10-1 Heat 10-2 Calorimetry 10-3 Enthalpy 10-4 Standard-State Enthalpies 10-5 Bond Enthalpies 10-6 The First Law of Thermodynamics

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1 Chapter 10 Thermochemistry 10-1 Heat 10-2 Calorimetry 10-3 Enthalpy 10-4 Standard-State Enthalpies 10-5 Bond Enthalpies 10-6 The First Law of Thermodynamics OFB Chap. 10 1

2 OFB Chap. 10 2

3 Thermite Reaction 2 Al (s) + Fe 2 O 3 (s) Al 2 O 3 (s) + 2Fe (s) OFB Chap. 10 3

4 Chapter 10 Thermochemistry Heat Capacity, Cp, is the amount of heat required to raise the temperature of a substance by one degree at constant pressure. Cp is always a positive number Q and T must be both negative or positive If q is negative, then heat is evolved or given off and the temperature decreases If q is positive, then heat is absorbed and the temperature increases OFB Chap. 10 4

5 Heat Capacity (continued) C p units are energy per temp. change C p units are Joule/ o K or JK -1 Molar heat capacity Units are J/K/mole or JK -1 mol -1 OFB Chap. 10 5

6 OFB Chap. 10 6

7 Specific Heat Capacity The word Specific before the name of a physical quantity very often means divided by the mass Specific Heat Capacity is the amount of heat required to raise the temperature of one gram of material by one degree Kelvin (at constant pressure) c s Hg (l) SiO O H 2 O 4.18 OFB Chap. 10 7

8 OFB Chap. 10 8

9 OFB Chap T mc q Tm q m C c Equating some realtionships s p s m T q / s p p p s p p s p Mc c m C M c c c M m nc mc C Equating some relationships

10 Chapter 10 Thermochemistry Example (not in book) a.) Calculate the molar heat capacity of quartz (SiO 2 ) if c SiO2 s J/K/g b) Calculate the amount of heat required to raise 45.0 Kg of rock (quartz) by 15 C. Strategy a) Use relationship c p Mc s b) Use q mc s T OFB Chap

11 Example (not in book) a.) Calculate the molar heat capacity of quartz (SiO 2 ), if c s SiO J/K/g b) Calculate the amount of heat required to raise 45.0 Kg of rock (quartz) by 15 C. Solution a) Find the molar mass of quartz and Use relationship c p Mc s c p Mc s 60.08g mol b) Use q mc s T 0.739J Kg 44.4J Kmol q mc s T OFB Chap

12 Exercise 10-1 Exactly kj of heat is absorbed at a constant pressure by a sample of gaseous helium. The temperature increases by 15.0K. a.) Compute the heat capacity of the sample b.) The mass of the helium sample is 6.42 kg. Compute the specific heat capacity and molar heat capacity of helium. Strategy a.) Use the relationship C p q/ T B.) Use c s C p /m and use c p C p /n OFB Chap

13 c c s p Exercise 10-1 Exactly kj of heat is absorbed at a constant pressure by a sample of gaseous helium. The temperature increases by 15.0K. a.) Compute the heat capacity of the sample b.) The mass of the helium sample is 6.42 kg. Compute the specific heat capacity and molar heat capacity of helium. Solution a.) Use the relationship C p q/ T C p C n p p q 500kJ 500x10 T 15 K 15 K x10 J K b.) Use c s C p /m and use c p C p /n C m 33.33x x10 3 J K 3 g 33.33x10 J K x10 g 4g/mol 1 1 OFB Chap J 5.19JK 20.8JK 1 1 g 1 mol 1

14 Equilibration Temperature When 2 bodies are placed in contact, heat is exchanged until they reach a common final temperature Heat gained by the cooler body equals the heat lost by the warmer body If q is positive, heat is gained If q is negative, heat is lost q n 1 1 q c p1 T 2 1 n c 2 p2 T 2 n 1 c p1 T f T i 1 n 2 c p2 T f T i 2 Can also write similar equations for c s OFB Chap

15 Chapter 10 Thermochemistry Example (not in book) A 43.9g piece of Copper (c s J g -1 K -1 ) at 135 C is plunged into 254g of water (c s 4.18 J g -1 K -1 ) at 39 C. Assuming no heat is lost to the surroundings, what will be the final temperature? a C b C c C d C e. None of these OFB Chap

