Chapter 5 THERMO. THERMO chemistry. 5.4 Enthalpy of Reactions 5.5 Calorimetry 5.6 Hess s Law 5.7 Enthalpies of Formation

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1 Chapter 5 THERMO THERMO chemistry 5.4 Enthalpy of Reactions 5.5 Calorimetry 5.6 Hess s Law 5.7 Enthalpies of Formation

2 Chemical Equations 1 st WRITE the Chemical Equation 2 nd BALANCE the Chemical Equation 3 rd INTERPRET the Chemical Equation Now when Interpreting Chemical Equations must also include ENERGY

3 Involved in Chemical Processes Physical Process H 2 O(gas) H 2 O(liquid) + HEAT or Chemical Process CH 4 (g) + 2O 2 (g) CO 2 (g) + 2H 2 O + HEAT

4 Chemical reactions can RELEASE when they occur CH 4 (g) + 2 O 2 (g) CO 2 (g) + 2 H 2 O + HEAT or Chemical reactions can ABSORB when they occur 2 C (s) + 2 H 2 (g) + HEAT C 2 H 4 (g)

5 predict whether heat is absorbed endothermic or released exothermic by the system for : (1) An ice cube melts (2) butane is burned

6 Exo thermic and Endo thermic Processes thermic: transfers heat TO THE surroundings An exothermic process feels HOT thermic: absorbs heat FROM THE surroundings An endothermic process feels cold

7 Two (2) Ways to express heat 1. Heat can be expressed as q - or - 2. Expressed as H called Enthalpy - or - H Change in

8 Table 5.1 Sign Convention EXO thermic Heat is transferred FROM SYSTEM to the surroundings: q > 0 ; H < 0 ENDO thermic Heat is transferred FROM SURROUNDINGS to the system: q < 0 ; H > 0

9

10 System & Surroundings I. SYSTEM the portion of the universe that is singled out for study II. SURROUNDINGS everything outside the system III. CONSERVATION OF ENERGY

11 Open, Closed, & Isolated Systems

12 HEAT LOST = HEAT GAIN Something is gaining Heat While Something else looses Heat. IF YOU KNOW ONE OF THESE {Heat Lost - or - Heat Gained} THEN YOU KNOW

13 THERMO chemistry Two parts I. EXPERIMENTAL II. MATHEMATICAL

14 Energy Changes Involved With Part 1. PHYSICAL Changes a) Phase Changes b) WITHIN a Phase Part 2. CHEMICAL Changes

15 Part 1a Energy Changes Involved Physical Changes PHASE Changes Gas Liquid Solid

16

17

18 Energy Expressed In Terms of q for a Change Of State H 2 O (solid) H 2 O (liq) - Energy H 2 O(solid) H 2 O(liq) kj/mole The Sign Means Heat is Needed

19 Energy Can Also Be Expressed As A CHANGE In ENTHALPY ( H) H 2 O (solid) H 2 O (liq) - Energy H 2 O (solid) H 2 O (liq) H = kj/mole The Sign Means Heat is Needed!!!! NOTE THE SIGN CHANGE!!!!

20

21 Example 1: How much energy is needed to melt [ H 2 O (solid) H 2 O (liq) +/- Heat ] 18 grams of H 2 O at 0 o C? [The Heat of fusion of H 2 O = KJ / mole] 18 grams of water = 1.0 mole of water therefore need KJ of heat

22 Example 2: What quantity of Heat is required to vaporize 18 grams of H 2 O at 100 o C? H 2 O (liq) H 2 O (gas) +/- Heat [The Heat of vaporization = KJ / mole ] 18 grams of water = 1.0 mole of water therefore need KJ of heat

23 Part 1b [NO CHANGE IN PHASE] Energy Change WITHIN A State Gas Gas Liquid Liquid Solid Solid

24 Specific Heat Specific Heat- The heat required to raise the temperature of 1 gm of a substance by 1 o C EVERY SUBSTANCE HAS ITS OWN UNIQUE SPECIFIC HEAT (SH) For Water :S.H. = 4.18 JOULES (Grams) ( T)

25 UNIQUE SPECIFIC HEAT

26

27 Specific heat = quantity of heat transferred (grams of substance) x (temperature change)

28 How much heat energy is required to heat one pound of water from 25 o C (room temp) to its boiling point (100 o C)? LET THE UNITS SOLVE THE PROBLEM. Energy = (Specific Heat)x(grams)x(change in Temp) For Water :S.H. = 4.18 JOULES (Grams) ( T)

29 Energy required to heat one pound of water from 25 to 100 o C? Joules = Joules 4.18 C g ( ( ) o 454g (75 ) )( T ) Heat Energy = 142,329 Joules How many Significant Figures? Therefore answer is?????? Joules

30 Large beds of rocks are used in some solar-heated homes to store heat Calculate the quantity of heat absorbed by 50.0 kg of granite if the temperature increases by 12.0 C [The specific heat of granite is 0.79 J/g-K]

31 How much heat is absorbed by 50.0 kg of cement if the temperature increases 12.0 C [The specific heat of cement is 0.88 J/g-K] Let UNITS solve the problem Joules = (Specific Heat)x(grams)x(change in Temp) Joules = (0.88 J / g-k)(50.0x10 3 g)(12.0 C) Joules =

32 How much heat is absorbed by 50.0 kg of Rocks J Cement J Water J What statement can be made about specific heat in terms of substances absorbing or releasing heat?

