Chapter 5 Thermochemistry Lecture Presentation Chapter 5 Thermochemistry Day 1 Edited by M. Day James F. Kirby Quinnipiac University Hamden, CT

Agenda Lecture: Thermochemistry Practice Problems PRACTICE AP EXAM HIGHLY ENCOURAGE YOU TO COMPLETE: PRACTICE AP EXAM IN AP PRINCETON BOOK THIS WEEKEND! PRACTICE AP EXAM NEXT SATURDAY, MAY 5TH 8am-11:30

Energy Energy is the ability to do __________or _____________. Energy used to cause an object that has mass to move is called _________. Energy used to cause the temperature of an object to rise is called ___________. This chapter is about thermodynamics, which is the study of energy transformations and thermochemistry, which applies the field to chemical reactions.

Energy Energy is the ability to do work or transfer heat. Energy used to cause an object that has mass to move is called work. Energy used to cause the temperature of an object to rise is called heat. This chapter is about thermodynamics, which is the study of energy transformations, and thermochemistry, which applies the field to chemical reactions, specifically.

Kinetic Energy Kinetic energy is energy an object possesses by virtue of its _________:

Kinetic Energy Kinetic energy is energy an object possesses by virtue of its motion:

Potential Energy Potential energy is energy an object possesses by virtue of its position or chemical composition. The most important form of potential energy in molecules is electrostatic potential energy, Eel: Q1 and Q2 are two interacting objects. K = 8.99 x 109 J-m/C and is the proportionality constant.

Potential Energy Potential energy is energy an object possesses by virtue of its _________ or ________________. The most important form of potential energy in molecules is ________________, Eel: Q1 and Q2 are two interacting objects. K = 8.99 x 109 J-m/C and is the proportionality constant.

Units of Energy The SI unit of energy is the _________ An older, non-SI unit is still in widespread use, the ___________ 1 cal = _______ J (Note: this is not the same as the calorie of foods; the food calorie is 1 kcal!)

Units of Energy The SI unit of energy is the joule (J): An older, non-SI unit is still in widespread use, the calorie (cal): 1 cal = 4.184 J (Note: this is not the same as the calorie of foods; the food calorie is 1 kcal!)

Definitions: System and Surroundings The _________ includes the molecules we want to study (here, the hydrogen and oxygen molecules). The ___________ are everything else (here, the cylinder and piston).

Definitions: System and Surroundings The system includes the molecules we want to study (here, the hydrogen and oxygen molecules). The surroundings are everything else (here, the cylinder and piston).

Definitions: Work Energy used to move an object over some distance is _______: ___________ where w is work, F is the force, and d is the distance over which the force is exerted.

Definitions: Work Energy used to move an object over some distance is work: w = F  d where w is work, F is the force, and d is the distance over which the force is exerted.

Heat Energy can also be ___________ as heat. Heat flows _______ warmer objects _______ cooler objects.

Heat Energy can also be transferred as heat. Heat flows from warmer objects to cooler objects.

Conversion of Energy Energy can be ___________ from one type to another. The cyclist has __________as she sits on top of the hill. As she coasts down the hill, her potential energy is converted to kinetic energy until the bottom, where the energy is converted to kinetic energy.

Conversion of Energy Energy can be converted from one type to another. The cyclist has potential energy as she sits on top of the hill. As she coasts down the hill, her potential energy is converted to kinetic energy until the bottom, where the energy is converted to kinetic energy.

First Law of Thermodynamics Energy is neither _________ nor ___________. In other words, the total energy of the universe is a constant If the system _______ energy, it must be _______ by the surroundings, and vice versa.

First Law of Thermodynamics Energy is neither created nor destroyed. In other words, the total energy of the universe is a constant If the system loses energy, it must be gained by the surroundings, and vice versa.

Internal Energy The internal energy of a system is the ____________________________of all components of the system; we call it _____.

Internal Energy The internal energy of a system is the sum of all kinetic and potential energies of all components of the system; we call it E.

Internal Energy ________________ By definition, the change in internal energy, E, is the final energy of the system minus the initial energy of the system: ________________

Internal Energy E = Efinal − Einitial By definition, the change in internal energy, E, is the final energy of the system minus the initial energy of the system: E = Efinal − Einitial

Changes in Internal Energy If E > 0,______________ Therefore, the system ___________ energy from the surroundings. This energy change is called __________.

Changes in Internal Energy If E > 0, Efinal > Einitial Therefore, the system absorbed energy from the surroundings. This energy change is called endergonic.

