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First Law of Thermodynamics System, surrounding, and thermodynamic universe Heat (q), work (w) and internal energy (E) Calculation of heat gained or lost by system State Functions Enthalpy of reactions Calorimetry; determination of enthalpy of reactions Hesss law of enthalpy summation
Kinetic Energy:
energy associated with the translational motion of an object. Kinetic energy depends on the mass and speed of the object. EK = mv2
q = m.s.Dt
where m = mass; s = specific heat capacity of the substance, and Dt = change in temperature Enthalpy change (DH):
Heat gained or lost during a chemical reaction at constant pressure.
Heat of Neutralization
To determine the molar enthalpy of acid-base reaction using coffee cup calorimeter.
50.0 mL of 2.0 M HCl was reacted with 50.0 mL of 2.0 M NaOH in a coffee cup calorimeter. The reaction was exothermic, which caused the temperature of the solution to increase from 22.0oC to 35.6oC. Assume the density of solution as 1.0 g/mL, its specific heat capacity as 4.18 J/g.oC, and the heat capacity of calorimeter as 10.J/oC. Calculate the total amount of heat produced by the reaction. Calculate the enthalpy change (DH, in kJ/mol) for the following reaction:
Bomb Calorimeter
Heat of Combustion
To calculate the enthalpy of combustion using bomb calorimeter When a 1.010-g sample of sucrose (cane sugar) is completely combusted in a bomb calorimeter, the temperature of the calorimeter was increased by 4.50oC. If the heat capacity of calorimeter is 3.75 kJ/oC, how much heat was absorbed by the calorimeter? Calculate the molar enthalpy of combustion of sucrose according to the following equation: C12H22O11(s) + 12O2(g) 12CO2(g) + 11H2O(l)
Enthalpy of Reactions
Applying Hesss law to calculate enthalpy of reactions.
Given: C(s) + O2(g) CO2(g); DHo = -394 kJ (1) CO(g) + O2(g) CO2(g); DHo = -283 kJ (2) Calculate DH for the following reaction:
C(s) + O2(g) CO(g)
Enthalpy of Formation
Enthalpy of Combustion
Calculating enthalpy of combustion of diborane, B2H6, using the molar enthalpy of formation data: Given:
(1) 4B(s) + 3O2(g) 2B2O3(s); (2) 2B(s) + 3H2(g) B2H6(g); (3) 2H2(g) + O2(g) 2H2O(g); DHf(1) = -2546 kJ DHf(2) = 36.4 kJ DHf(3) = -483.7 kJ
Calculate DH for the following combustion reaction: B2H6(g) + 3O2(g) B2O3(s) + 3H2O(g);
2B(s) + 3H2(g) + 3O2(g) __________ DHf = 0.0 kJ 3H2O(g) ____________ DHf = -726 kJ
Enthalpy Diagram
Reaction: C3H8(g) + 5O2(g) 3CO2(g) + 4H2O(g)
3C(s) + 4H2(g) + 5O2(g) ____________ DHf = 0.0 kJ C3H8(g) ____________ DHf = -104 kJ
Substances Hydrogen gas (H2) Natural gas (CH4) Gasoline Crude petroleum Animal fat Coal Charcoal Ethanol Methanol Paper Dry biomass (wood)
Petroleum
thick, dark liquid composed of mixture of hydrocarbons Composition varies from one location to another, but mostly hydrocarbon compounds containing C5 to > C25
Natural Gas
Consists mostly methane (CH4, >90%) and some ethane (C2H6), propane (C3H8) and butane (C4H10)
Petroleum Refining
Petroleum refining
Fractional distillation of crude petroleum yields the following fractions: Gasoline (C5 C10); Kerosene & jet fuel (C10 C18); Diesel fuel, heating, and lubricating oil (C15 C25), Asphalt (>C25) More gasoline is produced by pyrolytic (high temperature) cracking of larger HC compounds (> C25)
Coal
Formed from fossilized plant remains that have been subjected to high temperature and pressure for many millions years Coal matures through 4 stages:
Lignite, subbituminous, bituminous, and anthracite;
Composition by mass%:
Lignite: 71% C, 4% H, 23% O, 1% N, and 1% S; Subbituminous: 77% C, 5% H, 16% O, 1% N, and 1% S; Bituminous: 80% C, 6% H, 8% O, 1% N, and 5% S; Anthracite: 92% C, 3% H, 3% O, 1% N, and 1% S. The relative carbon content increases and those of hydrogen and oxygen decrease as coal matures.
Processing Coal
Coal gasification - converting coal into gaseous fuel Treating coal with air and steam at high temperature produces mixture of CO, H2, and CH4. Some CO2 and SO2 are also formed Mixture of CO and H2 is also called syngas Reactions in coal gasification: C(s) + O2(g) CO2(g); DH = -394 kJ C(s) + O2(g) CO(g); DH = -111 kJ C(s) + H2O(g) CO(g) + H2(g); DH = 131 kJ C(s) + 2H2(g) CH4(g); DH = -75 kJ
Note: both exothermic and endothermic reactions occur. An energy balance can be maintained by controlling the temperature, the rate of coal feed, and the flow of air and steam.
Hydrogen Fuel
Combustion of H2: H (g) + O2(g) H2O(l); DH = -286 kJ H2(g) + O2(g) H2O(g); DH = -242 kJ Combustion of H2 produces 2.5 times more energy per gram than natural gas Combustion of H2 only produces water. However, production, storage and transportation of the gas pose major problems
Electrolysis: H2O(l) H2(g) + O2(g); DH = 286 kJ Thermochemical decomposition of H2O: 2HI(g) H2(g) + I2(s); (425oC) 2H2O(l) + SO2(g) + I2(s) H2SO4(aq) + 2HI(aq); (90oC) H2SO4(aq) SO2(g) + H2O(l) + O2(g); (825oC) Net Reaction: H2O(l) H2(g) + O2(g);
Alternative Fuels
Hydrogen gas is most efficient and clean fuel It produces the most energy per gram, Transportation and storage are difficult It requires a much large fuel tank than gasoline; May be compressed into liquid form, but poses explosion hazard An alternative way is to convert it into a solid metal hydride (MH2) one that is able to release H2 when heated. Most likely the hydrogen will be used to power fuel cells that will be installed in automobiles
Alternative Fuels
Oil shale
Shale rocks contain complex HC called kerogen Huge deposits in western states, especially Colorado; Kerogen is not fluid like petroleum - cannot be pumped; Rocks containing fuel must be heated to >250oC to decompose the kerogen into smaller HC molecules; Process produces large quantities of waste rocks a negative environmental impact.
Alternative Fuels
Ethanol:
Produced by fermentation of sugar (from sugar cane or corn) Pure ethanol produces about 27 kJ/g of energy Use as fuel supplement Added to gasoline as gasohol (which contains ca. 10% ethanol) Pure ethanol not suitable for motor fuel in USA, especially in winter, because it does not vaporize easily in cold climate. Pure ethanol is widely used as motor fuel in Brazil where the climate is warmer.
Alternative Fuels
Methanol:
Methanol produces about 20 kJ/g of energy when completely combusted It has been used in race cars as a mixture of 85% methanol and 15% gasoline. California is evaluating methanol as motor fuel Arizona and Colorado are considering similar step.
New Energy?