THERMOCHEMISTRY

Engr. Edgie L. Estopace

School of Chemical Engineering and Chemistry
Mapua Institute of Technology
1
Outline
1. Principles of heat flow
2. Measurement of heat flow; calorimetry
3. Enthalpy
4. Thermochemical equations
5. Enthalpies of formation
6. Bond enthalpy
7. The first law of thermodynamics
Principles of Heat Flow
 Definitions
 The system: that part of the universe on which
attention is focused
 The surroundings: the rest of the universe
 Practically speaking, it is possible to consider only the
surroundings that directly contact the system
Figure 6.1 – Systems and Surroundings
Chemical Reactions
 When we study a chemical reaction, we
consider the system to be the reactants and
products
 The surroundings are the vessel (beaker, test
tube, flask) in which the reaction takes place
plus the air or other material in thermal
contact with the reaction system
Forms of Energy
 Two broad categories of energy: potential
energy and kinetic energy.

 Potential energy - associated with the relative

position of an object.

 Kinetic energy - associated with motion.

1 2
Kinetic energy = mv
2
Forms of Energy
 Internal energy - the combined kinetic and
potential energies of atoms and molecules that
make up an object or system.

 Chemical energy - energy released or

absorbed during a chemical reaction.

 Other forms of energy include radiant,

mechanical, thermal, electrical, and nuclear.
Heat and Work
 Heat is the flow of energy between two
objects because of a difference in
temperature.

 Heat flows from the warmer object to the cooler

object.
 Work is the transfer of energy accomplished
by a force moving a mass some distance
against resistance.
State Properties
 The state of a system is specified by
enumerating:
 Composition
 Temperature
 Pressure
 State properties depend only on the state of
the system, not on the path the system took to
reach the state
 Mathematically for a state property X:
 ΔX is the change in X
 ΔX = Xfinal – Xinitial
Direction and Sign of Heat Flow
 Heat is given the symbol, q
 q is positive when heat flows into the system
from the surroundings
 q is negative when heat flows from the system
into the surroundings
 Endothermic processes have positive q
 H2O (s)  H2O (ℓ) q>0
 Exothermic processes have negative q
 CH4 (g) + 2O2 (g)  CO2 (g) + H2O (ℓ) q < 0
Exothermic and Endothermic Processes
Magnitude of Heat Flow
 In any process, we are interested in both the
direction of heat flow and in its magnitude
 q is expressed in joules (or kilojoules)
 James Joule (1818-1889); calorimetry
 Alternate unit: calorie
 1 calorie = 4.184 J
 1 kilocalorie = 4.184 kJ
 Nutritional calories are kcal
The Calorimetry Equation
 q = C x Δt
 Δt = tfinal – tinitial
 C (uppercase) is the heat capacity of the system:
it is the quantity of heat needed to raise the
temperature of the system by 1 °C
 q = m x c x Δt
 c (lowercase) is the specific heat: the quantity of
heat needed to raise the temperature of one gram
of a substance by 1 °C
 c depends on the identity and phase of the
substance
Heat Capacity and Specific Heat
 The amount of heat energy absorbed can be quantified.
q  mcT
q  nC p T
 Heat Capacity and Specific Heat

 Specific heat and molar heat capacities for some

common substances.
Example Problem 2
 Heating a 24.0 g aluminum can raises its
temperature by 15.0ºC. Find the value of q for
the can.
Example Problem 3
 The molar heat capacity of liquid water is 75.3
J/mol K. If 37.5 g of water is cooled from 42.0
to 7.0ºC, what is q for the water?
Specific Heat
 The specific heat of a substance, like the
density or melting point, is an intensive
property that can be used to identify a
substance or determine its purity
 Water
 Water has an unusually large specific heat
 A large quantity of heat is required to raise the
temperature of water
 Climate is moderated by the specific heat of water
 Only two states in the US have never recorded
temperatures over 100 °F – one is Alaska (cold North)
and the other is Hawaii (moderated by water)
Table 6.1
Example 6.1
Measurement of Heat Flow:
Calorimetry
 A calorimeter is a device used to measure the
heat flow of a reaction
 The walls of the calorimeter are insulated to
block heat flow between the reaction and the
surroundings
 The heat flow for the system is equal in
magnitude and opposite in sign from the heat
flow of the calorimeter
 qreaction = - qcalorimeter
 qreaction = - Ccal Δt
Calorimetry
 Heat flow is measured using a calorimeter.