16 q 1 q m c 1 s1 2 T 1 m c 2 s2 T g T ( Tf 135C) ( 254gH20) ( Tf 39.0C) T T f Cu ( Tf 135C) ( Tf 39.0C) f 0.385J gcu K Tf f 4.18J g K C or answer d Also Try 10-2 Example and Exercise OFB Chap

17 Enthalpy Heat is a means by which energy is transferred among systems For processes carried out at constant pressure, the heat absorbed equals a change in Enthalpy, H. Enthalpy Change (note p denotes constant pressure) Enthalpy is a state property, which means it depends on its initial and final state, not the path to get there. Enthalpy is the heat content of a substance OFB Chap

18 OFB Chap

19 Enthalpy of Reaction If a chemical reaction occurs at constant pressure then (Heat absorbed) q p H H may be either positive or negative If H positive H > 0 q > 0 Means heat is absorbed And is called Endothermic If H negative H < 0 q < 0 Means heat is given off And is called Exothermic OFB Chap

20 CO (g) + ½ O 2 (g) CO 2 (g) H -283kJ An exothermic reaction If doubled (x2), double H 2CO (g) + 1O 2 (g) 2CO 2 (g) H -566kJ If the original reaction is reversed CO 2 (g) CO (g) + ½ O 2 (g) H +283kJ An endothermic reaction You can Try Example 10-5 OFB Chap

21 Phase Changes Phase changes are not chemical reactions but involve enthalpy change H 2 O(s) H 2 O(l) H fusion + 6 kj at 0C H fusion + means endothermic (add heat) if reversed H 2 O(l) H 2 O(s) H freeze - 6 kj H freeze - H fusion at melting point H vaporization at Boiling point - H Condensation Note that there are no T units, these occur at constant temperatures for freezing, fusion, vaporization or condensation OFB Chap

22 OFB Chap

23 How much heat energy is needed to decompose 9.74g of HBr (g) (M 80.9 g/mol) into its elements? H 2 + Br 2 2HBr (g) H kjmol -1 Strategy: Decomposition is actually the reverse reaction H to decompose 2 moles of HBr is +72.8kJ/mol OFB Chap

24 How much heat energy is needed to decompose 9.74g of HBr (g) (M 80.9 g/mol) into its elements? Solution: H 2 + Br 2 2HBr (g) H r kjmol -1 2HBr (g) H 2 + Br 2 H kjmol -1 q H 4.38 kj 72.8 kj 2 moles HBr 9.76 g HBr g HBr mole OFB Chap

25 Hess s Law Sometimes its difficult or even impossible to conduct some experiments in the lab. Because Enthalpy (H) is a State Property, it doesn t matter what path is taken as long as the initial reactants lead to the final product. Hess s Law is about adding or subtracting equations and enthalpies. Hess s Law: If two or more chemical equations are added to give a new equation, then adding the enthalpies of the reactions that they represent gives the enthalpy of the new reaction. OFB Chap

26 Standard State Enthalpies Designated using a superscript (pronounced naught) This is needed because Enthalpy varies with conditions Is written as H If no temperature is indicated in the subscript, assume 25 C. OFB text appendix D lists standard enthalpies of formation for a variety of chemical species at 1 atm and 25 C. Standard State conditions OFB Chap

27 Standard State Enthalpies H r is the sum of products minus the sum of the reactants For a general reaction a A + b B c C + d D from Hess s Law OFB Chap

28 Chapter 10 Thermochemistry Exercise 10-7 Suppose hydrazine and oxygen react to give dinitrogen pentaoxide and water vapor: 2N 2 H 4 (l) + 7O 2 (g) 2N 2 O 5 (s) + 4H 2 O (g) Calculate the H of this reaction, given that the reaction: N 2 (g) + 5/2O 2 (g) N 2 O 5 (s) has a H of -43 kj. OFB Chap

29 10-7 Exercise 2N 2 H 4 (l) + 7O 2 (g) 2N 2 O 5 (s) + 4H 2 O (g) H r What values to use? H f N 2 O 5 (s) given H kjmol -1 H f H 2 O (g) look up in App. D H f N 2 H 4 (l) look up in App. D H f O 2 (g) look up in App. D H r ( ) kjmol -1 OFB Chap