33 Heat Flow Heat spontaneously flows from a hot object to a cold one until the temperature of the two objects are the same

34 Every substance has its own unique specific heat Use that information to identify an unknown 1. Put into a Styrofoam cup ¾ full of water a piece of hot metal 2. Measure temperature change of water

35 A 2.61 gram block of metal was heated to o C and put into an insulated cup containing g of water. The water temperature rose from to o C

36 When the Hot Metal is dropped into the cup of water HEAT Flows from the metal to the water Heat Lost by Metal = Heat Gain by Water Heat spontaneously flows from a hot object to a cold one until the temperature of the two objects are the same

37 Metal: 2.61 grams ; initial temp = 100 o C Water: grams; initial temp = o C final temp = C 1. What was the final temperature of the Metal? 2. How much energy did the water gain? 3. How much energy did the Metal lose? 4. What is the specific heat of Metal?

38 Joules Heat GAIN by Water Joules = 4.18 C g ( ( ) o 28.0g ( ) )( T ) = 173 Joules {Heat Gained by Water equals Heat LOST by Metal Metal LOST 173 Joules FOR THE METAL: 173 Joules = S.H x (2.61 g) x ( )

39 SpecificHeat = ( 173Joules 2.61g )( ) =???? WHAT WAS THE UNKNOWN METAL?

40 Review of Part 1 Energy Changes Involved With PHYSICAL Changes a) Phase Changes b) WITHIN a Phase

41 How much Energy required to heat 1.0 gram of ice at 10 o C to steam at 110 o C Ice Ice Liq Liq Gas Gas -10 o C 0 o C 0 o C 100 o C 100 o C 110 o C What information do you need to work this problem

42 Data Required for problem Heat of fusion = kj / mole Heat of vaporization = kj / mole Specific heat: Ice J / g - K Liq J / g K Steam J / g - K

43 Energy required to heat 1.0 gram of ice at 10 o C to ice at 0 o C? Heat required to melt 1.0 gram of ice? Heat required to heat 1.0 gram of water at 0 o C to water at 100 o C? Heat required to vaporize 1.0 grams of H 2 O? Heat required to heat 1.0 gram of steam at 100 o C to steam at 110 o C?

44 How much Energy required to heat 1.0 gram of ice at 10 o C to steam at 110 o C Add all the numbers 21 J kj J kj + 18 J How many significant figures in answer?

45

46 Part 2 CHEMICAL REACTIONS Reactants Products +/-ENERGY

47 Chemical reactions can release or absorb heat Energy is stored in Chemical BONDS It TAKES Energy To BREAK Bonds Energy Is RELEASED When A Bond Is Formed

48 Enthalpies of Reaction For a reaction: H = H final H initial = H products H reactants

49 HEAT OF REACTION CH O 2 CO H 2 O + HEAT The PLUS Sign Means Heat Is Given Off OR CH O 2 CO H 2 O H = - # The MINUS Sign Means Heat Is Given Off

50 DETERMINATION of HEATS of REACTIONS 1. THE DIRECT METHOD EXPERIMENTAL Use A Calorimeter 2. THE INDIRECT METHOD MATHEMATICAL Use HESS S Law

51 1. The Direct Method EXPERIMENTAL Go to Lab and Use A Calorimeter HEAT LOST = HEAT GAINED

52 Two (2) types of CALORIMETERS 1. OPEN { to the atmosphere and 2. CLOSED {to the atmosphere

53 OPEN CALORIMETER Also called a CONSTANT PRESSURE CALORIMETER Styrofoam cup

54 100 ml of 0.5 M HCl added to 100 ml of 0.5 M NaOH

55 Data Collected from experiment Volume of M NaOH(aq) = 1.00 x 10 2 ml Volume of M HCl(aq) = 1.00 x 10 2 ml Initial Temperature = o C Final Temperature = o C

56 Detemine the heat of the reaction PER MOLE (the Heat of neutralization) What GIVES OFF THE HEAT? The reaction! 1 HCl(aq) + 1 NaOH (aq) H 2 O + NaCl (aq) + HEAT What ABSORBS THE HEAT? The solution

