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THERMOCHEMISTRY CHAPTER 5 WHY ENERGY? • • • • • Life requires energy From plants – photosynthesis To equipment – electricity Vehicles – fossil fuels To animals - food ENERGY FROM WHERE? • Most of our energy as humans – From food – i.e. from chemical reactions • In the world – From chemical reactions WHAT IS THERMOCHEMISTRY? Quantitative study of chemical reactions involving heat changes Produce energy Consume energy Examples: Food we eat - provides us with energy Burning coal- to produce electrical energy Energy from the sun - responsible for chemical reactions in plants which make them grow RECALL • FORCE (F) – push/pull exerted on an object • WORK (w) – energy used to cause an object to move against a force (w = Fd) • HEAT (q) – energy transfer as a result of a temperature difference. Heat always flows from a hotter to a colder object until they have the same temperature • ENERGY (E) – capacity to do work or to transfer heat HOT STUFF? • Can something transfer cold? • Does ice make a drink cold? When you blow hot soup do you make it cold? SO IN FACT: • In theory stirring soup long enough and fast enough could make it boil Heat always flows from a hotter to a colder object until they have the same temperature BUT I KNOW IT’S COLD!! Heat from our body is transferred, making something feel cold because we lose heat from the area touching the cold object NATURE OF ENERGY 2 types of energy Kinetic energy Potential energy Energy due to motion of object Energy due to position of object relative to others (Stored energy) KINETIC ENERGY 1 Ek mv 2 2 Note: Ek increases as velocity increases and Ek increases as mass increases. Atoms and molecules have mass and are in motion, thus they have kinetic energy! Thermal energy energy an object possesses because of its temperature. Associated with kinetic energy of atoms and molecules. The higher the temperature, the faster the atoms and molecules move the more kinetic energy molecules and atoms have the greater the thermal energy of the object. The total thermal energy of the object is the sum of the individual energies of the atoms or molecules. MISSING: KINETIC ENERGY, PLEASE HELP • What is it to have no kinetic energy? – Absolute zero! • Can we detect that? – No! – Why?! – Because in order to detect it we would have to interact with it which would heat it POTENTIAL ENERGY We know Ep = mgh Forces other than gravity that lead to potential energy = ELECTROSTATIC forces Attractions and repulsions due to oppositely charged objects (e.g. positive and negative ions) Recall: kQ1Q 2 Eel d Describes the electrostatic energy between 2 charges. Eel = electrostatic energy k = Coulomb constant Q = charge d = distance between charges UNITS OF ENERGY SI unit = J (Joule) 1 J = 1 kg.m2.s-2 Ek=0.5mv2 =(kg)(m.s-1)2 (Others 1 cal (calorie) = 4.184 J) (The amount of heat energy to raise temp of 1g H2O by 1oC) A BRAINTEASER • If everything has kinetic energy • And chemical potential energy • Why is everything not moving around constantly? • Why are solids not felt to vibrate? SYSTEM AND SURROUNDINGS Portion singled out for study System Everything else Surroundings System + surroundings = universe Open system – can exchange both energy and matter with the surroundings Closed system – exchanges energy but NOT matter with the surroundings Isolated system – neither energy nor matter can be exchanged with the surroundings A QUOTE NOT TO LIVE BY “Thermodynamics is a funny