30 Typical Exam question Given the following thermo chemical equations, calculate the standard enthalpy of formation for propane, C 3 H 8 (g). 1. C(s) + O 2(g) CO 2(g) Answers H 2(g) + C3H 8(g) o r 1/2O 2(g) H H + H o r 5O 2(g) o r A. (-3131) kjmol -1 B. 129 C D. (-1773) (-393) kjmol H2O(l) (-286) kjmol CO 2(g) (-2452) kjmol H2O(l) OFB Chap

31 General aa + bb cc + dd H o o c H C + d H o D a H o A b H o B C(s) + H 2(g) C3H 8(g) O 2(g) + o f (CO2 1/2O 2(g) H H + H o f (H2 5O 2(g) o r CO 2(g) O) ) (-393) kjmol H2O(l) (-286) kjmol 3CO 2(g) (-2452) kjmol H2O(l) OFB Chap

32 Bond Enthalpy Bond Enthalpy ( H Dissociation ) is the enthalpy change in a reaction in which a chemical bond is broken in the gas phase. Bond Energy is the energy needed to break 1 mol of the particular bond. Energy is released when bonds are formed (exothermic) Energy must be supplied when bonds are broken (endothermic) OFB Chap

33 Bond Enthalpies The breaking of chemical bonds in stable substances often generates highly reactive products (or intermediates) CH 4 CH3 + H H kjmol -1 Called Bond Enthalpy OFB Table 10-3 p 462 gives Average Bond Enthalpies OFB Chap

34 Average Bond Enthalpies C 2 H 6 C 2 H 5 + H H kjmol -1 CHF 3 CF 3 + H H kjmol -1 CHCl 3 CCl 3 + H H kjmol -1 CHBr 3 CBr 3 + H H kjmol -1 average H C-H kjmol -1 Applications of Bond Enthalpy Given a reaction 1 st Step is break all bonds to give free atoms in the gas phase (Endothermic) 2 nd Step is form new bonds for the products. (Exothermic) OFB Chap

35 Applications of Bond Enthalpy Given a reaction 1 st Step is break all bonds to give free atoms in the gas phase (Endothermic) 2 nd Step is form new bonds for the products. (Exothermic) OFB Chap

36 Exercise Estimate the Standard Enthalpy of reaction for the gas-phase reaction that forms methanol from methane and water and compare it with the H r obtained from the data in Appendix D. CH 4 (g) + H 2 O(g) CH 3 OH(g) + H 2 (g) OFB Chap

37 CH 4 (g) + H 2 O(g) CH 3 OH(g) + H 2 (g) H H C H H + H H O H H C O H H + H H Broken 4 C-H or 2 O-H or + kjmol -1 Endothermic Formed 3 C-H or 1 O-H or 1 C-O or 1 H-H or - kjmol -1 Exothermic H H bonds broken + H bonds formed (estimated) Using Appendix D H 116 kjmol -1 OFB Chap

38 Chapter 10 Thermochemistry First Law of Thermodynamics The change in the internal energy of a system is equal to the work done on it plus the heat transferred to it. Second Law of Thermodynamics In a real spontaneous process the Entropy of the universe (meaning the system plus its surroundings) must increase. Third Law of Thermodynamics In any thermodynamic process involving only pure phases at equilibrium, the entropy change, S, approaches zero at absolute zero temperature; also the entropy of a crystalline substance approaches zero. OFB Chap

39 First Law of Thermodynamics E q + w q was previously defined as the Heat Absorbed by a system If q > 0, heat is absorbed If q < 0, heat is given off w is the work done on the body Recall w F x d w E Kinetic (1/2mv 2 ) w E potential mg h In chemistry this kind of mechanical work is Pressure- Volume work (P-V) OFB Chap

40 Force exerted by heating P 1 A Where P 1 is the pressure inside the vessel Where A is the Area of the piston P ext P 1 if balanced V A h Units are atm L or L atm Where 1 L atm Joules OFB Chap

41 Expansion V > 0 therefore w < 0 The system does work on the surroundings Compression V < 0 therefore w > 0 The surroundings have done work on the system Try Example and Exercise Calculate the work done on a gas and express it in Joules OFB Chap