Changes in Internal Energy If E < 0, ______________ Therefore, the system ___________energy to the surroundings. This energy change is called _________.

Changes in Internal Energy If E < 0, Efinal < Einitial Therefore, the system released energy to the surroundings. This energy change is called exergonic.

integral energy. dynamic energy. internal energy. work. The sum of all of the kinetic and potential energies of a system is called the integral energy. dynamic energy. internal energy. work. Answer: c

integral energy. dynamic energy. internal energy. work. The sum of all of the kinetic and potential energies of a system is called the integral energy. dynamic energy. internal energy. work. Answer: c

1) The internal energy of a system is always increased by ________. A) adding heat to the system B) having the system do work on the surroundings C) a volume compression D) adding heat to the system and having the system do work on the surroundings E) withdrawing heat from the system 2)  The internal energy of a system ________. A) is the sum of the kinetic energy of all of its components B) is the sum of the potential and kinetic energies of the components C) refers only to the energies of the nuclei of the atoms of the component molecules D) is the sum of the rotational, vibrational, and translational energies of all of its components E) none of the above Which one of the following conditions would always result in an increase in the internal energy 3) of a system? A) The system gains heat and does work on the surroundings. B) The system gains heat and has work done on it by the surroundings. C) The system loses heat and does work on the surroundings. D) The system loses heat and has work done on it by the surroundings. E) None of the above is correct. 4) When a system ________, ∆E is always negative. A) absorbs heat and does work B) absorbs heat and has work done on it C) gives off heat and has work done on it D) gives off heat and does work E) None of the above is always negative. 4)

Changes in Internal Energy When energy is exchanged between the system and the surroundings, it is ____________ as either heat (q) or work (w). That is, ___________.

Changes in Internal Energy When energy is exchanged between the system and the surroundings, it is exchanged as either heat (q) or work (w). That is, E = q + w.

E, q, w, and Their Signs

Exchange of Heat between System and Surroundings When ___________ ______by the system from the surroundings, the process is ______________.

Exchange of Heat between System and Surroundings When heat is absorbed by the system from the surroundings, the process is endothermic.

Exchange of Heat between System and Surroundings When ________ ___________by the system into the surroundings, the process is _____________.

Exchange of Heat between System and Surroundings When heat is released by the system into the surroundings, the process is exothermic.

State Functions Usually we have no way of knowing the internal energy of a system; finding that value is simply too complex a problem. However, we do know that the internal energy of a system is independent of the path by which the system achieved that state. In the system below, the water could have reached room temperature from either direction. https://www.youtube.com/watch?v=SEapOFaYDlA

State Functions Therefore, internal energy is a state function. It depends only on the present state of the system, not on the path by which the system arrived at that state. And so, E depends only on Einitial and Efinal.

State Functions However, __________functions. Whether the battery is shorted out or is discharged by running the fan, its ____________ But q and w are different in the two cases.

State Functions However, q and w are not state functions. Whether the battery is shorted out or is discharged by running the fan, its E is the same. But q and w are different in the two cases.

A system absorbs heat during an _______ process. exothermic isothermal endothermic isobaric Answer: c

A system absorbs heat during an _______ process. exothermic isothermal endothermic isobaric Answer: c

When a piece of iron at 356 K is placed in water at 298 K, what happens? Energy flows from iron to water. Energy flows from water to iron. Energy does not flow. Energy is not conserved. Answer: a

When a piece of iron at 356 K is placed in water at 298 K, what happens? Energy flows from iron to water. Energy flows from water to iron. Energy does not flow. Energy is not conserved. Answer: a

Work Usually in an open container the only work done is by a gas pushing on the surroundings (or by the surroundings pushing on the gas).

Work We can measure the work done by the gas if the reaction is done in a vessel that has been fitted with a piston: ___________

Work We can measure the work done by the gas if the reaction is done in a vessel that has been fitted with a piston: w = −PV

Enthalpy If a process takes place at constant ______________ (as the majority of processes we study do) and the only work done is this pressure–volume work, we can account for heat flow during the process by measuring the ___________________. Enthalpy is the ____________plus the product of _________________: _________

Enthalpy If a process takes place at constant pressure (as the majority of processes we study do) and the only work done is this pressure–volume work, we can account for heat flow during the process by measuring the enthalpy of the system. Enthalpy is the internal energy plus the product of pressure and volume: H = E + PV

Enthalpy When the system changes at constant pressure, the change in enthalpy, H, is H = (E + PV) This can be written _______________

Enthalpy When the system changes at constant pressure, the change in enthalpy, H, is H = (E + PV) This can be written H = E + PV

Enthalpy Since E = q + w and w = −PV, we can substitute these into the enthalpy expression: H = E + PV H = (q + w) − w __________ So, at constant pressure, the change in enthalpy is the heat ___________.