subject. The first time you go through it, you don't understand it at all. The second time you go through it, you think you understand it, except for one or two small points. The third time you go through it, you know you don't understand it, but by that time you are so used to it, it doesn't bother you anymore.” http://www.eoht.info/page/Thermodynamics+humor FIRST LAW OF THERMODYNAMICS Energy is neither created nor destroyed, it is merely converted from one form into another. Energy is transferred between the system and the surroundings in the form of work and heat. The total energy of the universe remains constant. INTERNAL ENERGY (U) Also given as E Internal energy (of the system) = sum of all Ek and Ep of all components of the system Symbol for change = Change in internal energy of the system U U = UFinal - Uinitial Number & Unit Magnitude Sign Direction (in which energy is transferred) U = UFinal - Uinitial Usyst > 0 Uf > Ui GAINED energy from surroundings Usyst < 0 Uf < Ui LOST energy to surroundings RELATING U TO WORK AND HEAT General ways to change ENERGY of a closed system: HEAT lost/gained by system WORK Done by/on system Relationship: When a system undergoes a chemical/physical change U = q + w We can’t measure U, but we can determine U. SIGN CONVENTION q<0 Heat transferred FROM system w<0 Work done BY system SYSTEM q>0 Heat transferred TO system w>0 Work done ON system The sign of U will depend on the sign and magnitude of q and w since U = q + w. Example: Calculate the change in internal energy for a process in which the system absorbs 120 J of heat from the surroundings and does 64 J of work on the surroundings. System 120 J heat 64 J work U = q + w = (120 J) + (- 64 J) = 56 J SOME DEFINITIONS Extensive property – dependent on the amount of matter in the system. E.g. mass, volume etc Intensive Property – NOT dependent on the amount of matter in the system. E.g. density, temperature etc State function – a function that depends on the state or conditions of the system and NOT on the details of how it came to be in that state. A B C DEFINITIONS APPLIED TO INTERNAL ENERGY Recall: Total internal energy of a system = sum of all Ek and Ep of all components of the system Thus total internal energy of a system total quantity of matter in system U is an extensive property Internal energy depends on the state or conditions of the system (e.g. pressure, temperature, location) Does not depend on how it came to be in that state. state function U only depends on Ui and Uf and not how the change occurred. e.g. if a gas sample undergoes: A pressure A heat Y X heat pressure B, or B U is the same in both cases. NOTE: Heat and work are not state functions! ENTHALPY (H) We cannot measure enthalpy (H), we can only measure change in enthalpy (H). Change in enthalpy (H) is the heat gained or lost by the system when a process occurs under constant pressure. E.g. atm pressure H = Hfinal - Hinitial = qp H is a state function and an extensive property NOTE: At constant pressure, most of the energy lost / gained is in the form of heat. Very little work is done for the expansion / contraction against the atmospheric force, especially if the reaction does not involve gases. qp<0 H<0 Exothermic process – system evolves heat SYSTEM qp>0 H>0 Endothermic process - system absorbs heat Example of an exothermic reaction: Example of an endothermic reaction: FINDING THE RELATIONSHIP BETWEEN U AND H – CONSIDER PV WORK We know that: U = q + w Assume we do PV work only (e.g. expanding gases in cylinder of a car does PV work on the piston) F P A Gas expands and moves piston distance d W = Fd But F = PA W = PAd W = PV Sign: system is doing work on the piston W = -PV U = q + w and w = -PV U = q - PV At constant volume, V = 0 U = qv At constant pressure: U = qp - PV But H = qp U = H - PV The volume change in many reactions is very small, thus PV is very small and hence the difference between U and H is small. ENTHALPIES OF REACTION enthalpy change that accompanies a reaction (heat of reaction) Hrxn = H(products) – H(reactants) final Thermochemical equation: 2H2(g) + O2(g) 2H2O(g) Balanced equation initial exothermic H = - 483.6 kJ H associated with the reaction Coefficients in balanced equation = no. of moles of reactant/product producing associated H (extensive) 2H2(g) + O2(g) 2H2O(g) H = -483.6 kJ Note: Since enthalpy is an extensive property, H depends on the amount of reactant consumed. 4H2(g) + 2O2(g) 4H2O(g) H = -967.2 kJ Also, H for a reaction is equal in magnitude, but opposite in sign to H for the reverse reaction. 2H2O(g) 2H2(g) + O2(g) H = +483.6 kJ Notes are available on http://hobbes.gh.wits.ac.za/chemnotes/fmain-chem1033-35.htm Go to the section for Mrs C Billing Lectures Chapter 7, Chapter 8 and Chapter 9 are this work We are busy with Chapter 7 at the moment Example: Calculate the heat needed to convert 25 ml water to steam at atmospheric pressure if the enthalpy change is 44 kJ/mol. (Assume the density of water is 1.0 kg/l) =1.0 g/ml H2O(l) H2O(g) H = 44 kJ/mol 25 ml m = v = (1.0 g/ml)(25 ml) = 25 g m 25 g n= = 1.4 mol = M 18.016 g/mol qp = H = 44 kJ/mol x 1.4 mol = 62 kJ Check - endothermic Example: Hydrogen peroxide can decompose to water and oxygen by the reaction: 2H2O2 (l) 2H2O (l) + O2 (g) H = -196 kJ Calculate the heat produced when 2.50 g H2O2 decomposes at constant pressure. m 2.50 g nH2O2 = = = 0.0735 mol 34.02 g/mol M qp = H = -196 kJ for 2 mol H2O2 = -7.2 kJ for 0.0735 mol Example – burning money: Ethanol burns in air to give water vapour and carbon dioxide 1. Calculate the enthalpy of reaction given enthalpy of formations of: ethanol (l) = -277.7 kJ/mol water (l) = -285.8 kJ/mol carbon dioxide (g)= -393.5 kJ/mol 2. Calculate the minimum amount of water needed to prevent the paper from burning after be soaked in 1g of ethanol First: find the balanced chemical equation C2H5OH (l) + 3O2 3H2O (l) + 2CO2 (g) Enthalpy of reaction: H = H°f(products) - H°f(reagents) = 2(-393.5) + 3(-285.8) – (-277.7 + 3x0) kJ/mol = -1365.8 kJ/mol Example – burning money: Ethanol burns in air to give water vapour and carbon dioxide 2. Calculate the minimum amount of water needed to prevent the paper from burning after be soaked in 1.00g of ethanol Find the heat released by burning 1.00 g of ethanol m 1.00 g n= M = 46.07 g/mol = 0.0217 mol qp = H = -1365.8 kJ/mol x 0.0217 mol = -29.6 kJ Recall: H2O(l) H2O(g) qp -29.6 kJ n= H = 44 kJ/mol H = 44 kJ/mol = 0.67 mol m = nM = (0.67 mol)(18.0148 g/mol) = 12 g CALORIMETRY The experimental determination of heat flow associated with a chemical reaction by measuring the temperature changes it produces. Heat Capacity The amount of heat required to raise the temperature by 1K. Recall: a change of 1K = a change of 1oC Units: J.K-1 Extensive property Molar Heat Capacity The heat capacity of 1 mol of substance. Units: J.K-1mol-1 Specific Heat Capacity (C) heat capacity of 1 g of substance Units: J.K-1g-1 determined by measuring the change in temperature that a known