 A calorimeter measures the heat evolved or

absorbed by the system of interest by
measuring the temperature change in the
surroundings.
qsystem =  qsurroundings
qgained =  qlost
Example Problem 9.4
 A glass contains 250.0 g of warm water at
78.0ºC. A piece of gold at 2.30ºC is placed in
the water. The final temperature reached by
this system is 76.9ºC. What was the mass of
gold? The specific heat of water is 4.184
J/gºC, and that of gold is 0.129 J/gºC.
Calorimetry
 There are two steps in a calorimetric
measurement.

 Calibration - the calorimeter constant, Ccalorimeter,

is determined by dividing the known amount of
heat released in the calorimeter by the
temperature change of the calorimeter.
q = Ccalorimeter  T
 Actual Measurement - heat released or absorbed
in a reaction of known quantity of material is
measured.
Calorimetry
 Actual Measurement - temperature change for
the calorimeter and the calorimeter constant
are used to determine the amount of heat
released by a reaction.

qcalorimeter = Ccalorimeter  Tcalorimeter

qreaction =  qcalorimeter
 Calorimetry

 Diagram of a bomb calorimeter and standard

choice for system and surroundings in a bomb
calorimetry experiment.
Example Problem 9.5
 In the calibration of a calorimeter, an
electrical resistance heater supplies 100.0 J of
heat and a temperature increase of 0.850ºC is
observed. Then, 0.245 g of a particular fuel is
burned in this same calorimeter and the
temperature increases by 5.23ºC. Calculate the
energy density of this fuel, which is the
amount of energy liberated per gram of fuel
burned.
Figure 8.2
 Coffee-cup Calorimeter
 For a reaction performed in a coffee-cup calorimeter
J
qreac tion  mwater  4.18   t
g C
Example 6.2
Example 6.2, (Cont’d)
Figure 6.3
Bomb Calorimeter
 The bomb calorimeter is more versatile than
the coffee-cup calorimeter
 Reactions involving high temperature
 Reactions involving gases
 The bomb is a heavy metal vessel that is
usually surrounded by water
 qreaction = -qcalorimeter
 qreaction = -CcalΔt
 Ccal is a function of the calorimeter and can be
measured experimentally
Example 8.3
Enthalpy
 The heat flow at constant pressure is equal to
the difference in enthalpy (heat content)
between products and reactants
 The symbol for enthalpy is H
 We measure changes in enthalpy using a
calorimeter and a reaction run at constant
pressure:
 ΔH = Hproducts – Hreactants
 The sign of the enthalpy change is the same as
for heat flow:
 ΔH > 0 for endothermic reactions
 ΔH < 0 for exothermic reactions
 Enthalpy is a state variable
Enthalpy
 The conditions under which heat flow, q,
occurs will have an impact on the
measurement that is made.

 Combustion of octane releases 5.45 x 103 kJ

under constant volume conditions, represented as
qv.
 Combustion of octane releases 5.48 x 103 kJ
under constant pressure conditions, represented as
qp.
Defining Enthalpy
 The internal energy change for a reaction
equals the sum of the heat flow and the work.
E  q  w
 During an expansion, w = –PV.
E  q  PV

 Under constant volume conditions, V = 0, and

E = qv. E  q v
Defining Enthalpy
 Enthalpy is the heat flow under conditions of
constant pressure.
 The enthalpy change can be expressed as
H  E  PV H  E  (PV )

H  (q  PV )  (PV )

