5.00 g Glucose 100 g solution g solution g Glucose 5.00 g Glucose 100 g solution Apply Solution Map: 5.00 g glucose 250.0 g solution 12.5 g glucose 100 g solution Answer: Dissolve 12.5 g of glucose in enough water to total 250.0 g Tro, Chemistry: A Molecular Approach 48 Solution Concentration PPM • grams of solute per 1,000,000 g of solution • mg of solute per 1 kg of solution • 1 liter of water = 1 kg of water for water solutions we often approximate the kg of the solution as the kg or L of water grams solute x 106 grams solution mg solute mg solute kg solution L solution 49 Ex 12.3 – What volume of 10.5% by mass soda contains 78.5 g of sugar? Given: 78.5 g sugar Find: volume, mL Concept Plan: g solute 100 g sol' n 10.5 g sugar g sol’n 1 mL sol' n 1.04 g sol' n mL sol’n Relationships: 100 g sol’n = 10.5 g sugar, 1 mL sol’n = 1.04 g Solve: 100 g 1 mL 78.5 g sugar 719 mL 10.5 g sugar 1.04 g Check: the unit is correct, the magnitude seems reasonable as the mass of sugar 10% the volume of solution Tro, Chemistry: A Molecular Approach 50 Solution Concentrations Mole Fraction, XA • the mole fraction is the fraction of the moles of one • • • component in the total moles of all the components of the solution total of all the mole fractions in a solution = 1 unitless the mole percentage is the percentage of the moles of one component in the total moles of all the components of the solution = mole fraction x 100% mole fraction of A = XA = Tro, Chemistry: A Molecular Approach moles of components A total moles in the solution 51 Ex 12.4a – What is the molarity of a solution prepared by mixing 17.2 g of C2H6O2 with 0.500 kg of H2O to make 515 mL of solution? Tro, Chemistry: A Molecular Approach 52 Ex 12.4b – What is the molality of a solution prepared by mixing 17.2 g of C2H6O2 with 0.500 kg of H2O to make 515 mL of solution? Tro, Chemistry: A Molecular Approach 53 Ex 12.4c – What is the percent by mass of a solution prepared by mixing 17.2 g of C2H6O2 with 0.500 kg of H2O to make 515 mL of solution? Tro, Chemistry: A Molecular Approach 54 Ex 12.4d – What is the mole fraction of a solution prepared by mixing 17.2 g of C2H6O2 with 0.500 kg of H2O to make 515 mL of solution? Tro, Chemistry: A Molecular Approach 55 Vapor Pressure of Solutions • the vapor pressure of a solvent above a solution is lower than the vapor pressure of the pure solvent the solute particles replace some of the solvent molecules at the surface Eventually, reAddition of aequilibrium nonvolatileissolute The pure solvent establishes an established, smaller number reduces thebut ratea of vaporization, liquidmolecules vapor equilibrium ofdecreasing vapor – therefore the the amount of vapor vapor pressure will be lower Tro, Chemistry: A Molecular Approach 56 Thirsty Solutions • a concentrated solution will draw solvent molecules toward it due to the natural drive for materials in nature to mix • similarly, a concentrated solution will draw pure solvent vapor into it due to this tendency to mix • the result is reduction in vapor pressure Tro, Chemistry: A Molecular Approach 57 Thirsty Solutions When equilibrium Beakers with equalis liquid levelsthe established, of pure liquid solvent level in and the solution a solution are place beaker is in higher a bellthan jar. Solvent the solution molecules level in the evaporate pure solvent from beaker each– onethirsty the and fillsolution the bell jar, establishing grabs and holds an solvent equilibrium vapor more effectively with the liquids in the beakers. Tro, Chemistry: A Molecular Approach 58 Raoult’s Law • the vapor pressure of a volatile solvent above a solution is equal to its mole fraction of its normal vapor pressure, P° Psolvent in solution = csolvent∙P° since the mole fraction is always less than 1, the vapor pressure of the solvent in solution will always be less than the vapor pressure of the pure solvent Tro, Chemistry: A Molecular Approach 59 Ex 12.5 – Calculate the vapor pressure of water in a solution prepared by mixing 99.5 g of C12H22O11 with 300.0 mL of H2O Tro, Chemistry: A Molecular Approach 60 Ionic Solutes and Vapor Pressure • according to Raoult’s Law, the effect of solute on • • the vapor pressure simply depends on the number of solute particles when ionic compounds dissolve in water, they dissociate – so the number of solute particles is a multiple of the number of moles of formula units the effect of ionic compounds on the vapor pressure of water is magnified by the dissociation since NaCl dissociates into 2 ions, Na+ and Cl, one mole of NaCl lowers the vapor pressure of water twice as much as 1 mole of C12H22O11 molecules would Tro, Chemistry: A Molecular Approach 61 Effect of Dissociation Tro, Chemistry: A Molecular Approach 62 Ex 12.6 – What is the vapor pressure of H2O when 0.102 mol Ca(NO3)2 is mixed with 0.927 mol H2O @ 55°C? Tro, Chemistry: A Molecular Approach 63 Raoult’s Law for Volatile Solute • when both the solvent and the solute can evaporate, • both molecules will be found in the vapor phase the total vapor pressure above the solution