mass of substance undergoes when it gains/loses a specific quantity of heat. q C m T Specific Heats for Some Subst’s at 298K H2O (l) 4.18 J.K-1g-1 N2 (g) 1.04 J.K-1g-1 Al (s) 0.90 J.K-1g-1 Fe (s) 0.45 J.K-1g-1 Hg (l) 0.14 J.K-1g-1 Example: a) How much heat is needed to warm 1.00 L of water from 23.0oC to 98.0oC? (Assume the density of water is 1.00 kg/L). b) What is the molar heat capacity of water? a) How much heat is needed to warm 1.00 L of water from 23.0oC to 98.0oC? (Assume the density of water is 1.00 kg/L). q C m T m = v = (1.00 L)(1.00 kg.L-1) = 1.00x103 g T = 98.0 – 23.0 = 75.0oC = 75.0 K q CmT q = (4.18 J.g-1.K-1)(1.00x103 g)(75.0 K) q = 3.14x105 J b) What is the molar heat capacity of water? C = 4.18 J.g-1.K-1 MH2O = 18.016 g.mol-1 4.18 J g.K x 18.016 g mol = 75.3 J.mol-1.K-1 CONSTANT PRESSURE CALORIMETRY Any calorimeter at atmospheric pressure has a constant pressure, e.g. “coffee-cup” calorimeter. The heat produced by a reaction is entirely absorbed by the solution at constant pressure. i.e. heat does not escape the calorimeter Recall: H = qp Can calculate qsoln = CmT, but we want qrxn Since heat given off by the reaction is absorbed by the solution: qrxn = -qsoln Example: When 4.25 g solid ammonium nitrate dissolves in 60.0 g water in a coffee-cup calorimeter, the temperature drops from 22.0oC to 16.9oC. Calculate H (in kJ/mol NH4NO3) for the dissolution process. Assume the specific heat of solution is the same as that for pure water. NH4NO3(s) NH4+(aq) + NO3-(aq) When 4.25 g solid ammonium nitrate dissolves in 60.0 g water in a coffee-cup calorimeter, the temperature drops from 22.0oC to 16.9oC. Calculate H (in kJ/mol NH4NO3) for the dissolution process. T = 16.9 – 22.0 = -5.1oC = -5.1 K m = 60.0 +4.25 = 64.3 g assumption qrxn = -CmT qrxn = -(4.18 J.g-1.K-1)(64.3 g)(-5.1 K) qrxn = 1.4x103 J endothermic When 4.25 g solid ammonium nitrate dissolves in 60.0 g water in a coffee-cup calorimeter, the temperature drops from 22.0oC to 16.9oC. Calculate H (in kJ/mol NH4NO3) for the dissolution process. qrxn = 1.4x103 J MNH4NO3 = 80.052 g.mol-1 m n= M 4.25 g = 80.052 g.mol-1 = 0.0531 mol 1.4x103 J H = qp = = 26.4 kJ.mol-1 0.0531 mol endothermic CONSTANT VOLUME CALORIMETRY – BOMB CALORIMETER Recall: U = qv At constant volume – measure U rather than H, but for most U H A bomb calorimeter is used to study combustion reactions etc. We calculate the heat of combustion from the measured change in temperature. We need to know the heat capacity of the calorimeter (Ccal). qrxn = -Ccal x T NB: This equation cannot be applied blindly!!! Always check units for Ccal. Always include units in calculations to ensure they cancel. Bomb Calorimeter Example: A 2.200 g sample of quinone, C6H4O2, is burned in a bomb calorimeter whose total heat capacity is 7.854 kJ/oC. The temperature of the calorimeter increases from 23.44oC to 30.57oC. What is the heat of combustion per gram of quinone? per mole of quinone? T = 30.57 – 23.44 = 7.13oC qrxn = -CcalT qrxn = -(7.854 kJ.oC-1)(7.13oC) qrxn = -56.0 kJ exothermic exothermic A 2.200 g sample of quinone, C6H4O2, is burned in a bomb calorimeter whose total heat capacity is 7.854 kJ/oC. The temperature of the calorimeter increases from 23.44oC to 30.57oC. What is the heat of combustion per gram of quinone? per mole of quinone? qrxn = -56.0 kJ -25.5 kJ produced by i.e. -25.5 kJ.g-1 -25.5 kJ.g-1 x 108.09 g.mol-1 = -2.75 x 103 kJ.mol-1 2.200 g quinone 1 g quinone Example: 50.0 g of water at 62.5oC was poured into a