Cairo University Faculty of Engineering Credit Hours System (CHS) Chemistry

THERMOCHEMISTRY

1- Thermochemistry

It is the study of heat released or absorbed during chemical or physical changes. Exothermic reactions. Endothermic reactions.

2-Energy
It is the capacity to do work.

Sources of Energy
Fossil fuels (petroleum, coke,..) C[Fuel] CO2+energy Nuclear, wind, solar, biomass Green house effect.

Types

of Energy

Potential, kinetic, heat, work, internal energy, chemical energy

Energy
Joule

Units

is the SI energy unit. Calorie is the past energy unit. 1 cal = 4.184 J (exactly) = the heat required to raise the temperature of 1 gm of water
from 14.5C to 15.5 C

3- calorimetry

Calorimeter : Is the device used to determine the heat associated with a chemical reaction.

3- Calorimetry (cont.)

Heat Capacity : It is the heat required to raise the temperature of a substance 1C. Specific Heat Capacity : Heat Capacity per gram, J/gmK Molar Heat Capacity : Heat capacity per mole, J/mol.K Cp: Heat capacity at constant pressure (*) . Cv: Heat capacity at constant volume.

Heat of Reaction

It is nominated according to: Physical conditions (constant pressure H=qp constant volume E=qv) Type of reaction - Formation = HF - Combustion = HC - Reaction = HR

4- Heat of Formation
It is the heat absorbed or rejected during the formation of 1 mole of a compound from its elements.

5- Heat of Combustion
It is the heat absorbed or rejected during the oxidation or combustion of 1 mole of a hydrocarbon completely to yield CO2 and H2O (HC)

6- Heat of Reaction
It is the heat absorbed or rejected during a chemical reaction. Exothermic H=-ve Endothermic H=+ve

Heat of Combustion
Types

of fuel Air or oxygen?? Excess vs theoretical? Hc of CO2 = 94.4 kcal/mole Hc of H2O = 68.4 kcal/mole Pollution: air vs O2

7- Hess Law
The change in enthalpy for any chemical reaction is constant, whether the reaction occurs in one step or in several steps. (Thermochemical data, therefore, may be treated algebraically)

Enthalpy

Change of Reactions HR from HF

The enthalpy change for a given reaction can be calculated by subtracting the enthalpies of formation of the reactants from the enthalpies of formation of products (each multiplied by its stoichiometric amounts and taking into account that HF for elements equal to zero.

Example
Ethanol (C2H5OH) has been proposed as an alternative fuel. Calculate the standard of enthalpy of combustion per gram of liquid ethanol. Knowing that the standard enthalpy of formation of ethanol (liquid) = -278 kJ/mol. (1 cal = 4.18 J) HF (ethanol) = - 66.5 Kcal

Keep in Mind
When a reaction is reversed, the magnitude of H remains the same, but its sign changes. When the balanced equation for a reaction is multiplied by an integer, the value of H for that reaction must be multiplied by the same integer. The change in enthalpy for a given reaction can be calculated from the enthalpies of formation of the reactants and products Hreaction= np Hf(products)- nr Hf(reactants) Elements at their standard states are not included in the Hf for an element in its standard state is zero.

Main Application of Heat of Reactions

From heat of combustion, determined experimentally, heat of formation may be calculated. Determination of the fuel suitability for direct uses from their HC. Knowing that HF of CO2 = 94.4 kcal/mole HF of H2O = 68.4 kcal/mole the heat of formation of any organic compound may be calculated from its heat of combustion Neglecting the heat of formation of fuel the heat of combustion may be estimated from HF of CO2 and HF of H2O

8- Present Sources of Energy

Petroleum Natural Gas Coal Green House Effect

Combustion Equation (Material Balance)

Balanced equation Balanced equation with Excess (air or oxygen) Theoretical air Excess air Volume of air (P, T) Volume of Product Mass of products Density of products Partial pressure of products

Example (#19)
Calculate the quantity of air needed for the combustion of 220 gm of propane (C3H8) in a furnace that uses 20% excess air. Calculate the volume of air at a pressure of 750 mmHg and a temperature of 32C. If the combustion products were cooled to 120C and a pressure of 730 mmHg, calculate the volume and density of the combustion products and the partial pressure of CO2.

