2 Energy is the capacity to do work Thermal energy is the energy associated with the random motion of atoms and moleculesChemical energy is the energy stored within the bonds of chemical substancesNuclear energy is the energy stored within the collection of neutrons and protons in the atomElectrical energy is the energy associated with the flow of electronsPotential energy is the energy available by virtue of an object’s position or composition.
3 Energy Changes in Chemical Reactions Heat is the transfer of thermal energy between two bodies that are at different temperatures.Temperature is a measure of the thermal energy.Temperature = Thermal Energy400C900Cgreater thermal energy
4 Thermochemistry is the study of heat change in chemical reactions. SURROUNDINGSThe system is the specific part of the universe that is of interest in the study.SYSTEMopenclosedisolatedExchange:mass & energyenergynothing
5 , pressure, volume, temperature ThermodynamicsState functions are properties that are determined by the state of the system, regardless of how that condition was achieved.energy, pressure, volume, temperaturePotential energy of hiker 1 and hiker 2 is the same even though they took different paths.
6 The specific heat (s) [most books use lower case c] of a substance is the amount of heat (q) required to raise the temperature of one gram of the substance by one degree Celsius.The heat capacity (C) of a substance is the amount of heat (q) required to raise the temperature of a given quantity (m) of the substance by one degree Celsius.C = msHeat (q) absorbed or released:q = msDtq = CDtDt = tfinal - tinitial
7 How much heat is given off when an 869 g iron bar cools from 940C to 50C? s of Fe = J/g • 0CDt = tfinal – tinitial = 50C – 940C = -890Cq = msDt= 869 g x J/g • 0C x –890C= -34,000 J
11 TWO Trends in NatureOrder Disorder High energy Low energy
12 2H2 (g) + O2 (g) 2H2O (l) + energy Exothermic process is any process that gives off heat – transfers thermal energy from the system to the surroundings.2H2 (g) + O2 (g) H2O (l) + energyH2O (g) H2O (l) + energyEndothermic process is any process in which heat has to be supplied to the system from the surroundings.energy + H2O (s) H2O (l)energy + 2HgO (s) Hg (l) + O2 (g)
13 DH = H (products) – H (reactants) Enthalpy (H) is used to quantify the heat flow into or out of a system in a process that occurs at constant pressure.DH = H (products) – H (reactants)DH = heat given off or absorbed during a reaction at constant pressureHproducts < HreactantsHproducts > HreactantsDH < 0DH > 0
14 Thermochemical Equations Is DH negative or positive?System absorbs heatEndothermicDH > 06.01 kJ are absorbed for every 1 mole of ice that melts at 00C and 1 atm.H2O (s) H2O (l)DH = 6.01 kJ
15 Thermochemical Equations Is DH negative or positive?System gives off heatExothermicDH < 0890.4 kJ are released for every 1 mole of methane that is combusted at 250C and 1 atm.CH4 (g) + 2O2 (g) CO2 (g) + 2H2O (l)DH = kJ
16 Thermochemical Equations The stoichiometric coefficients always refer to the number of moles of a substanceH2O (s) H2O (l)DH = 6.01 kJ/mol ΔH = 6.01 kJIf you reverse a reaction, the sign of DH changesH2O (l) H2O (s)DH = kJIf you multiply both sides of the equation by a factor n, then DH must change by the same factor n.2H2O (s) H2O (l)DH = 2 mol x 6.01 kJ/mol = 12.0 kJ
17 Thermochemical Equations The physical states of all reactants and products must be specified in thermochemical equations.H2O (s) H2O (l)DH = 6.01 kJH2O (l) H2O (g)DH = 44.0 kJHow much heat is evolved when 266 g of white phosphorus (P4) burn in air?P4 (s) + 5O2 (g) P4O10 (s) DHreaction = kJ1 mol P4123.9 g P4x3013 kJ1 mol P4x266 g P4= 6470 kJ
18 Standard enthalpy of formation (DH0) is the heat change that results when one mole of a compound is formed from its elements at a pressure of 1 atm.fThe standard enthalpy of formation of any element in its most stable form is zero.DH0 (O2) = 0fDH0 (C, graphite) = 0fDH0 (O3) = 142 kJ/molfDH0 (C, diamond) = 1.90 kJ/molf
20 The standard enthalpy of reaction (DH0 ) is the enthalpy of a reaction carried out at 1 atm. rxnaA + bB cC + dDDH0rxndDH0 (D)fcDH0 (C)=[+]-bDH0 (B)aDH0 (A)DH0rxn=SDH0 (products)f-SDH0 (reactants)fHess’s Law: When reactants are converted to products, the change in enthalpy is the same whether the reaction takes place in one step or in a series of steps.(Enthalpy is a state function. It doesn’t matter how you get there, only where you start and end.)
