5.3 Enthalpy

5.3 Enthalpy

  • We need to consider some of the concepts of thermodynamics as we focus on thermochemistry in this chapter.
  • Substances act as a source of energy, meaning that they can be added or removed.
    • The energy in a substance is stored in its atoms.
    • Increased translations, vibrations, or rotation of the atoms or molecules are some of the ways in which the greater kinetic energy can be found.
  • When thermal energy is lost, the motions become less intense.
  • When a system undergoes a change, its internal energy can change, and energy can be transferred from the system to the surroundings.
    • If the metal wire is immersed in hot water, it will absorb heat from the water, or if you bend the wire back and forth, it will become warmer.
    • The internal energy of the wire is increased by both processes.
    • When the system doesn't work on the surroundings, or when heat is lost from the system, energy is transferred out.

  • During the operation of an internal combustion engine, an example of this occurs.
    • The reaction of gasoline and oxygen is cold.
    • Some of the energy is given off as heat and some is used to push the cylinder.
    • The system and surroundings are the substances involved in the reaction.
    • The internal energy of the system decreases when heating and doing work on the surroundings.
    • How to determine the amount of work involved in a chemical or physical change will be considered.
  • The exothermic combustion reaction of a fuel such as gasoline into energy of motion is shown in this view.
  • The value of a state function is dependent on the state that the system is in.
    • An example of a state function is elevation.
    • If you are on the summit of Mt.
    • It doesn't matter if you hiked there or parachuted there, you are at an altitude of 5895 m. The distance traveled to the top of Kilimanjaro is not a state function.
    • You could either take a direct route or take a circuitous path to the summit.
    • The distance traveled is not a state function, but the elevation reached is.
  • There are two different routes to the summit.
    • Both have the same change in elevation, but they have different distances traveled, and it depends on the path.

  • The heat given off when you operate a Bunsen burner is equal to the enthalpy change of the methane combustion reaction that takes place, since it occurs at the constant pressure of the atmosphere.
  • The changes in matter and energy are represented by a thermochemical equation.
  • When 1 mole of hydrogen gas and 12 mole of oxygen gas at some temperature and pressure change to 1 mole of liquid water at the same temperature and pressure, 286 kJ of heat are released to the surroundings.
  • 12 x (-286kJ) is 2.
    • The enthalpy change of a reaction depends on the physical state of the reactants and products of the reaction, so these must be shown.
    • 286 kJ of heat is released when 1 mole of hydrogen gas and 12 mole of oxygen gas change to 1 mole of liquid water at the same temperature and pressure.
    • Only 242 kJ of heat can be released if water forms.

  • When 1 mole of HCl reacts, the enthalpy change is -58 kJ.

  • A gummy bear has 2.67 grams of sugar.
    • 43.7 kJ of heat is produced when it reacts with 7.19 g potassium chlorate.
  • We have 2.67 g x 1 mol 342.3 g and 7.19 g x 1 mol 122.5 g.
  • -5960 kJ is themol x -43.7 kJ 0.0587 mol KClO.
  • Enthalpy changes are calculated for reactions in which both reactants and products are at the same conditions.
    • The IUPAC standard state for chemists does not specify a temperature, but refers to materials under a pressure of 1 bar and solutions at 1 M. The enthalpy change symbol will have a superscripted "o" in it.
  • We will use a subscripted " " to designate the temperature since it is not technically standard.
    • enthalpy change is used to indicate a process occurring under these conditions.
  • The enthalpy changes for many chemical and physical processes can be found in the reference literature.
  • The amount of heat produced when one mole of ethanol undergoes complete combustion at 25 degC and 1 atmosphere pressure is called the enthalpy.
  • Some of the substances that have been measured are listed in Table 5.2.