H  q  PV  PV

H  qp
Defining Enthalpy
 When a system releases heat, the process is
said to be exothermic.
 The value of H is less than zero; the sign on H
is negative
 When a system absorbs heat, the process is
said to be endothermic.
 The value of H is greater than zero; the sign on
H is positive.
H of Phase Changes
 Phase changes occur under constant pressure
conditions.
 The heat flow during a phase change is an enthalpy change.
 During a phase change, temperature does not change with heat flow
due to formation or breaking of intermolecular attractive forces.
 ∆H of Phase Changes
 The heat required to convert a liquid to a gas is the
heat of vaporization, Hvap.
 Hvap is endothermic with a positive value.
 The heat released to convert a gas to a liquid is the
heat of condensation, Hcond.
 Hcond is exothermic with a negative value.
 Hcond = –Hvap
 The values of enthalpy changes in opposite directions
have equal numeric values and differ only in their
signs.
 The magnitude of enthalpy change depends on the
substance involved.
 ∆H of Phase Changes

 Standard molar enthalpies and temperatures for

phase changes of water.
∆H of Phase Changes
 The value of H for a phase change is
compound specific and has units of kJ/mol.

 The heat flow can be calculated using the number

of moles of substance, n, and the value of the
enthalpy change.
H  n  Hphase change
 ∆H of Phase Changes

 Heat curve for the heating of 500-g of ice at -50oC

to 200oC.
Example Problem
 Calculate the enthalpy change when 240. g of
ice melts.
Bonds and Energy
 The enthalpy change for a reaction can be estimated
using bond energies.
 During a chemical reaction, reactant bonds are
broken and product bonds are made.
 Breaking bonds requires energy.
 Making bonds releases energy.
 If the amount of energy released making product
bonds is greater than the amount of energy required
to break reactant bonds, the reaction is exothermic. If
the energy released is less than the energy required,
the reaction is endothermic.
 Bonds and Energy

CH 4  2O2  CO2  2H 2O

 The combustion of methane breaks 4 C-H bonds

and 2 O=O bonds. 2 C=O bonds and 4 O-H bonds
are made.
Bonds and Energy
 The accuracy of enthalpy changes calculated from
tabulated bond energies is not very good.
 The bond energies used are averages.
 Bond energy method used to estimate enthalpy changes
for reactions involving compounds with no available
thermochemical data.
 A thermochemical equation summarizes the overall
energetics for a chemical reaction.
 The sign on the H indicates whether the reaction is
endothermic or exothermic
CH 4 (g) + 2O2 (g) 
 CO2 (g) + 2H 2O(l )
H  890.4 kJ
Bonds and Energy
 The combustion of methane is an exothermic reaction and
releases 890.4 kJ of heat energy when 1 mole of methane
reacts with 2 moles of oxygen.
CH 4 (g) + 2O2 (g) 
 CO2 (g) + 2H 2O(l )
H  890.4 kJ
2CH 4 (g) + 4O2 (g) 
 2CO2 (g) + 4H2O(l )
H  1780.8 kJ
 For thermochemical equations, if the stoichiometric
coefficients are multiplied by some factor, the heat of reaction
must also be multiplied by the same factor.
Heats of Reaction for Some Specific Reactions

 Some classes of chemical reactions are given

their own labels for heats of reactions.
 Heat of combustion, Hcomb
 Heat of neutralization, Hneut
 Heat of formation, Hf, is the heat of reaction for
formation of substances.
1
C(s) + O 2 (g) 
 CO(g)
2
Fractional coefficients are allowed for formation reactions
because only one mole of product can be formed.
Heats of Reaction for Some Specific Reactions
 A formation reaction is the chemical reaction
by which one mole of a compound is formed
from its elements in their standard states.

 The standard state is the most stable form of

an element at room temperature, 25oC, and
pressure, 1 atm, indicated with a superscript o.

 Hfo = 0 for an element in its standard state.

Hess’s Law and Heats of Reaction
 Direct calorimetric determinations of some reactions
may be too difficult or dangerous to perform.
 An indirect method is needed to obtain heats of reaction.
 Hess’s law: the enthalpy change for any process is
independent of the particular way the process is
carried out.
 Enthalpy is a state function.
 A state function is a variable whose value depends only
on the state of the system and not its history.
 Hess’s Law

 Conceptual diagram representing Hess’s law.

