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Thermochemistry
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· The Nature of Energy
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Slide 1 / 118 Slide 2 / 118 Thermochemistry Slide 3 / 118 Table of Contents The Nature of Energy State Functions** Click on the topic to go to that section Enthalpy Measuring Enthalpy Changes: Calorimetry Energy Associated with
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The SI unit of energy is the Joule (J).
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3 kJ
Initial state Final state E of system decreases Internal energy, E E < E0
E E0 Energy lost to surroundings Initial state Final state E of system increases Internal energy, E Energy gained from surroundings E > E0
E E0
The system includes the reactants and products (here, the hydrogen, oxygen and water molecules). The surroundings are everything else (here, the cylinder and piston). Surroundings system When considering energy changes, we need to focus on a well- defined, limited part of the universe. The portion we focus on is called the system and everything else is called the surroundings. Consider the following reaction occurring within a metal cylinder.
If ∆E > 0, Efinal > Einitial The system absorbed energy from the surroundings. If ∆E < 0, Efinal < Einitial The system released energy from the surroundings. H2 (g) + O2 (g)
Internal energy, E
(negative)
(positive)
H2 O(l)
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System ∆E>0 Heat q > 0 Work w > 0 Surroundings When energy is exchanged between the system and the surroundings, it is either exchanged as either heat (q)
q
system gains heat
w
work done on system
net gain of energy by system
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Cooling Heating
#
These multiple paths explains how engines, air conditioners, batteries, heaters, etc. operate.
For instance, 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. If the battery shorts
heat, whereas if it is used to run the fan, some energy is used to do work. Q and w are NOT state functions.
The word "enthalpy" is derived from the Greek noun "enthalpos" which means heating. The enthalpy of a system (H) is a combination of the internal energy of a system (E) plus the work that needs to be done to create the space for the substance to occupy. It is impossible to measure enthalpy, H, directly. Only the change (∆H) can be measured.
At constant pressure, the change in enthalpy is the heat gained or lost by the system.
Note: This is only true at constant pressure. See ** for more information (W = P∆V)
The enthalpy of a system (H) is a combination of the internal energy of a system (E) plus the work that needs to be done to create the space for the substance (PV) to occupy. It is impossible to measure enthalpy, H, directly. Only the change (∆H) can be measured.
Enthalpy is an extensive property; its value depends on the quantity of the substance present. Combustion of 16 grams of CH4 ∆H = -891 kJ Combustion of 32 grams of CH4 ∆H = -1782 kJ
but opposite in sign, to ∆H for the reverse reaction. CH4(g) + 2O2(g) --> CO2(g) + 2H2O(g) ∆H = -891 kJ 2H2O(g) + CO2(g) --> CH4(g) + 2O2(g) ∆H = +891 kJ
the state of the reactants. CH4(g) + 2O2(g) --> CO2(g) + 2H2O(g) ∆H = -891 kJ CH4(g) + 2O2(g) --> CO2(g) + 2H2O(l) ∆H = -979 kJ
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The amount of energy required to raise the temperature of a substance by 1 K (1°C) is its heat capacity. The amount of energy required to raise the temperature of one gram of a substance by 1 K (1°C) is its specific heat (c).
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Many chemical reactions happen in aqueous solutions. The apparatus to the left is a calorimeter. How could you use it to measure the heat change for a chemical reaction in an aqueous solution?
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Many chemical reactions happen in aqueous solutions. The apparatus to the left is a calorimeter. How could you use it to measure the heat change for a chemical reaction in an aqueous solution?
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By carrying out a reaction in aqueous solution in a simple calorimeter like this one, the heat change for a system can be indirectly measured by measuring the heat change for the water in the calorimeter.
Because the specific heat for water is well known (4.184 J/g-K), we can measure ∆H for the reaction with this equation: D∆H = q = mc∆T (at constant pressure)
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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.
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Chemical and physical changes are usually accompanied by changes in energy. Recall the following terms: When energy is put into the system, the process is called _____________. When energy is released by the system, the process is called _____________.
Chemical and physical changes are usually accompanied by changes in energy. Recall the following terms: When energy is put into the system, the process is called _____________. When energy is released by the system, the process is called _____________.
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Energy is taken into the system from the surroundings (∆H > 0) Energy is released from the system to surroundings (∆H < 0)
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This graph is called a heating curve. It illustrates how temperature changes over time as constant heat is applied to a pure solid substance. Temperature (
0C)
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Temperature (
0C)
Heat added (each division corresponds to 4 kJ) Liquid water Ice and liquid water (melting) Liquid water and vapor (vaporization) Water vapor
25 75 125 50 100 Ice A B C D E F
Recall that any given substance has a different value for specific heat as a solid, as a liquid and as a gas. Additionally, melting one mole of a substance (∆Hfus) and vaporizing one mole of the same substance (∆Hvap) require different amounts of energy.
Sample Problem: Calculate the enthalpy change (in kJ) for converting 10.0 g of ice at -15.0°C to water at 25.0 °C.
Sample Problem: Calculate the enthalpy change (in kJ) for converting 10.0 g of ice at -15.0°C to water at 25.0 °C. Segment 1 Warming the ice from -15.0°C up to the substance's MP which is 0°C.
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Sample Problem: Calculate the enthalpy change (in kJ) for converting 10.0 g of ice at -15.0°C to water at 25.0 °C. Segment 2 Melting the ice at 0°C.
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Sample Problem: Calculate the enthalpy change (in kJ) for converting 10.0 g of ice at -15.0°C to water at 25.0 °C. Segment 3 Warming the liquid from 0°C to 25°C.
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We are now ready to apply either the calorimetry equation or ∆Hfus or ∆Hvap. Sample Problem: Calculate the enthalpy change (in kJ) for converting 10.0 g of ice at -15.0°C to water at 25.0 °C.
Segment 1 Warming the ice from -15.0°C up to the substance's MP which is 0°C.
Sample Problem: Calculate the enthalpy change (in kJ) for converting 10.0 g of ice at -15.0°C to water at 25.0 °C.
Segment 2 Melting the ice at 0 °C.
Sample Problem: Calculate the enthalpy change (in kJ) for converting 10.0 g of ice at -15.0°C to water at 25.0 °C.
Segment 3 Warming the water from 0 °C to 25.0 °C.
Sample Problem: Calculate the enthalpy change (in kJ) for converting 10.0 g of ice at -15.0°C to water at 25.0 °C.
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This quantity, ∆H, is called the enthalpy of reaction or the heat of
balloon below is an exothermic reaction and the energy released is equal to the heat of reaction.
How much energy is released when 4.0 mol of HBr is formed in this reaction? H2(g) + Br2(g) --> 2HBr(g) ∆H = -72 kJ
How much energy is released when 4.0 mol of HBr is formed in this reaction? H2(g) + Br2(g) --> 2HBr(g) ∆H = -72 kJ