calorimeter containing 50.0 g water at 18.7oC. The final temperature was 35.0oC. How much heat was lost to the surroundings during this process? (Heat capacity of water = 4.184 J.oC-1.g-1) Ans: -2.34 kJ 50.0 g of water at 62.5oC was poured into a calorimeter containing 50.0 g water at 18.7oC. The final temperature was 35.0oC. How much heat was lost to the surroundings during this process? (Heat capacity of water = 4.184 J.oC-1.g-1) H2O 1: m = 50.0 g Ti = 62.5oC Tf = 35.0oC T = -27.5oC H2O 2: m = 50.0 g Ti = 18.7oC Tf = 35.0oC T = 16.3oC qsoln = CmT q1 = (4.184)(50.0)(-27.5) q1 = -5753 J q2 = (4.184)(50.0)(16.3) q2 = 3410 J q1 + q2 = -2343 J = -2.34 kJ Negative q heat lost by soln to the surroundings HESS’S LAW If a reaction is carried out in a series of steps, H for the reaction will be equal to the sum of the enthalpy changes for the individual steps. A+BX+Y H1 X+YC+D H2 A+BC+D H1+ H2 H for a reaction is calculated from H data of other reactions. Recall that enthalpy is a state function H is independent of the path followed. It is useful to use Hess’s Law in cases where H cannot be measured. Example: Carbon occurs in two forms, graphite and diamond. The enthalpy of combustion of graphite is –393.5 kJ/mol and that of diamond is –395.4 kJ/mol. Calculate H for the conversion of graphite to diamond. C(s,graph) + O2(g) CO2(g) H = –393.5 kJ/mol C(s,diam) + O2(g) CO2(g) H = –395.4 kJ/mol C(s,graph) C(s,diam) H = ? C(s,graph) + O2(g) CO2(g) H = –393.5 kJ/mol C(s,diam) + O2(g) CO2(g) H = –395.4 kJ/mol C(s,graph) C(s,diam) H = ? C(s,graph) + O2(g) CO2(g) H = -393.5 kJ/mol CO2(g) C(s,diam) + O2(g) H = +395.4 kJ/mol C(s,graph) C(s,diam) H = -393.5 + -(-395.4) = 1.9 kJ/mol Example: From the following enthalpies of reaction: H2(g) + F2(g) 2HF(g) C(s) + 2F2(g) CF4(g) 2C(s) + 2H2(g) C2H4(g) H = -537 kJ H = -680 kJ H = 52.3 kJ Calculate H for the reaction of ethylene with F2: C2H4(g) + 6F2(g) 2CF4(g) + 4HF(g) H2(g) + F2(g) 2HF(g) C(s) + 2F2(g) CF4(g) 2C(s) + 2H2(g) C2H4(g) H = -537 kJ H = -680 kJ H = 52.3 kJ C2H4(g) + 6F2(g) 2CF4(g) + 4HF(g) C2H4(g) 2C(s) + 2H2(g) 2C(s) + 4F2(g) 2CF4(g) 2H2(g) + 2F2(g) 4HF(g) H = -(52.3 kJ) H = 2(-680 kJ) H = 2(-537 kJ) C2H4(g) + 6F2(g) 2CF4(g) + 4HF(g) H = -(52.3 kJ) + 2(-680 kJ) + 2(-537 kJ) H = -2.49x103 kJ STANDARD STATES The magnitude of H depends on conditions of temperature, pressure, and state of products and reactants. In order to compare enthalpies, need same set of conditions. Standard state of a substance = pure form at 1 atm and at the temperature of interest (usually 298 K (25oC)) Standard enthalpy (Ho) when all products and reactants are in their standard states STANDARD ENTHALPIES OF FORMATION Hfo change in enthalpy for the reaction that forms 1 mol of a substance from its elements in their standard states. Units: kJ/mol Note: If there is more than one form of the element present under standard conditions, use the most stable form. Hfo = 0 kJ/mol for the most stable form of any element Examples of most stable form: Oxygen(g) can exist as O2 or O3 (ozone) at 1 atm and 298 K Most stable form = O2 Hfo(O2(g)) = 0 kJ/mol Carbon(s) can exist as graphite or diamond at 1 atm and 298 K Most stable form = graphite Hfo(C(s,graphite)) = 0 kJ/mol Tabulated data of enthalpies of formation can be used to calculate enthalpies of reaction as follows: o Hrxn mHof (products) nHof (reac tan ts) Stoichiometric coefficients Table of standard enthalpies of formation General Knowledge Gray tin and white tin are two solid forms