1) Heat is a form of energy that is transferred between objects at different temperatures. Heat transfer occurs when samples are in contact and energy moves from the higher temperature sample to the lower temperature sample.
2) Enthalpy is a measurement of the total energy of a system and includes both the internal energy and pressure-volume work term. The enthalpy change of a reaction can be determined from standard enthalpies of formation values.
3) Hess's law states that the enthalpy change of an overall chemical process is equal to the sum of the enthalpy changes of the individual steps in that process.
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ENERGY AS HEAT
1. Energy as Heat
• A sample can transfer energy to another
sample.
• One of the simplest ways energy is
transferred is as heat.
• Heat is the energy transferred between
objects that are at different temperatures
• Though energy has many different forms, all
energy is measured in units called joules (J).
2. • Temperature is a measure of how hot (or
cold) something is; specifically, a measure of
the average kinetic energy of the particles in
an object.
• When samples of different temperatures are
in contact, energy is transferred from the
sample that has the higher temperature to the
sample that has the lower temperature.
3. • Temperature is an intensive property,
which means that the temperature of a
sample does not depend on the amount
of the sample.
• Heat is an extensive property, which
means that the amount of energy
transferred as heat by a sample
depends on the amount of the sample.
4. • Changes in energy content can be
determined.
• If 73 J of energy enter a piece of silver
and no change in pressure occurs, we
know that the enthalpy of the silver has
increased by 73 J.
• Enthalpy, which is represented by
the symbol H, is the total energy
content of a sample.
5. • Enthalpy is the sum of the internal
energy of a system plus the product
of the system’s volume multiplied
by the pressure that the system
exerts on its surroundings.
6. • The particles in a sample are in constant
motion.
• The enthalpy of a sample includes the total
kinetic energy of its particles.
• Both the total and average kinetic energies of
a substance’s particles are important to
chemistry, because these quantities account
for every particle’s kinetic energy.
7. • Molar heat capacity can be used to determine
the enthalpy change of a sample.
• The molar heat capacity of a pure substance is
the energy as heat needed to increase the
temperature of 1 mol of the substance by 1 K.
• Molar heat capacity has the symbol C and the
unit J/K•mol.
8. • When a substance receives energy in the
form of heat, its enthalpy increases and
the kinetic energy of the particles that
make up the substance increases.
• The direction in which any particle moves
is not related to the direction in which its
neighboring particles move. The motions
of these particles are random.
9. • Because enthalpy is the total energy of a
system, it is an important quantity.
• The only way to measure energy is through a
change. Absolute values cannot be measured.
• The enthalpy change for one mole of a pure
substance is called molar enthalpy change.
10. • When a pure substance is only
heated or cooled, the amount of heat
involved is the same as the enthalpy
change.
∀∆H = q for the heating or cooling of
substances
11. • A change in enthalpy during a reaction
depends on many variables.
• Temperature is one of the most important variables.
• To standardize the enthalpies of reactions, data
are often presented for reactions in which both
reactants and products have the standard
thermodynamic temperature of 25.00°C or
298.15 K.
12. • Chemists usually present a thermodynamic
value for a chemical reaction by using the
chemical equation.
1 1
H2 ( g ) + Br2 ( l ) → HBr ( g ) ∆H = -36.4 kJ
2 2
• This equation shows that when 0.5 mol
of H2 reacts with 0.5 mol of Br2 to
produce 1 mol HBr and all have a
temperature of 298.15 K, the enthalpy
decreases by 36.4 kJ.
13. • For the H2 and Br2 reaction, in which ∆H is
negative, the total energy of the reaction
decreases.
• The energy is released as heat by the system.
• If the reaction was endothermic, energy in the
form of heat would be absorbed by the system
and the enthalpy would increase.
14. • The experimental measurement of an enthalpy
change for a reaction is called calorimetry.
• Calorimetry is the measurement of heat-related
constants, such as specific heat or latent heat
• Combustion reactions are always exothermic.
• The enthalpy changes of combustion reactions
are determined using a bomb calorimeter.
• A calorimeter Is a device used to measure the heat
absorbed or released in a chemical or physical
change
16. • Inside the pressurized oxygen atmosphere of a
bomb calorimeter, most organic matter, including
food, fabrics, and plastics, will ignite easily and
burn rapidly.
• Sample sizes are chosen so that there is excess
oxygen during the combustion reactions.
• Under these conditions, the reactions go to
completion and produce carbon dioxide, water,
and possibly other compounds.
17. • Any two processes that both start with the
same reactants in the same state and finish
with the same products in the same state will
have the same enthalpy change.
• Hess’s law states that the overall enthalpy
change in a reaction is equal to the sum of the
enthalpy changes for the individual steps in the
process.
18. • When phosphorus is burned in excess chlorine 4
mol of phosphorus pentachloride, PCl5, is
synthesized.
P4(s) + 10Cl2(g) → 4PCl5(g) ∆H = -1596 kJ
• Phosphorus pentachloride may also be prepared
in a two-step process.
Step 1: P4(s) + 6Cl2(g) → 4PCl3(g) ∆H = -1224 kJ
Step 2: PCl3(g) + Cl2(g) → PCl5(g) ∆H = -93 kJ
19. • The second reaction must take place four times
for each occurrence of the first reaction in the
two-step process.
• This two-step process is more accurately
described by the following equations.
P4(s) + 6Cl2(g) → 4PCl3(g)
∆H = -1224 kJ
4PCl3(g) + 4Cl2(g) → 4PCl5(g)
∆H = 4(-93 kJ) = -372 kJ
20. • So, the total change in enthalpy by the two-step
process is as follows:
(-1224 kJ) + (-372 kJ) = -1596 kJ
• This enthalpy change, ∆H, for the two-step
process is the same as the enthalpy change for
the direct route of the formation of PCl5.
• This example is in agreement with Hess’s law.
21. • The enthalpy of the formation of CO, when
CO2 and solid carbon are reactants, is found
using the equations below.
2C(s) + O2(g) → 2CO(g) ∆H = -221 kJ
C(s) + O2(g) → CO2(g) ∆H = -393 kJ
• You cannot simply add these equations
because CO2 would not be a reactant.
22. • Adding the two equations gives the equation for
the formation of CO by using CO2 and C.
2C(s) + O2(g) → 2CO(g) ∆H = – 221 kJ
CO2(g) → C(s) + O2(g) ∆H = 393 kJ
2C(s) + O2(g) + CO2(g) → 2CO(g) + C(s) +
O2(g)
∆H = 172 kJ
• Oxygen and carbon that appear on both sides
of the equation can be canceled.
23. • The enthalpy change in forming 1 mol of a
substance is called the standard enthalpy of
formation of the substance, ∆ Hf0
• The values of the standard enthalpies of
formation for elements are 0.
• The following equation is used to
determine the enthalpy change of a
chemical reaction from the standard
enthalpies of formation.
∆Hreaction = ∆Hproducts - ∆Hreactants