  • The process of burning gasoline is a highly exothermic one.
    • Assuming isooctane is the same as that of gasoline, we can determine the amount of heat produced by burning 1.00 L of gasoline.
    • The isooctane has a density of 0.692 g/mL.
  • The burning of gasoline is very hot.
  • We can perform conversions between units until we arrive at the desired amount of heat or energy.
    • One of the necessary conversions is provided by the enthalpy of combustion.
    • This value is given in Table 5.2 as -5460 kJ per 1 mole of isooctane.
  • 33,100 kJ of heat is produced by the combustion of 1.00 L of isooctane.
  • As reserves of fossil fuels diminish and become more costly to extract, the search is ongoing for replacement fuel sources for the future.
    • Some of the most promising fuels are derived from algae.
  • Among the world's fastest growing organisms are the species of algae used.
  • 50% of the algal weight is oil, which can be converted into fuel.
    • It can yield more energy than other crops.
    • Some strains of algae can grow in water that is not suitable for growing other crops.
    • Biodiesel, butanol, methane, and even jet fuel can be produced by algae.
  • The US Air Force is currently producing jet fuel from algae at a cost of under $5 per gallon.
  • A variety of renewable fuels are created by the conversion of sunlight and carbon dioxide into oil by algae.
  • For more on the problem ofpentagon fuel, see http://www.theguardian.com/environment/2010/feb/12/algae-solve-pentagon-fuel-problem.
  • Click on the process to create the biofuel.
  • These values are useful for computing or predicting enthalpy changes for chemical reactions that are impractical or dangerous to carry out, or for processes that are difficult to make measurements.
    • If we have values for the appropriate standard enthalpies of formation, we can determine the enthalpy change for any reaction, which we will practice in the next section.
  • The carbon present in the reactants at a pressure of 1 atm and 25 degC is the most stable form of carbon under these conditions.
  • You can find a table of standard enthalpies of formation of many common substances in these values.
    • The standard enthalpy of formation of an element in its most stable form is zero under standard conditions, which is 1 atm for gases and 1 M for solutions.
  • The energy that drives this reaction in the upper atmosphere comes from ultraviolet radiation.

  • There are two ways to determine the amount of heat involved in a chemical change.
    • It is difficult to investigate and make accurate measurements in some reactions.
    • It is convenient to be able to determine the heat involved in a reaction without having to do an experiment.
  • The enthalpy is a state function and it is valid because it depends on where a chemical process starts and ends.
    • The reaction of carbon with oxygen to form carbon dioxide can be thought of as a two-step process.

  • The products are at a lower enthalpy than the reactants.
  • If we divide an equation by a number, the enthalpy change should also be divided by the same number.

  • This is a less straightforward example of the thought process involved in solving a law problem.

  • If the corresponding enthalpies of formation of the reactants and products are available, we can use Hess's law to determine the enthalpy change of any reaction.
    • The stepwise reactions we consider are: decomposition of the reactants into their component elements for which the enthalpy changes are proportional to the negative of the enthalpies of formation of the reactants, followed by re-combinations of the elements The standard enthalpy change of the overall reaction is the same as the sum of the standard enthalpies of formation of the reactants.

  • This procedure is used in the general equation.

  • The capacity to do work is called energy.
    • The potential energy is based on relative position, composition, or condition.
    • Energy is not created or destroyed when it is converted from one form to another.
  • The thermal energy of Matter is due to the average ke of its molecules.
    • The energy that is transferred between objects at different temperatures is called heat.
    • Chemical and physical processes can release heat.
    • The joule is the SI unit of energy, heat, and work.
  • Specific heat and heat capacity are measures of the energy needed to change the temperature.
  • The amount of heat released by a substance depends on a number of factors.
  • Calorimetry measures the amount of thermal energy transferred in a process.
    • This requires careful measurement of the temperature change that occurs during the process.
    • The amount of heat produced or consumed in the process is calculated using known mathematical relations.
  • Calorimeters are used to minimize energy exchange between the system being studied and its surroundings.
  • Coffee cup calorimeters are used by introductory chemistry students, while bomb calorimeters are used to determine the energy content of food.
  • Under standard state conditions, reactions occur at 298 deg.
  • enthalpy of formation, fusion, and vaporization are examples of enthalpy changes.
    • If the reactants and products of a reaction are available, the enthalpy change can be calculated.
  • You wouldn't sit around a burning match on a fall evening to stay warm if the temperature was the same.
  • There are several energy transitions that take place during the typical operation of an automobile.
  • A piece of unknown substance weighs 44.7 g and requires 2110 J to increase its temperature.
  • A piece of unknown solid substance weighs 437.2 g and requires 8460 J to increase its temperature.
  • An aluminum kettle weighs more than one kilo.
  • Most people find waterbeds uncomfortable if the water temperature is not maintained.
    • Unless it is heated, a waterbed with 892 L of water will cool from 85 to 72 degrees in 24 hours.
    • Estimate the amount of electrical energy required to keep the bed cool.
    • Assume that the density of water is 1.0 g/mL, and that 1 kilowatt-hour is 3.6 x 106 J.
  • A bottle of water at room temperature and a bottle of water at the same temperature were placed in a refrigerator.
    • The bottle of water cooled to the temperature of the refrigerator after 30 minutes.
    • The water cooled to the same temperature an hour later.
    • One student said that both bottles lost the same amount of heat because they started at the same temperature and finished at the same temperature.
    • A student thought that the bottle of water lost more heat because there was more water.
    • A third student thought that the bottle of water lost more heat because it cooled more quickly.
    • A fourth student thought that it was not possible to tell because we don't know the initial and final temperatures of the water.
    • Explain the error in each of the other answers if the answers are correct.
  • Coffee and water have the same density and heat.
  • Coffee has the same density and heat as water.
  • The temperature of the coffee and the spoon become equal when the spoon is placed in 180 mL of coffee.
  • Coffee has the same heat as water.
  • A 0.500g sample of KCl is added to 50.0 g of water in a calorimeter.
  • The approximate amount of heat produced by the solution and products is assumed to be 4.20 J/g degC.