21 2C6H6 (l) + 15O2 (g) 12CO2 (g) + 6H2O (l) Benzene (C6H6) burns in air to produce carbon dioxide and liquid water. How much heat is released per mole of benzene combusted? The standard enthalpy of formation of benzene is kJ/mol.2C6H6 (l) + 15O2 (g) CO2 (g) + 6H2O (l)DH0rxnDH0 (products)f=SDH0 (reactants)-DH0rxn6DH0 (H2O)f12DH0 (CO2)=[+]-2DH0 (C6H6)DH0rxn=[ 12 × × ] – [ 2 × ] = kJ-6535 kJ2 mol= kJ/mol C6H6
22 Calculate the standard enthalpy of formation of CS2 (l) given that: C(graphite) + O2 (g) CO2 (g) DH0 = kJrxnS(rhombic) + O2 (g) SO2 (g) DH0 = kJrxnCS2(l) + 3O2 (g) CO2 (g) + 2SO2 (g) DH0 = kJrxn1. Write the enthalpy of formation reaction for CS2C(graphite) + 2S(rhombic) CS2 (l)2. Add the given rxns so that the result is the desired rxn.rxnC(graphite) + O2 (g) CO2 (g) DH0 = kJ2S(rhombic) + 2O2 (g) SO2 (g) DH0 = x2 kJrxn+CO2(g) + 2SO2 (g) CS2 (l) + 3O2 (g) DH0 = kJrxnC(graphite) + 2S(rhombic) CS2 (l)DH0 = (2x-296.1) = 86.3 kJrxn6.6
23 Chemistry in Action: Fuel Values of Foods and Other Substances C6H12O6 (s) + 6O2 (g) CO2 (g) + 6H2O (l) DH = kJ/mol1 cal = J1 Cal = 1 kcal = 1000 cal = 4184 J
24 The enthalpy of solution (DHsoln) is the heat generated or absorbed when a certain amount of solute dissolves in a certain amount of solvent.DHsoln = Hsoln - HcomponentsWhich substance(s) could be used for melting ice?Which substance(s) could be used for a cold pack?
25 The Solution Process for NaCl DHsoln = Step 1 + Step 2 = 788 – 784 = 4 kJ/mol
26 Energy Diagrams Exothermic Endothermic Activation energy (Ea) for the forward reactionActivation energy (Ea) for the reverse reaction(c) Delta H50 kJ/mol300 kJ/mol150 kJ/mol100 kJ/mol-100 kJ/mol+200 kJ/mol
27 H2O (s) H2O (g)Molar heat of sublimation (DHsub) is the energy required to sublime 1 mole of a solid.SublimationDepositionDHsub = DHfus + DHvap( Hess’s Law)
28 Molar heat of fusion (DHfus) is the energy required to melt 1 mole of a solid substance.
30 Sample ProblemHow much heat is required to change 36 g of H2O from -8 deg C to 120 deg C?Step 1: Heat the ice Q=mcΔTQ = 36 g x 2.06 J/g deg C x 8 deg C = J = 0.59 kJStep 2: Convert the solid to liquid ΔH fusionQ = 2.0 mol x 6.01 kJ/mol = 12 kJStep 3: Heat the liquid Q=mcΔTQ = 36g x J/g deg C x 100 deg C = J = 15 kJ
31 Now, add all the steps together Sample ProblemHow much heat is required to change 36 g of H2O from -8 deg C to 120 deg C?Step 4: Convert the liquid to gas ΔH vaporizationQ = 2.0 mol x kJ/mol = kJStep 5: Heat the gas Q=mcΔTQ = 36 g x 2.02 J/g deg C x 20 deg C = J = 1.5 kJNow, add all the steps together0.59 kJ + 12 kJ + 15 kJ + 88 kJ kJ = 118 kJ
32 Bond Enthalpies (Bond Energy) Strength of a chemical bond is measured by the bond enthalpy, DHBBond enthalpies are positive, because heat must be supplied to break a bond.Bond breaking is endothermic (DH is positive).Bond formation is exothermic (DH is negative).H2(g) --> 2 H DHo = +436 kJDHB = 436 kJ/mol
34 Mean bond enthalpy: average molar enthalpy change accompanying the dissociation of a given type of bond.
35 Estimate the enthalpy change of the reaction between gaseous iodoethane and water vapor. CH3CH2I(g) + H2O(g) --> CH3CH2OH(g) + HI(g)Reactant: break a C-I bond and an O-H bondDHo = 238 kJ kJ = 701 kJProduct: to form a C-O bond and an H-I bondDHo = -360 kJ kJ = -659 kJOverall enthalpy change = 701 kJ kJ = 42 kJ