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Chapter 5 Thermochemistry
Thermochemistry
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Overview of Thermochemistry
System vs. Surroundings Energy vs. Work Potential energy vs. Kinetic Energy Changes in internal energy endothermic vs. exothermic changes
Thermochemistry
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Units of Energy
The SI unit of energy is the joule (J). kg m2 1 J = 1 s2 An older, non-SI unit is still in widespread use: the calorie (cal). 1 cal = 4.184 J
Thermochemistry
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Thermochemistry
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Work
w=Fxd
In chemical systems, only P/V work (contraction or expansion of a gas) is of significance, and only when there is an increase or a decrease in the amount of gas present. There must be a change in volume in order for the system to do work on the surroundings (or have work done on it by the surroundings).
Thermochemistry
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State Functions
Usually we have no way of knowing the internal energy of a system; finding that value is simply too complex a problem.
Thermochemistry
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State Functions
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.
Thermochemistry
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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.
Thermochemistry
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Enthalpy
Enthalpy = the heat transferred between the system and the surroundings during a chemical reaction carried out under constant pressure = is the internal energy plus the product of pressure and volume: H = E + PV
Thermochemistry
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Enthalpy
When the system changes at constant pressure, the change in enthalpy, H, is H = (E + PV) This can be written H = E + PV
Thermochemistry
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Enthalpy
Since E = q + w and w = -PV, we can substitute these into the enthalpy expression: H = E + PV H = (q+w) w H = q So, at constant pressure, the change in enthalpy is the heat gained or lost.
Thermochemistry
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Enthalpy
Heat from surroundings system endothermic, H > 0 Heat from system surroundings exothermic, H < 0 Enthalpy is a state function doesnt matter how it got there.
Thermochemistry
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Thermochemistry
2009,
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Thermochemistry
2009,
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Thermochemistry
2009,
Prentice-Hall, Inc.
Thermochemistry
2009,
Prentice-Hall, Inc.
Thermochemistry
2009,
Prentice-Hall, Inc.
Enthalpy
H = change in enthalpy = the heat transferred between the system and surroundings during a chemical reaction carried out under constant pressure
Thermochemistry
2009,
Prentice-Hall, Inc.
Enthalpy
Heat from surroundings system endothermic, H > 0 Heat from system surroundings exothermic, H < 0 Enthalpy is a state function doesnt matter how it got there.
Thermochemistry
2009,
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Overview of Thermochemistry
Our focus:
Enthalpy is a state function. H and stoichiometry
Specific Heat q = c x m x T (and related calculations, including calorimetry) Hesss Law and its application, including enthalpies of formation
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Enthalpy of Reaction
The change in enthalpy, H, is the enthalpy of the products minus the enthalpy of the reactants:
H = Hproducts Hreactants
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Enthalpy of Reaction
This quantity, H, is called the enthalpy of reaction, or the heat of reaction.
Thermochemistry
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Thermochemistry
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H = 88 kJ
Thermochemistry
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Calorimetry
Since we cannot know the exact enthalpy of the reactants and products, we measure H through calorimetry, the measurement of heat flow.
Thermochemistry
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Thermochemistry
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Thermochemistry
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Thermochemistry
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Thermochemistry
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Bomb Calorimetry
Reactions can be carried out in a sealed bomb such as this one. The heat absorbed (or released) by the water is a very good approximation of the enthalpy change for the reaction.
Thermochemistry
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Bomb Calorimetry
Because the volume in the bomb calorimeter is constant, what is measured is really the change in internal energy, E, not H. For most reactions, the difference is very small.
Thermochemistry
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Thermochemistry
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Thermochemistry
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Hesss 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.
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Hesss Law
Hesss law states that 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.
Thermochemistry
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Hesss Law
Because H is a state function, the total enthalpy change depends only on the initial state of the reactants and the final state of the products.
Thermochemistry
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Hesss Law
Combustion of methane
CH4(g) + 2O2(g) CO2(g) + 2H2O(g) H = 802 kJ 2H2O(g) 2H2O(l) H = 88 kJ __________________________________________ CH4(g) + 2O2(g) CO2(g) + 2H2O(l) H = 890 kJ
Thermochemistry
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Thermochemistry
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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.
Thermochemistry
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Thermochemistry
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Heats of Formation
We can use the heats of formation to predict the H of a particular reaction another version of Hesss Law
Thermochemistry
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Thermochemistry
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Calculation of H
C3H8 (g) + 5 O2 (g) 3 CO2 (g) + 4 H2O (l)
Imagine this as occurring in three steps:
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)
Thermochemistry
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Calculation of H
C3H8 (g) + 5 O2 (g) 3 CO2 (g) + 4 H2O (l)
Imagine this as occurring in three steps:
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)
Thermochemistry
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Calculation of H
C3H8 (g) + 5 O2 (g) 3 CO2 (g) + 4 H2O (l)
Imagine this as occurring in three steps:
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)
Thermochemistry
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Calculation of H
C3H8 (g) + 5 O2 (g) 3 CO2 (g) + 4 H2O (l)
The sum of these equations is:
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)
Thermochemistry
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Calculation of H
We can use Hesss law in this way:
H = n Hfproducts m Hf reactants where n and m are the stoichiometric coefficients.
Thermochemistry
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Calculation of H
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
Thermochemistry
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