of tin. The denser white metallic form is the most stable phase above 13oC, and the powdery gray form is more stable below 13oC. The formation of gray tin is said to have contributed to Napoleon’s defeat at Moscow, when his soldier’s buttons fell off their clothes at the low temperatures they encountered there. Example: Nitroglycerine is a powerful explosive, giving four different gases when detonated: 2C3H5(NO3)3 (l) 3N2(g) + 1/2O2(g) + 6CO2(g) + 5H2O(g) Given that the enthalpy of formation of nitroglycerine is Hfo = -364 kJ.mol-1, calculate the enthalpy change when 10.0 g of nitroglycerine is detonated. Hfo {C3H5(NO3)3 (l)} = -364 kJ.mol-1 Hfo {H2O (g)} = -241.8 kJ.mol-1 Hfo {CO2 (g)} = -393.5 kJ.mol-1 Hfo {O2 (g)} = Hfo {N2 (g)} = 0 kJ.mol-1 2C3H5(NO3)3 (l) 3N2(g) + 1/2O2(g) + 6CO2(g) + 5H2O(g) Calculate the enthalpy change when 10.0 g of nitroglycerine is detonated. Hfo {C3H5(NO3)3 (l)} = -364 kJ.mol-1 Hfo {H2O (g)} = -241.8 kJ.mol-1 Hfo {CO2 (g)} = -393.5 kJ.mol-1 o Hrxn mHof (products) nHof (reac tan ts) Horxn = [3(0) + 1/2(0) + 6(-393.5) + 5(-241.8)] - [2(-364)] Horxn = [-3570]-[-728] Horxn = -2842 kJ 2C3H5(NO3)3 (l) 3N2(g) + 1/2O2(g) + 6CO2(g) + 5H2O(g) Calculate the enthalpy change when 10.0 g of nitroglycerine is detonated. Horxn = -2842 kJ nC3H5 (NO3 )3 10.0 g m 0.0440 mol 1 227.1 g.mol M -2842 kJ for 2 mol NG x kJ for 0.0440 mol NG x = -62.5 kJ for 10.0 g Example: For you to do! Calculate Ho for the decomposition of limestone: CaCO3(s) CaO(s) + CO2(g) Hence calculate the heat required to decompose 1 kg of limestone. Hfo {CaCO3 (s)} = -1207.1 kJ.mol-1 Hfo {CaO (s)} = -635.5 kJ.mol-1 Hfo {CO2 (g)} = -393.5 kJ.mol-1 Answer: Ho = 178.1 kJ for 1 mol qp = Ho = 1779 kJ for decomposition of 1 kg CaCO3 BOND ENTHALPIES The stability of a molecule is related to the strengths of the covalent bonds it contains. The strength of a covalent bond between two atoms is determined by the energy required to break that bond. Bond enthalpy = enthalpy change for breaking a particular bond in a mole of gaseous substance. Can determine approximate value for Horxn if we have the values of average bond enthalpies. Horxn is calculated by determining the energy required to break all bonds minus the energy evolved to form all bonds. o Hrxn BE(bonds broken) BE(bonds formed) Reactants Products initial final This is only an approximation because the average bond enthalpies used as the bond enthalpies are not exactly the same in all molecules. e.g. C-H bond energy in CH4 is slightly different to that in C2H6 and so on. H H-C-H H H H H-C–C-H H H You must know these: O2 O=O N2 NN CO CO CO2 O=C=O CN CN H2CO H C=O H Example: Hydroiodic acid reacts with chlorine as follows: 2HI(aq) + Cl2(g) 2HCl(aq) + I2(s) Approximate Ho for the reaction using tabulated bond energies. 2HI(aq) + Cl2(g) 2HCl(aq) + I2(s) H-I H-I Cl-Cl H-Cl H-Cl I-I 2HI(aq) + Cl2(g) 2HCl(aq) + I2(s) Bonds Broken 2 x H-I 1 x Cl-Cl Bonds Formed 2 x H-Cl 1 x I-I Bond Energy / kJ.mol-1 2(297) 239 833 2(431) 149 1011 o Hrxn BE(bonds broken) BE(bonds formed) = 833 – 1011 = -178 kJ.mol-1 Example: Estimate H using bond enthalpies for the following reaction: C2H6(g) + 7/2O2(g) 2CO2(g) + 3H2O(g) H H O=O H-C–C-H H O=C=O O H H H 6 x C-H 1 x C-C 7/ x O=O 2 4 x O=C 6 x O-H C2H6(g) + 7/2O2(g) 2CO2(g) + 3H2O(g) Bonds Broken 6 x C-H 1 x C-C 7/ x O=O 2 Bonds Formed 4 x O=C 6 x O-H Bond Energy / kJ.mol-1 6(413) 348 7/ (494) 2 4555 4(707) 6(463) 5606 o Hrxn BE(bonds broken) BE(bonds formed) = 4555 – 5606 = -1051 kJ.mol-1