Enthalpy Since E = q + w and w = −PV, we can substitute these into the enthalpy expression: H = E + PV H = (q + w) − w H = qp So, at constant pressure, the change in enthalpy is the heat gained or lost.

Endothermic and Exothermic A process is endothermic when H is _________. A process is exothermic when H is _________.

Endothermic and Exothermic A process is endothermic when H is positive. A process is exothermic when H is negative.

Enthalpy of Reaction The change in enthalpy, ________, is the enthalpy of the products minus the enthalpy of the reactants: _____________________

Enthalpy of Reaction The change in enthalpy, H, is the enthalpy of the products minus the enthalpy of the reactants: H = Hproducts − Hreactants

Enthalpy of Reaction This quantity, H, is called the enthalpy of reaction, or the ________________.

Enthalpy of Reaction This quantity, H, is called the enthalpy of reaction, or the heat of reaction.

The Truth about Enthalpy Enthalpy is an __________ property. H for a reaction in the forward direction is __________, but opposite in sign, to H for the reverse reaction. H for a reaction depends on the state of the __________ and the state of the ____________.

The Truth about Enthalpy Enthalpy is an extensive property. H for a reaction in the forward direction is equal in size, but opposite in sign, to H for the reverse reaction. H for a reaction depends on the state of the products and the state of the reactants. Extensive property – depends on the amount of substance

Calorimetry Since we cannot know the exact enthalpy of the reactants and products, we measure H through __________, the measurement of heat flow. The instrument used to measure heat flow is called a ___________.

Calorimetry Since we cannot know the exact enthalpy of the reactants and products, we measure H through calorimetry, the measurement of heat flow. The instrument used to measure heat flow is called a calorimeter.

Heat Capacity and Specific Heat The amount of energy required to raise the temperature of a substance by 1 K (1 C) is its ________________, usually given for one mole of the substance.

Heat Capacity and Specific Heat The amount of energy required to raise the temperature of a substance by 1 K (1 C) is its heat capacity, usually given for one mole of the substance.

Heat Capacity and Specific Heat We define ________________(or simply specific heat) as the amount of energy required to raise the ___________________________________________________

Heat Capacity and Specific Heat We define specific heat capacity (or simply specific heat) as the amount of energy required to raise the temperature of 1 g of a substance by 1 K (or 1 C).

Heat Capacity and Specific Heat Specific heat, then, is

Constant Pressure Calorimetry By carrying out a reaction in aqueous solution in a simple calorimeter, the heat change for the system can be found by measuring the heat change for the water in the calorimeter. The specific heat for water is well known (4.184 J/g∙K). We can calculate H for the reaction with this equation: q = m  Cs  T

Hess’s Law H is well known for many reactions, and it is inconvenient to measure H for every reaction in which we are interested. However, we can estimate H using published H values and the properties of enthalpy.

Hess’s Law Hess’s law: If a reaction is carried out in a series of steps, H for the overall reaction will be ___________________for the individual steps. Because H is a state function, the total enthalpy change depends only on the -________(reactants) and the ________(products) of the reaction.

Hess’s Law Hess’s law: If a reaction is carried out in a series of steps, H for the overall reaction will be equal to the sum of the enthalpy changes for the individual steps. Because H is a state function, the total enthalpy change depends only on the initial state (reactants) and the final state (products) of the reaction.

Enthalpies of Formation An __________________, Hf, is defined as the enthalpy change for the reaction in which a compound is made from its constituent elements in their ____________________.

Enthalpies of Formation An enthalpy of formation, Hf, is defined as the enthalpy change for the reaction in which a compound is made from its constituent elements in their elemental forms.

Standard Enthalpies of Formation Standard enthalpies of formation, ∆Hf°, are measured under standard conditions (25 ºC and 1.00 atm pressure).