Enthalpy is a state function, so any convenient
path can be used to calculate the enthalpy change.
 Hess’s Law

 Enthalpy diagram for the combustion of methane. The

CH4 is converted to CO, then the CO is converted to CO2.
The H for each step is used to calculate the H for the
overall reaction. The H will be the same for both paths.
Example Problem
 One origin of SO3 is the combustion of sulfur,
which is present in small quantities in coal,
according to the following equation.
3
S(s)  O2 (g)  SO3 (g)
2
S(s)  O2 (g)  SO2 (g) H o  296.8 kJ
2SO2 (g)  O2 (g)  2SO3 (g) H o  197.0 kJ
 Given the thermochemical information below,
determine the heat of reaction for this
reaction.
 Formation Reactions and Hess’s Law

 Conceptual diagram showing how to use tabulated

enthalpies of formation to calculate the enthalpy
change for a chemical reaction.
Formation Reactions and Hess’s Law
 The enthalpy change for a reaction can be
calculated using Hess’s law and heats of
formation.

H = vi H (products)i   v j H (reactants) j
o o
f
o
f
i j
Example Problem 9.8
 Use tabulated data to find the heat of
combustion of one mole of propane, C3H8, to
form gaseous carbon dioxide and liquid water.
Example Problem 9.9
 Ethanol, C2H5OH, is used to introduce oxygen
into some blends of gasoline. It has a heat of
combustion of 1366.8 kJ/mol. What is the
heat of formation of ethanol?
Energy and Stoichiometry
 A thermochemical equation allows for the
stoichiometric treatment of energy.
 For an exothermic reaction, energy is treated as a product.
 For an endothermic reaction, energy is treated as a
reactant.
 The thermochemical equation is used to convert
between the number of moles of a reactant or
product and the amount of energy released or
absorbed.
 The stated value of H for a thermochemical equation
corresponds to the reaction taken place exactly as written,
with the indicated numbers of moles of each substance
reacting.
Energy and Stoichiometry

 Flow chart detailing the sequence of steps needed to

calculate the amount of energy released or absorbed
when a chemical reaction is carried out using a given
amount of material.
 Thermochemical Equations
 A thermochemical equation is a chemical equation with the ΔH
for the reaction included
 Example
 NH4NO3 (s)  NH4+ (aq) + NO3- (aq)
 Experiment gives qreaction = 351 J for one gram of ammonium
nitrate
 For one mole, this is
351J 80 .05 g
  2.81 X 10 4 J  28 .1kJ
1.00 g 1mol

 The thermochemical equation is

 NH4NO3 (s)  NH4+ (aq) + NO3- (aq) ΔH = +28.1 kJ
Conventions for Thermochemical
Equations
1. The sign of ΔH indicates whether the reaction
is endothermic or exothermic
2. The coefficients of the thermochemical
equation represent the number of moles of
reactant and product
3. The phases of all reactant and product species
must be stated
4. The value of ΔH applies when products and
reactants are at the same temperature, usually 25
°C
Rules of Thermochemistry
1. The magnitude of ΔH is directly proportional
to the amount of reactant or product
2. ΔH for the reaction is equal in magnitude but
opposite in sign for ΔH for the reverse of the
reaction
3. The value of ΔH is the same whether the
reaction occurs in one step or as a series of
steps
This rule is a direct consequence of the fact that ΔH
is a state variable
This rule is a statement of Hess’s Law
Example 6.4
Example 6.4, (Cont’d)
 Enthalpy of Phase Changes
 Phase changes involve enthalpy
 There is no change in temperature during a phase change
 Endothermic: melting or vaporization
 Exothermic: freezing or condensation
 Pure substances have a value of ΔH that corresponds to melting
(reverse, fusion) or vaporization (reverse, condensation)
Example 6.5
Example 6.6
Example 6.6, (Cont’d)
Recap of the Rules of Thermochemistry
 ΔH is directly proportional to the amount of
reactant or product
 If a reaction is divided by 2, so is ΔH
 If a reaction is multiplied by 6, so is ΔH
 ΔH changes sign when the reaction is
reversed
 ΔH has the same value regardless of the
number of steps
 Enthalpies of Formation Hf