Petroleum
C H S compounds (C5 to C25) Distillation (fractional) Kerosene (C10-C18) Gasoline (C5-C10) (obtained recently by pyrolytic cracking) - to decrease knocking tetraethyl lead is added which causes pollution - decrease pollution by catalytic converters (destroyed by Pb) - Leaded gasoline have been phased out

Natural Gas

CH4 associated with petroleum. Steam reforming yield hydrogen. CH4(g) + H2O(g) 3H2(g) + CO(g)

Coal

Lignite (least value) Sub bituminous Bituminous Anthracite (most valuable)

According to carbon content, coal matures through four stages (depends on C/O & C/H):-

S impurities may form acid rain ?

Green House Effect

Infrared radiated by the Earth

Green House gases (CO2, H2O, CH4,..)

 New

Energy Sources

Factors affecting new fuels choice - economics - environmental - climatic - supply

Methanol CH3OH Coal Slurries

CO(g) + 2H2(g) CH3OH(l)

Fine particles of coal + water coal slurries

Kerogen
Oil shale

Biodiesel (Chemical Impact)

Fuel made by esterifying fatty acids in vegetable and used oils

Syngas Coal gasification

Coal + air + steam CO + H2 CH4
Coal (C) +steam[H2O(g)] +air [O2(g)]
Heat

CH4(g), CO(g), CO2(g), H2(g), H2O(g) +sulfur-containing impurities (sulfur compounds)

Separate

CO(g) + H2O(g) CO2(g) +H2(g) CO(g) + 3H2(g) CH4(g) + H2O(g) Remove CO2, H2O, impurities

CH4(g)

CH4(g) Syngas [CO(g), H2(g)]

Hydrogen Fuel
H2(g) + O2(g) H2O(l) H= -286 KJ (HC of H2 = 2.5 HC of natural gas) per gram Hydrogen may be produced from - Natural gas by steam reforming - Electrolysis of water - From corn starch - Thermal decomposition of water - Thermo chemical decomposition of water Environmental aspects of H2 uses as fuels - Storage(!) and transportation - Risk due to leakage

Chemical Impact Farming the wind

In the Midwest (USA), the wind blows continuously across the plains. One of the farmers erected 17 wind turbines on six acres of land. Such turbines can generate as much as 10MW of electricity which he sells to the local electrical utility. Wind farms are now being developed in a lot of windy areas across the USA. Farmers who own the land welcome the increased income derived from the wind blowing across their land.

 Another

possible scenario for wind farms is to use the electrical power generated to decompose water to produce H2 gas that can be carried to cities by pipelines and used as a fuel. One real benefit of H2 is that it produces water as its only combustion product i.e. it is pollution free. The most impressive thing about wind power is its magnitude of supply. Within a few years wind power could be a major source of electricity.

For Review
Calorie, cal: The approximate quantity of heat required to raise the temperature of 1 g of water from 14.5C to 15.5C defined by the relationship: 1 cal = 4.184 J (exactly)
Calorimeter: A device used to measure the heat transferred in chemical reactions and physical changes. Endothermic reaction: A chemical reaction in which heat is absorbed. Energy: The capacity to do work

Enthalpy, H: The heat content of a sample of matter, for a reaction run at constant pressure, the change in enthalpy, H, is the heat transferred (liberated or absorbed). Enthalpy of formation : For a given compound, the enthalpy change for a reaction in which 1 mol of the compound is prepared from the most stable forms of its elements. A standard enthalpy of formation, Hf, pertains to a formation reaction run at 1 atm presure and at a designated reference temperature (usually 25C)

Heat: The form of energy that flows spontaneously from a body at a higher temperature to a body at a lower temperature. Heat Capacity: The amount of heat required to raise the temperature of a given mass by 1C. Joule, J: The SI unit for all energy measurements; 1 kg m2/s2.

Law of Hess, law of constant heat summation: The change in enthalpy for any chemical reaction is constant, whether the reaction occurs in one step or in several steps.

Specific heat: The amount of heat required to raise the temperature of 1 g of a substance by 1C Temperature: Degree of hotness or coldness; that property of matter that determines the direction in which heat flows spontaneously.
Thermochemistry: Study of the energy changes that accompany chemical and physical changes