57 How do you determine the Heat of the reaction? From the HEAT GAINED by the SOLUTION Joules = (Specific Heat) x (grams) x (Temp Change) of the solution from density from experiment

58 Number of GRAMS =? 100 ml HCl (aq) ml NaOH (aq) ml of each = ml total 2. Relationship between weight & volume? 3. DENSITY of solution 4. If Density = 1.00 g / ml 5. Have grams of solution

59 Let UNITS solve the problem Joules = (Specific Heat) x (grams) x (change in T) change in Temp =? grams = 200 grams of solution Specific Heat = Joules 4.18 gram x temp change Joules = (Specific Heat) x (grams) x (change in T) Joules = (4.184)(200)(3.42) =

60 Joules = (4.184)(200)(3.42) = kj 1 HCl(aq) + 1 NaOH (aq) H 2 O + NaCl (aq) + Heat kj of heat given off when 1.00 x 10 2 ml of M HCl (aq) is mixed with 1.00 x 10 2 ml of M NaOH (aq) How much heat given off per mole of water formed?

61 heat of neutralization per mole? How many moles of water formed? 1.00 x 10 2 ml of both M of HCl(aq) & NaOH Moles = Molarity x Volume = H + (aq) OH - (aq) 0.05 H 2 O kj 1.00 H + (aq) OH - (aq) 1.00 H 2 O +

62 Calorimeter [Used For Gas Reactions] CONSTANT VOLUME CALORIMETER It is called a BOMB CALORIMETER Because the Chemical Reaction Occurs in a CLOSED Container

63 See Text Fig 5.19 Page 186

64 Chemical Reaction takes place in Bomb HEAT IS GIVEN off by Reaction (SYSTEM) HEAT IS ABSORBED by SURROUNDINGS Surroundings are 1. WATER In Calorimeter 2. Everything else {thermometer, stirrer, metal bomb itself, etc

65 Example grams Of Mg Was Burned In a Constant Volume Calorimeter Write & Balance the COMBUSTION Reaction Mg + O MgO + HEAT 2 Heat Lost by = Heat Gain by Chemical 1. Water + Reaction 2. Calorimeter

66 Data Collected from experiment The Calorimeter had a Heat Capacity = 1769 J/ 0 C Calorimeter Contained 3.00x10 2 ml of Water Initial Temperature = 22.5 o C Final Temperature = 42.4 o C

67 1. Heat Gain by Water = S. H. x grams x Temp q water = (4.184 x 300 x 19.9 ) 2. Heat Gain by Calorimeter = Heat Cap x Temp Change q Calorimeter = (1769 x 19.9 ) Total Heat Gained = Water + Calorimeter

68 = (1769 x 19.9 ) + (4.184 x 300 x 19.9 ) = (35,203.1) + (24,978.48) Joules = Joules for grams of Mg HEAT LOST = HEAT GAIN How do you convert from grams to moles?

69 Record Data Record results in Tabular Form

70 Heats of Combustion (- H) per mole in kj at 25 o C HC 2 H 3 O 2 (aq) { Acetic Acid (aq) CH 4 (g) { Methane C 2 H 6 (g) C 6 H 6 (liq) C 6 H 12 (liq) Sucrose (s)

71 Enthalpy is an EXTENSIVE property ( H is directly proportional to amount): CH 4 (g) + 2 O 2 (g) CO 2 (g) + 2 H 2 O(liq) H = kj 2 CH 4 (g) + 4 O 2 (g) 2 CO 2 (g) + 4 H 2 O(liq) H = kj Phase (solid, liquid, gas) is Important CH 4 (g) + 2 O 2 (g) CO 2 (g) + 2 H 2 O(gas) H = kj 4 CH 4 (g) + 8 O 2 (g) 4 CO 2 (g) + 8 H 2 O(g) H = kj Note the state of water

72 Next, DETERMINATION OF HEATS OF REACTIONS Using 2. THE INDIRECT METHOD MATHEMATICAL Use Of HESS S Law

73 I. COMBUSTION of hydrocarbons CH 4 (g) + 2 O 2 (g) CO 2 (g) + 2 H 2 O (g) II. FORMATION Reactions e.g., CH 4 (Methane) C(s) + 2 H 2 (g) CH 4 (g)

74 Standard State The Standard State of a substance is the state the pure substance is in at atmospheric pressure ( 1 atm) and 25 o C The standard state of carbon is graphite and not diamond The standard state of hydrogen is H 2 not H

75 STANDARD ENTHALPIES OF FORMATION For example H 2 O (liq) is formed from its elements as they exist in nature H 2 (gas) + ½ O 2 (gas) H 2 O (liq) H = kj

76

77 STANDARD ENTHALPIES OF FORMATION THE STANDARD ENTHALPY OF FORMATION ( H f ) OF ANY ELEMENT IN ITS MOST STABLE FORM IS ZERO (BY DEFINATION)

78 HESS S LAW ENTHALPY CHANGES ARE ADDITIVE

79 Example 1 Calculate [using Hess Law] the heat of reaction for CO(g) + ½ O 2 (g) CO 2 (g) What DATA Do You Need From Table?