 The standard molar enthalpy of formation, , is equal to the

enthalpy change
 For one mole of a compound
 At constant pressure of 1 atm
 At a fixed temperature of 25 °C
 From elements in their stable states at that temperature and
pressure
 Enthalpies of formation are tabulated in Table 8.3 and in Appendix
1 in the back of the textbook
Table 6.3
Table 6.3, (Cont’d)
Table 6.3, (Cont’d)
Enthalpies of Formation of Elements and of H+ (aq)

 The enthalpy of formation of an element in its standard state at 25

°C is zero
HfBr2 (l )  HfH2O(l )  0

 The enthalpy of formation of H+ (aq) is also zero

Calculation of ΔH°

H   Hf products   Hf reactants

 The symbol Σ refers to “the sum of”

 Elements in their standard states may be
omitted, as their enthalpies of formation are
zero
 The coefficients of reactants and products in
the balanced equation must be accounted for
Example 6.7
Example 6.7, (Cont’d)
Example 6.8
The First Law of Thermodynamics
 Thermodynamics
 Deals with all kinds of energy effects in all kinds
of processes
 Two types of energy
 Heat (q)
 Work (w)
 The Law of Conservation of Energy
 ΔEsystem = - ΔEsurroundings
 The First Law
 ΔE = q + w
 The total change in energy is equal to the sum of the
heat and work transferred between the system and
the surroundings
Conventions
 q and w are positive
 When the heat or work enters the system from the
surroundings
 q and w are negative
 When the heat or work leaves the system for the
surroundings
Energy Transformation and Conservation of Energy

 For a system or surroundings, the only

possible forms of energy flow are heat, q, and
work, w.
E = q  w
 The delta, , means “change in” and is
defined as the difference in the final and
initial states.
E = Efinal  Einitial
Example Problem
 If 515 J of heat is added to a gas that does 218
J of work as a result, what is the change in the
energy of the system?
Energy Transformation and Conservation of Energy

 The sign resulting from the difference in the

final and initial states indicates the direction
of the energy flow.

 Negative values indicate energy is being released.

 Positive values indicate energy is being absorbed.

Energy Transformation and Conservation of Energy

 First law of thermodynamics states that

energy can be transformed from one form to
another but cannot be created or destroyed.

Euniverse = Esurroundings + Esystem  0

Figure 8.10
Example 6.9
Heat
 Ordinarily, when a chemical reaction is
carried out in the laboratory, energy is
evolved as heat
 CH4 (g) + 2O2 (g)  CO2 (g) + H2O (ℓ) ΔE = -
885 kJ
 The combustion of methane in a Bunsen burner
produces nearly 885 kJ of heat per mol
 The decrease in volume that takes place is a 1%
work effect
Work
 In an internal combustion engine, a significant
fraction of the energy of combustion is
converted to useful work
 The expansion of the combustion gases produces
a volume and a pressure change
 The system does work on its surroundings
 Propels the car forward
 Overcomes friction
 Charges battery
 Like ΔH, ΔE is a state variable
 q and w are not state variables
Figure 6.11 – Pressure-Volume Work
ΔH and ΔE
 Constant pressure
 Coffee-cup calorimeter
 ΔH = qp
 Constant volume
 In a bomb calorimeter, there is no pressure-
volume work done
 ΔE = qv
ΔH and ΔE, (Cont’d)
 H = E + PV
 ΔH = ΔE + PΔV
 The PV product is important only where gases are
involved; it is negligible when only liquids or
solids are involved
 ΔH = ΔE + ΔngRT
 Δng is the change in the number of moles of gas
as the reaction proceeds
Example 8.10
 End of Chapter 15
 Fireworks are beautiful exothermic
chemical reactions.

96
 THERMOCHEMISTRY

Engr. Edgie L. Estopace

School of Chemical Engineering and Chemistry
Mapua Institute of Technology
97