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Thermochemistry (General Chem)
Thermochemistry (General Chem)
Chapter 7: Thermochemistry
Philip Dutton University of Windsor, Canada Prentice-Hall 2002
Prentice-Hall 2002
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Contents
7-1 7-2 7-3 7-4 7-5 7-6 7-7 Getting Started: Some Terminology Heat Heats of Reaction and Calorimetry Work The First Law of Thermodynamics Heats of Reaction: U and H The Indirect Determination of H: Hesss Law
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Contents
7-7 7-8 7-9 The Indirect Determination of H, Hesss Law Standard Enthalpies of Formation Fuels as Sources of Energy Focus on Fats, Carbohydrates, and Energy Storage
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System Surroundings
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Terminology
Energy, U
The capacity to do work.
Work
Force acting through a distance.
Kinetic Energy
The energy of motion.
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Energy
Kinetic Energy ek = Work w = Fd 1 2 mv2 kg m2 = J [ek ] = 2 s
kg m m = J [w ] = 2 s
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Energy
Potential Energy
Energy due to condition, position, or composition. Associated with forces of attraction or repulsion between objects.
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Heat
Energy transferred between a system and its surroundings as a result of a temperature difference. Heat flows from hotter to colder.
Temperature may change. Phase may change (an isothermal process).
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Units of Heat
Calorie (cal)
The quantity of heat required to change the temperature of one gram of water by one degree Celsius.
Joule (J)
SI unit for heat
1 cal = 4.184 J
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Heat Capacity
The quantity of heat required to change the temperature of a system by one degree.
Molar heat capacity.
System is one mole of substance.
q = mcT q = CT
Heat capacity
Mass specific heat.
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Conservation of Energy
In interactions between a system and its surroundings the total energy remains constant energy is neither created nor destroyed. qsystem + qsurroundings = 0 qsystem = -qsurroundings
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Example 7-2
Determining Specific Heat from Experimental Data. Use the data presented on the last slide to calculate the specific heat of lead. qlead = -qwater qwater = mcT = (50.0 g)(4.184 J/g C)(28.8 - 22.0)C qwater = 1.4x103 J qlead = -1.4x103 J = mcT = (150.0 g)(c)(28.8 - 100.0)C clead = 0.13 Jg-1C-1
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Heats of Reaction
Exothermic reactions.
Produces heat, qrxn < 0.
Endothermic reactions.
Consumes heat, qrxn > 0.
Calorimeter
A device for measuring quantities of heat.
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Bomb Calorimeter
qrxn = -qcal qcal = qbomb + qwater + qwires +
heat
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Example 7-3
Using Bomb Calorimetry Data to Determine a Heat of Reaction. The combustion of 1.010 g sucrose, in a bomb calorimeter, causes the temperature to rise from 24.92 to 28.33C. The heat capacity of the calorimeter assembly is 4.90 kJ/C. (a) What is the heat of combustion of sucrose, expressed in kJ/mol C12H22O11
(b) Verify the claim of sugar producers that one teaspoon of sugar (about 4.8 g) contains only 19 calories.
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Example 7-3
Calculate qcalorimeter: qcal = CT = (4.90 kJ/C)(28.33-24.92)C = (4.90)(3.41) kJ = 16.7 kJ Calculate qrxn: qrxn = -qcal = -16.7 kJ per 1.010 g
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Example 7-3
Calculate qrxn in the required units: -16.7 kJ qrxn = -qcal = = -16.5 kJ/g 1.010 g qrxn 343.3 g = -16.5 kJ/g 1.00 mol = -5.65 103 kJ/mol (a)
(b)
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qrxn = -qcal
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7-4 Work
In addition to heat effects chemical reactions may also do work.
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w=Fd
= (P A) h
= PV w = -PextV
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V = 1.88-1.02 L = 0.86 L
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101 J ) 1 L atm
Where did the conversion factor come from? Compare two versions of the gas constant and calculate. 8.3145 J/mol K 0.082057 L atm/mol K 1 101.33 J/L atm
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State Functions
Any property that has a unique value for a specified state of a system is said to be a State Function.
Water at 293.15 K and 1.00 atm is in a specified state. d = 0.99820 g/mL This density is a unique function of the state. It does not matter how the state was established.
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Functions of State
U is a function of state.
Not easily measured.
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U = Uf - Ui
U = qrxn + w In a system at constant volume: U = qrxn + 0 = qrxn = qv
Heats of Reaction
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Heats of Reaction
qV = qP + w We know that w = - PV and U = qP, therefore: U = qP - PV qP = U + PV
U = H - PV
= -563.5 kJ/mol = qV
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50.0 g = (50.0 g)(4.184 J/g C)(25.0-10.0)C + 44.0 kJ/mol 18.0 g/mol = 3.14 kJ + 122 kJ = 125 kJ
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Standard State
The pure element or compound at a pressure of 1 bar and at the temperature of interest.
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Enthalpy Diagrams
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H = +180.50 kJ
H = +90.25 kJ
H = -90.25 kJ
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Hesss Law
Hesss law of constant heat summation
If a process occurs in stages or steps (even hypothetically), the enthalpy change for the overall process is the sum of the enthalpy changes for the individual steps. N2(g) + O2(g) NO(g)
NO(g) + O2(g) NO2(g) N2(g) + O2(g) NO2(g)
H = +90.25 kJ
H = -57.07 kJ H = +33.18 kJ
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Enthalpy of Reaction
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Chapter 7 Questions
1, 2, 3, 11, 14, 16, 22, 24, 29, 37, 49, 52, 63, 67, 73, 81
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