UNIT 5

THERMOCHEMISTRY 1

A study of the energy

produced by
Chemical Reactions
 HEAT
 Energy: The ability to do work
 HEAT: form of energy transferred from a body
at high temperature to one at lower temperature
 TEMPERATURE: average kinetic energy of the
molecules of a substance; measures heat flow
 JOULES (J) or (kJ): unit of measure of heat (or
any form of energy)
 PHASE: state of matter and depends on
temperature and pressure
 Heat
 System: part of the universe on which
attention is focused
 Surrounding- exchanges energy with the
system, make up the rest of the universe
 Example: a beaker with water sitting on a
hot plate warming.
 System: water
 Surroundings: beaker, hot plate, air
surrounding the beaker
 HEAT is represented by q
 ENDOTHERMIC: heat flows from surroundings
into system; heat absorbed; +q
 50 g of water is being warmed on the hot plate

 EXOTHERMIC: heat flows from system into

surroundings; heat escapes; -q
 The hot plate is turned off and the water starts
heating its surroundings. The temp of water
decreases and the temp of the surroundings increase
 Measuring Heat
 HEAT CAPACITY: amount of heat to raise the
temperature 1oC; C = J/ D oC (will sometimes be
given in KJ

 SPECIFIC HEAT: amount of heat to raise 1 g of

a substance 1oC; c = J/g D oC
 Specific heat is an intensive property.

***Note that Heat Capacity is a Big C and

Specific Heat is a little c
 Calorimeter

 A device to measure heat flow. Walls are

insulated do no exchange with outside air.
 Two-types
 Coffee-cup calorimeter
 Bomb calorimeter (used for gases)

q reaction = - q calorimeter
 Calorimeter

 q = m c Dt (q in J, m in g, t in Celsius)
 q = -C Dt

 Exothermic when q reaction is < 0, q

calorimeter is +
 Endothermic when q reaction is > 0, q
calorimeter is -
 Example: Coffee-Cup
Calorimeter
 When 1 gram of calcium chloride is added
to 50 grams of water in a coffee-cup
calorimeter, it dissolves. The temperature
rises from 25oC to 28.51oC. Assuming that
all the heat given off by the reaction is
transferred to the water, calculate q for
the reaction system. Is this exothermic or
endothermic?
 Example: Bomb Calorimeter

 The reaction between hydrogen and

chlorine can be studied in a bomb
calorimeter. It is found that when a 1.00
gram of hydrogen completely reacts, the
temperature rises from 20oC to 29.82oC.
Taking the heat capacity of the
calorimeter to be 9.33 kJ/oC, calculate the
amount of heat evolved in the reaction.
 Enthalpy

 The is the measure of heat from at

constant pressure between reactants and
products.
 DH rxn = DHproducts - DH reactants
 q= DH rxn
Exothermic vs Endothermic
Energy Diagram
 Thermochemical equations
 An equation will be given and it will tell
you the overall DH rxn
 The sign of DH rxn indicates whether the
reaction is endothermic and exothermic.
 The coefficients represent the number of
moles
 The phase symbols must be used
 Again, this is at constant pressure and at
25oC
 Rules of Thermochemistry

1. the magnitude of DH is directly

proportional to the amount of reactant
and product
 Heat of fusion: solid to liquid
 Heat of vaporization: liquid to gas

 If going from in opposite direction (liquid to

solid) Heat of fusion is same but opposite
 Calorimetry

 A 2.200 g sample of quinone, C6H4O2, is

burned in a bomb calorimeter whose heat
capacity is 7.854 kJ/oDC. The temperature
increases from 23.44oC to 30.57oC.
 What is the heat of combustion per gram?
 Per mole?
 Calorimetry

 The heat of combustion of glucose,

C6H12O6, is 15.57 kJ/g. A 2.500 g sample
burned in a bomb calorimeter raises the
temperature from 20.55oC to 23.25oC.
 What is the heat capacity of the
calorimeter?
 Calorimetry

 A 1.200 g sample of benzoic acid,

HC7H5O2, is burned in a calorimeter with a
heat capacity of 2.423 kJ/oDC. When the
calorimeter contains 1.500 kg of water,
the temperature rises from 22.45oC to
26.10oC.
 What is the heat of combustion of benzoic
acid in kJ/mol?
 Phase Changes
 The phase of a material changes based on
temperature and pressure.
 The phase is dependent on the motion of
the molecules of the substance.
 When a substance melts(freezes) or
boils(condenses), there is no temperature
change, but there is a change of heat
involved.
Phase Diagrams
 PHASE
DIAGRAM

 Normal melting (freezing) and boiling (condensing) points at

standard pressure
 Triple point: 3 phases exist at same T&P
 Critical temperature: above this T, only exists as a gas
 Critical pressure: the pressure to cause condensation at critical
temperature
 Sublimation: from solid to vapor directly
 Example

 How much heat is needed to melt 25 g of

ice?
 Example

 How much heat is evolved when one mole

of water cools from 100oC to 5oC?
 Rules of Thermochemistry
2. DH for a reaction is equal in magnitude by
opposite in sign to DH for the reverse
reaction.
3. The value of DH for a reaction is the
same whether it occurs in one step or in a
series
 AKA: Hess’s Law
 DHtotal = DH1 + DH2, etc..
 How much heat?

 Calculate DH for the decomposition of

liquid sulfuric acid to steam, oxygen and
sulfur dioxide gas.
 How much heat will be generated when
25 g of sulfuric acid decomposes?
 What is the Hf?

 Chlorine trifluoride reacts with ammonia to

form nitrogen, chlorine and hydrogen
fluoride gases. When two moles of
chlorine trifluoride reacts, 1196 kJ of heat
is evolved.
 Find Hf for chlorine trifluoride.
 Enthalpy Change and Hf
 Acetylene, C2H2, and benzene, C6H6, have the
same empirical formula. Benzene can be made
from acetylene: 3C2H2C6H6.
 The heats of combustion for C2H2 and C6H6 are -
1299.4 kJ/mol and -3267.4 kJ/mol, respectively.
 Calculate the heat of formation for each and the
heat of reaction of the formation of benzene
from acetylene.