will be the sum of the vapor pressures of the solute and solvent for an ideal solution Ptotal = Psolute + Psolvent • the solvent decreases the solute vapor pressure in the same way the solute decreased the solvent’s Psolute = csolute∙P°solute and Psolvent = csolvent∙P°solvent Tro, Chemistry: A Molecular Approach 64 Ideal vs. Nonideal Solution • in ideal solutions, the made solute-solvent interactions are equal to the sum of the broken solute-solute and solvent-solvent interactions ideal solutions follow Raoult’s Law • effectively, the solute is diluting the solvent • if the solute-solvent interactions are stronger or weaker than the broken interactions the solution is nonideal Tro, Chemistry: A Molecular Approach 65 Vapor Pressure of a Nonideal Solution • when the solute-solvent interactions are stronger than the solute-solute + solvent-solvent, the total vapor pressure of the solution will be less than predicted by Raoult’s Law because the vapor pressures of the solute and solvent are lower than ideal • when the solute-solvent interactions are weaker than the solute-solute + solvent-solvent, the total vapor pressure of the solution will be larger than predicted by Raoult’s Law Tro, Chemistry: A Molecular Approach 66 Deviations from Raoult’s Law Tro, Chemistry: A Molecular Approach 67 Tro, Chemistry: A Molecular Approach 68 Freezing Point Depression • the freezing point of a solution is lower than the freezing point of the pure solvent for a nonvolatile solute therefore the melting point of the solid solution is lower • the difference between the freezing point of the solution and freezing point of the pure solvent is directly proportional to the molal concentration of solute particles (FPsolvent – FPsolution) = DTf = m∙Kf • the proportionality constant is called the Freezing Point Depression Constant, Kf the value of Kf depends on the solvent the units of Kf are °C/m Tro, Chemistry: A Molecular Approach 69 Kf Tro, Chemistry: A Molecular Approach 70 Ex 12.8 – What is the freezing point of a 1.7 m aqueous ethylene glycol solution, C2H6O2? Given: 1.7 m C2H6O2(aq) Find: Tf, °C Concept Plan: m DTf DT f m K f Relationships: DTf = m ∙Kf, Kf for H2O = 1.86 °C/m, FPH2O = 0.00°C Solve: DT f m K f ,H 2O FPH O FPsol'n DT f ( (1.7 m 1.86 DT f 3.2 C C m 2 0.00C FPsol'n 3.2C FPsol'n 3.2C Check: the unit is correct, the freezing point lower than the normal freezing point makes sense Tro, Chemistry: A Molecular Approach 71 Boiling Point Elevation • the boiling point of a solution is higher than the boiling point of the pure solvent for a nonvolatile solute • the difference between the boiling point of the solution • and boiling point of the pure solvent is directly proportional to the molal concentration of solute particles (BPsolution – BPsolvent) = DTb = m∙Kb the proportionality constant is called the Boiling Point Elevation Constant, Kb the value of Kb depends on the solvent the units of Kb are °C/m Tro, Chemistry: A Molecular Approach 72 Ex 12.9 – How many g of ethylene glycol, C2H6O2, must be added to 1.0 kg H2O to give a solution that boils at 105°C? Tro, Chemistry: A Molecular Approach 73 Osmosis • osmosis is the flow of solvent through a semipermeable membrane from solution of low concentration to solution of high concentration • the amount of pressure needed to keep osmotic flow from taking place is called the osmotic pressure • the osmotic pressure, P, is directly proportional to the molarity of the solute particles R = 0.08206 (atm∙L)/(mol∙K) P = MRT Tro, Chemistry: A Molecular Approach 74 Tro, Chemistry: A Molecular Approach 75 Ex 12.10 – What is the molar mass of a protein if 5.87 mg per 10 mL gives an osmotic pressure of 2.45 torr at 25°C? Tro, Chemistry: A Molecular Approach 76 Colligative Properties • colligative properties are properties whose value depends only on the number of solute particles, and not on what they are Vapor Pressure Depression, Freezing Point Depression, Boiling Point Elevation, Osmotic Pressure • the van’t Hoff factor, i, is the ratio of moles of solute • particles to moles of formula units dissolved measured van’t Hoff factors are often lower than you might expect due to ion pairing in solution Tro, Chemistry: A Molecular Approach 77 Tro, Chemistry: A Molecular Approach 78 Colloids • a colloidal suspension is a heterogeneous mixture in which one substance is dispersed through another most colloids are made of finely divided particles suspended in a medium • the difference between colloids and regular suspensions is generally particle size – colloidal particles are from 1 to 100 nm in size Tro, Chemistry: A Molecular Approach 79 Properties of Colloids • the particles in a colloid exhibit Brownian motion • colloids exhibit the Tyndall Effect scattering of light as it passes through a suspension colloids scatter short wavelength (blue) light more effectively than long wavelength (red) light Tro, Chemistry: A Molecular Approach 80 Tro, Chemistry: A Molecular Approach 81 Tro, Chemistry: A Molecular Approach 82 Tro, Chemistry: A Molecular Approach 83