80 H f From Table WRITE AND BALANCE REACTIONS Formation of CO (g) is : 1. C (s) + ½ O 2 (g) CO(g) H = kj Formation of CO 2 (g) is : 2. C (s) + O 2 (g) CO 2 (g) H = kj

81 Want CO (g) + ½ O 2 (g) CO 2 (g) 1. C (s) + ½ O 2 (g) CO(g) H = kj REWRITE Eq 1 1b. CO (g) C (s) + ½ O 2 (g) H = kj also 2. C (s) + O 2 (g) CO 2 (g) H = kj

82 CO (g) C (s) + ½ O 2 (g) H = kj C (s) + O 2 (g) CO 2 (g) H = kj Add Equations To Get Reaction Wanted: CO (g) + ½ O 2 (g) CO 2 (g) Add H s To Get : H = kj kj =

83 Example 2 Find the Enthalpy of Formation of C 3 H 8 (g) Given Enthalpy of combustion of C 3 H 8 (g) = kj Enthalpy of formation of CO 2 (g) = kj Enthalpy of formation of H 2 O(g) = kj

84 Write and balance the following reactions Combustion of one mole of C 3 H 8 (g) Formation of one mole of CO 2 (g) Formation of one mole of H 2 O(g) Formation of one mole of C 3 H 8 (g) 3 C (s) +4 H 2 (g) C 3 H 8 (g) H =???

85 Example 3 Find the Enthalpy of Formation of C 3 H 8 (g) From Enthalpy of combustion of C 3 H 8 (g) = kj Enthalpy of formation of CO 2 (g) = kj Enthalpy of formation of H 2 O(g) = kj answer 3 C (s) +4 H 2 (g) C 3 H 8 (g) H = kj

86 Example 4 Find the Heat of Vaporization of Water From the following HEATS of COMBUSTION C 3 H 8 (g) + 5O 2 (g) 3CO 2 + 4H 2 O(g) C 3 H 8 (g) + 5O 2 (g) 3CO 2 + 4H 2 O(l) H = kj H = kJ NOTE: These reactions have Nothing to do with the vaporization of water

87 Want H for H 2 O (liquid) H 2 O (gas) C 3 H 8 (g) + 5O 2 (g) 3CO 2 + 4H 2 O(g) C 3 H 8 (g) + 5O 2 (g) 3CO 2 + 4H 2 O(l) H = kj H = kJ Rewrite last equation to get 3CO 2 + 4H 2 O(l) C 3 H 8 (g) + 5O 2 (g) H = kj WHY?

88 Want H for H 2 O (liquid) H 2 O (gas) C 3 H 8 (g) + 5O 2 (g) 3CO 2 + 4H 2 O(g) H = kj 3CO 2 + 4H 2 O(l) C 3 H 8 (g) + 5O 2 (g) H = kj Add Equations getting 4 H 2 O (liquid) 4 H 2 O (gas) H = kj H 2 O (liquid) H 2 O (gas) H =

89 Given the data N 2 (g) + O 2 (g) 2 NO(g) H = kj 2 NO(g) + O 2 (g) 2 NO 2 (g) H = kj 2 N 2 O(g) 2N 2 (g) + O 2 (g) H = kj Use Hess s law to calculate H For the reaction N 2 O(g) + NO 2 (g) 3 NO(g)

90 Example 4 Find H for N 2 O(g) + NO 2 (g) 3NO(g) Given N 2 (g) + O 2 (g) 2 NO(g) H = kj 2 NO(g) + O 2 (g) 2 NO 2 (g) H = kj 2 N 2 O(g) 2N 2 (g) + O 2 (g) H = kj Add The Following Equations N 2 (g) + O 2 (g) 2 NO(g) H = kj NO 2 (g) NO(g) + ½ O 2 (g) H = ½ [ kj] N 2 O(g) N 2 (g) + ½ O 2 (g) H = ½ [ kj]

91 Energy From Foods

92 Energy in our bodies comes from fats and carbohydrates (mostly) Carbohydrates converted into glucose, then: C 6 H 12 O O 2 6 CO H 2 O H = kj Fats: contain more energy; are not water soluble, so are good for energy storage. 2 C 57 H 110 O O CO H 2 O H = - 75,520 kj

93 Which releases the greatest amount of energy per gram upon metabolism (a) carbohydrates (b) proteins (c) fats

94 Energy From Fuels

95 Which releases the greatest amount of energy per gram upon combustion (a) Methane (b) gasoline (c) hydrogen

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