Calculation of H C3H8(g) + 5 O2(g)  3 CO2(g) + 4 H2O(l) Step 1) Decomposition of propane to the elements: C3H8(g)  _____________________

Calculation of H C3H8(g) + 5 O2(g)  3 CO2(g) + 4 H2O(l) Step 1) Decomposition of propane to the elements: C3H8(g)  3 C(graphite) + 4 H2(g)

Calculation of H C3H8(g) + 5 O2(g)  3 CO2(g) + 4 H2O(l) Step 2) Formation of CO2: 3 C(graphite) + 3 O2(g) _______________

Calculation of H C3H8(g) + 5 O2(g)  3 CO2(g) + 4 H2O(l) Step 2) Formation of CO2: 3 C(graphite) + 3 O2(g) 3 CO2(g)

Calculation of H C3H8(g) + 5 O2(g)  3 CO2(g) + 4 H2O(l) Step 3) Formation of H2O: 4 H2(g) + 2 O2(g)  _________

Calculation of H C3H8(g) + 5 O2(g)  3 CO2(g) + 4 H2O(l) Step 3) Formation of H2O: 4 H2(g) + 2 O2(g)  4 H2O(l)

Calculation of H C3H8(g) + 5 O2(g)  3 CO2(g) + 4 H2O(l) So, all steps look like this: C3H8(g)  3 C(graphite) + 4 H2(g) 3 C(graphite) + 3 O2(g) 3 CO2(g) 4 H2(g) + 2 O2(g)  4 H2O(l)

Calculation of H C3H8(g) + 5 O2(g)  3 CO2(g) + 4 H2O(l) The sum of these equations is the overall equation! C3H8(g)  3 C(graphite) + 4 H2(g) 3 C(graphite) + 3 O2(g) 3 CO2(g) 4 H2(g) + 2 O2(g)  4 H2O(l) __________________________________

Calculation of H C3H8(g) + 5 O2(g)  3 CO2(g) + 4 H2O(l) The sum of these equations is the overall equation! C3H8(g)  3 C(graphite) + 4 H2(g) 3 C(graphite) + 3 O2(g) 3 CO2(g) 4 H2(g) + 2 O2(g)  4 H2O(l) C3H8(g) + 5 O2(g)  3 CO2(g) + 4 H2O(l)

Calculation of H We can use Hess’s law in this way: H = nHf,products – _______________ where___and ___ are the stoichiometric coefficients.

Calculation of H We can use Hess’s law in this way: H = nHf,products – mHf°,reactants where n and m are the stoichiometric coefficients.

Calculation of H using Values from the Standard Enthalpy Table C3H8(g) + 5 O2(g)  3 CO2(g) + 4 H2O(l) H = [3(−393.5 kJ) + 4(−285.8 kJ)] – [1(−103.85 kJ) + 5(0 kJ)] = [(−1180.5 kJ) + (−1143.2 kJ)] – [(−103.85 kJ) + (0 kJ)] = (−2323.7 kJ) – (−103.85 kJ) = __________

Calculation of H using Values from the Standard Enthalpy Table C3H8(g) + 5 O2(g)  3 CO2(g) + 4 H2O(l) H = [3(−393.5 kJ) + 4(−285.8 kJ)] – [1(−103.85 kJ) + 5(0 kJ)] = [(−1180.5 kJ) + (−1143.2 kJ)] – [(−103.85 kJ) + (0 kJ)] = (−2323.7 kJ) – (−103.85 kJ) = −2219.9 kJ

Energy in Foods Most of the fuel in the food we eat comes from ______________ and _________.

Energy in Foods Most of the fuel in the food we eat comes from carbohydrates and fats.

Energy in Fuels The vast majority of the energy consumed in this country comes from fossil fuels.

Other Energy Sources Nuclear fission produces 8.5% of the U.S. energy needs. Renewable energy sources, like solar, wind, geothermal, hydroelectric, and biomass sources produce 7.4% of the U.S. energy needs.

A substance’s specific heat is its heat capacity per mole. gram. joule. kelvin. Answer: b

A substance’s specific heat is its heat capacity per mole. gram. joule. kelvin. Answer: b

Warm Up: Fill in the blanks qsol vs. qrxn If we conduct a reaction between two substances in aqueous solution, then the enthalpy of the reaction can be indirectly calculated with the following equation: q = Cp x m x ΔT If q of the solution (qsol) is positive, it means the solution ______ heat. And, therefore, q of the reaction (qrxn) is _______, because the reaction _____ heat energy.

qsol vs. qrxn “If we conduct a reaction between two substances in aqueous solution, then the enthalpy of the reaction can be indirectly calculated with the following equation: q = Cp x m x ΔT If q of the solution (qsol) is positive, it means the solution gains heat. And, therefore, q of the reaction (qrxn) is negative, because the reaction loses or produces heat energy. It is exothermic! Final – Initial Specific Heat of H2O at constant pressure Masssol