  • The temperature increases when a 0.740-g sample of trinitrotoluene is burned in a bomb calorimeter.
    • The calorimeter has a heat capacity of 534 J/degC and has water in it.
  • One way of generating electricity is by burning coal to heat water, which produces steam that drives an electric generator.
    • To determine the rate at which coal is to be fed into the burner in this type of plant, the heat of combustion per ton of coal must be determined using a bomb calorimeter.
    • When 1.00 g of coal is burned in a bomb calorimeter, the temperature increases.
    • Determine the heat produced by burning a ton of coal if the calorimeter has a heat capacity of 21.6 kJ/degC.
  • 16 calories is the number of calories in a cup of common sugar.
  • 1100 calories can be found in a quart of premium ice cream.
  • A serving of breakfast cereals contains a lot of food.
  • The heat produced by the isooctane under standard conditions can be compared to the nutrition of the cereals.
    • 130 calories can be found in a 1.0 ounce serving of the cereals.

  • Consider the conditions for which the data is reported.
  • 125 kJ of heat is produced when 2.50 g of methane burns.
  • A sample of carbon is burned in a bomb calorimeter to make carbon dioxide.
    • The heat released from the reactants and products is proportional to the enthalpy of the fire.
    • The temperature of the calorimeter goes up from 26.74 to 27.93.
  • Sulfur dioxide was used in household refrigerators before the introduction of chlorofluorocarbons.
  • The hot water may be pumped through the radiators.
    • When 100 g of steam is cooled to 100 degC, what mass of water will provide the same amount of heat.

  • In 1774, Joseph Priestly prepared oxygen by heating red mercury(II) oxide with sunlight.

  • Determine the total energy change for the production of one mole of nitric acid.

  • H2O2 has been used to provide thrust in the control jets of various space vehicles.
    • The data was used under standard conditions.
  • The formation of propane has a enthalpy of 104 kJ/mol.
  • The enthalpy of formation of butane is 126 kJ/mol.
  • Gaseous fuels include propane and butane.
  • For this reaction and for the condensation of liquid methanol.
  • In the early days of automobiles, acetylene, C2H2, was burned to provide illumination at night.
    • Some cave explorers still use acetylene as a source of light despite no longer being used as an auto headlamps.
  • The enthalpy of gasoline is 1.28 x 105 kJ/gal, while the enthalpy of hard coal is -35 kJ/g.
    • The density of gasoline is the same as isooctane.
  • In Brazil, C2H5OH is used as a fuel for motor vehicles.

  • Among the 50 chemical compounds produced commercially in the largest quantities, ethylene, C2H2, is fourth.
    • Synthetic Ethanol is made from the reaction of ethylene with water in the presence of a suitable catalyst.

  • The same products are given by the metabolism of glucose, even though it reacts with oxygen in a series of steps in the body.
  • The air has 23% oxygen by mass.
    • During the month, the average density of air was 1.22 g/L.
  • In a house, electricity is efficient in producing heat.
  • In a coal-fired power plant, the efficiency of production and distribution is 40%.
    • 2.26 kWh per pound is provided by a certain type of coal.