Thermochemistry

• The study of the heat changes

that accompany chemical
reactions and phase changes.
 ENERGY
• The capacity to do work or produce heat.
• Potential energy-energy of position or
composition
• Kinetic energy – energy of motion
 Chemical Potential Energy

• Energy stored in the chemical bonds of

a substance.
• Gasoline
• Wood
 Units of Heat Energy

• calorie-the amount of heat needed to

raise the temp. of 1g of water 1°C
• Calorie = 1000 calories
• Joule (J) SI unit of energy 4.184J = 1cal
 Temperature

• A property that reflects the random

motion of particles in a substance.
• The average kinetic energy of the
system.
 Heat (q)
• The transfer of energy between two
objects because of a temperature
difference.
• Heat flows from a warmer object to a
cooler one.
 Law of conservation of energy

• In any chemical process energy can be

converted from one form to another,
but cannot be created or destroyed.
 Thermochemical
processes

• System - the part of the universe where

the reaction is taking place.
• Surroundings - the rest of the universe.
Thermochemical processes
• Exothermic - energy is flowing out of the
system into the surroundings.
• q will have a negative value.
• Endothermic - energy is flowing into the
system out of the surroundings.
• q will have a positive value.
 Calorimetry

• The science of measuring heat based

on temperature change when a body
absorbs or gives off heat.
 Specific Heat Capacity (J/g°C)
• Specific heat (C)
• Amount of heat energy needed to raise
the temperature of 1g of a substance 1°C
• Depends only on chemical composition.
• Table R 7 for elements R 9 for
compounds.
 Enthalpy(H)
• The heat content of a system at constant
pressure.
 H = q = m CT
m = mass
C = specific heat
T = change in temp.
 Constant Pressure
Calorimetry
• Atmospheric pressure is maintained
during the process.
• Styrofoam cup calorimeter.
• The temperature of a 95.4-g piece of
copper increases from 25.0oC to 48.0oC
when the copper absorbs 849J of heat.
• What is the specific heat of copper?
Figure 10.1: Schematic representations of
the three states of matter.

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 Molar heat of fusion (∆Hfus)
• The heat absorbed by one mole of a solid
substance melting to a liquid at a
constant temperature
• Since heat is absorbed ∆Hfus is positive
• 6.01 kJ/mol for water
 Molar heat of solidification ∆Hsol

• The heat released when one mole of a

liquid solidifies at a constant
temperature.
• Since heat is released ∆Hsol is negative.
• - 6.01 kJ/mol
Molar heat of vaporization ∆Hvap

• The amount of heat needed to vaporize

one mole of a liquid at constant
temperature.
• ∆Hvap is positive.
• 40.7 kJ/mol for water
Molar heat of condensation ∆Hcond
• The heat released by one mole of a gas
when it condenses to a liquid at
constant temperature.
• ∆Hcond is negative.
• - 40.7 kJ/ mol for water
For any substance

• ∆Hfus = -∆Hsol

• ∆Hvap = -∆Hcond
• How many grams of ice at 0°C
and 101.3 kPa could be melted by
the addition of 4000J of heat ?
• 12.0g
• How much heat must be removed
in order to freeze a 10.0g sample
of water at 0.0°C?
• How much water can be
converted to steam by the
addition of 144kJ?
• 63.7g
• How much heat is released when
5.00g of steam condenses
• 11.3 kJ
• When 435J of heat is added to 3.4 g of
olive oil at 21oC, the temperature rises
to 85oC.
• What is the specific heat of the olive
oil?
• How much heat is required to raise the
temperature of 250.0 g of mercury
52oC?
A small pebble is heated and placed
into a foam cup calorimeter containing
25.0 mL of water at 25.0oC. The water
reaches a max. temp. of 26.4oC. How
many joules of heat are released by the
pebble?
 Vaporization
• The conversion of a liquid to a gas or
vapor.
• Evaporation-vaporization of a
substance below its boiling point.
• Boiling- at boiling point
 Vapor Pressure

• A force due to the gas particles above a

liquid
• As temp. increases the vapor pressure
increases because more particles have
enough energy to escape as a gas.
 Phase Diagrams
• Show the phase a substance will be in at
certain conditions of temperature and
pressure.
• Critical temperature - the temperature above
which vapor will not liquify, no matter how
much pressure is applied.
The phase
diagram for
water.

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 Thermochemical
equation
• A chemical equation that includes
a heat change.
 Heat of reaction
• The heat change for a reaction
exactly as it is written. ∆H
• Standard conditions are
101.3kPa and 25°C.
 Write a thermochemical
equation for:
• When 2 mol magnesium combines
with 1 mol oxygen 2 mol of
magnesium oxide is formed
releasing 1204kJ of heat.
• H2 + F2  2HF. H = -536kJ
• How much heat energy is
produced when 15.0g hydrogen
reacts?
 Molar heat of combustion
∆Hcomb

• The heat of reaction for the

complete burning of one mole of a
substance.
• Table 3 page 528
• How much heat is released
when 12.5g of ethanol burns?
• 371kJ heat released
• ∆H= -371kJ
• How much heat energy is required
to convert 10.0g of ice at -10°C to
steam at 125°C
 HESS’S LAW

• In a chemical change, the

change in enthalpy is the same
whether the reaction takes place
in one step or in several steps.
 Hess’s Law
• If you add 2 or more
thermochemical equations to
give a final equation, you can
also add the heats of reaction
to give a total heat of reaction.
 Rules for heat change
• If the reaction is reversed the sign
on enthalpy is also reversed.
• If the reaction is multiplied by a
number the enthalpy must be
multiplied by the same number.
• C(s,diamond)  C (s, graphite)
• C (s, graphite) + O2(g)  CO2(g) H= -393.5 kJ
• C(s,diamond) + O2(g)  CO2(g) H= -395.4 kJ
Standard heat of formation

•∆H˚
Thefchange in enthalpy that
occurs when one mole of a
compound is formed from its
elements. All substances are in
their standard state.
 Standard States
• The state the element or
compound exists in at 1 atm
and 25˚C.
• ∆H˚f of an element is 0.
• Table R 11 page 985.
 Hreaction
H = Hf products - Hf reactants
• Determine the Hreaction for:
 2SO2(g) + O2(g)  2SO3(g)
• The combustion of one mole of ethane
to carbon dioxide and water.
 Entropy(S)
• A measure of the disorder of a
system.
• Systems naturally progress
from order to disorder.
• The driving force of a
spontaneous process is an
increase in the entropy of the
universe.
Entropy changes in chemical
reactions
• Change in positional entropy is
dominated by the relative numbers
of gas molecules in the reactants
and products.
Is entropy increasing or decreasing?
• Solid CO2 gaseous CO2
• N2 gas @ 1atm .001atm
• Solid sugar is added to water to make a
solution
• Iodine vapor condenses to form crystals on
a cold surface
 Free Energy (G)
• Thermodynamic function defined
by: G=H-T S
• H=enthalpy
• T= Kelvin temperature
• S= entropy
• Spontaneous reactions have (-)G
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Phase Changes

• When a system is at equilibrium

like during phase changes, boiling
freezing melting etc.,
G = 0
• At what temperatures is this
process spontaneous?
Br2(l)  Br2(g)
H° = 31.0 kJ/mol
S°= 93.0 J/K x mol