42 Typical exam questions (1-4) A gas is compressed from 39.92L to 12.97L at a constant pressure of 5.00 atm. In the course of this compression 9.82 kj of energy is released Q1 The heat q for this process is a 135 kj b -135 kj c kj d 9.82 kj e can not be determined OFB Chap

43 A gas is compressed from 39.92L to 12.97L at a constant pressure of 5.00 atm. In the course of this compression 9.82 kj of energy is released Q2 The work w for this process is a 135 L atm b -135 L atm c L atm d 9.82 L atm e can not be determined OFB Chap

44 A gas is compressed from 39.92L to 12.97L at a constant pressure of 5.00 atm. In the course of this compression 9.82 kj of energy is released Q3 E for the process is a kj b 3.86 kj c kj d 125 kj e none of these 1 st Law of thermodynamics E q + w OFB Chap

45 A gas is compressed from 39.92L to 12.97L at a constant pressure of 5.00 atm. In the course of this compression 9.82 kj of energy is released Q4 H for the process is Answer a kj b kj c 3.83 kj d 9.82 KJ e none of these OFB Chap

46 Enthalpy and Energy 1 st Law of Thermodynamics E q + w At constant volume V 0 Thus w -P ext V 0 E q v (constant volume) Recall as previously stated H q p (constant pressure) Enthalpy is defined as H E + PV or Expressed as a change in Enthalpy H E + (PV) Rearrange E H - (PV) If PV nrt is the ideal gas law OFB Chap

47 Chapter 10 Thermochemistry n g is the change in the total chemical amount of gases in a reaction n g Total moles of product gases minus the Total moles of reactant gases OFB Chap

48 Example Calculate the internal 25 C for the following reaction 1 C(graphite) + O 2(g) 2 H kj Strategy Step 1 calculate (PV) Step 2 calculate E at 25 C 1CO(g) OFB Chap

49 Example Calculate the internal 25 C for the following reaction 1 C(graphite) + O 2(g) 2 H kj 1CO(g) Solution Step 1 calculate (PV) (PV) RT n g n g 1 ½ ½ mol (PV) RT n g (8.35 kjmol -1 ) (298 K) (1/2 mol) 1.24 kj Step 2 calculate E at 25 C E H (PV) (1.24) kj OFB Chap

50 Chapter 10 Thermochemistry Summary c p Heat Capacity where Cp p units are JK C p denotes Heat Capacity at constant pressure T Molar Heat Capacity C n -1 mol T 1 q T f - T i heat absorbed T Specific Heat Capacity Cp -1 cs units are JK g m -1 n 1 Equilibration Temperature c p1 n 1 c p1 1 1 p2 ( f i ) 1 2 p2 ( f i ) 2 T T q T q n n 2 2 c c T T 2 T OFB Chap

51 Enthalpy, H. If H positive H > 0 q > 0 Means heat is absorbed And is called Endothermic If H negative H < 0 q < 0 Means heat is given off And is called Exothermic Hess s Law: If two or more chemical equations are added to give a new equation, then adding the enthalpies of the reactions that they represent gives the enthalpy of the new reaction. q p H (note p denotes constant pressure) Enthalpy is a state property, which means it depends on its initial and final state, not the path to get there. OFB Chap

52 Standard State Enthalpies H is the sum of products minus the sum of the reactants For a general reaction a A + b B c C + d D H o c H o f (C) + d H o f (D) a H o f (A) b H o f (B) Bond Enthalpies H H bonds broken + H bonds formed First Law of Thermodynamics The change in the internal energy of a system is equal to the work done on it plus the heat transferred to it. E q + w OFB Chap

53 Enthalpy and Energy Enthalpy is defined as H E + PV or Expressed as a change in Enthalpy H E + (PV) For gases, If PV nrt is the ideal gas law (PV) (nrt) RT ng OFB Chap

54 Chapter 10 Thermochemistry Examples / exercises 10-1, 10-2, 10-5, 10-6, 10-7, 10-8, 10-9, 10-10, 10-11, HW Problems 11, 13, 19, 23, 33, 37, 40, 43, 49, 53, 59, 63 OFB Chap