Principles and Modern Applications 8 th EDITION

Petrucci • Harwood • Herring

Chapter 7: Thermochemistry

Thermochemistry
7
1
Thermochemistry CONTENTS
7-1 Some Basic Terms in Thermochemistry

7-2 Heat
7-3 Heats of Reaction and Calorimetry

7-4 Work
7-5 The First Law of Thermodynamics

7-6 Heats of Reaction: DU and DH

7-7 Indirect Determination of DH: Hess’s Law

7-8 Standard Enthalpies of Formation

7-9 Fuels as Sources of Energy

2
 7-1 Some Basic Terms in Thermochemistry

• Potassium reacts with water, liberating sufficient heat to ignite

the hydrogen evolved. The transfer of heat between substances in
chemical reactions is an important aspect of thermochemistry.

• Thermochemistry is the study of energy changes

that occur during chemical reactions.
• System: the part of the universe being studied.
• Surroundings: the rest of the universe.

Focus is on heat and

Surroundings
Surroundings

Universe matter transfer between

System the system ...
and the
surroundings
Surroundings
3
 7-1 Some Basic Terms in Thermochemistry

Three common systems and Surroundings

• An open system freely exchanges energy

and matter with its surroundings.

• A closed system can exchange energy with

its surroundings, but not matter.

• An isolated system does not interact with its

surroundings.

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• Energy, U
• The capacity to do work (to displace or move matter).

• Work, w
• Force acting through a distance.
w=Fxd
𝐦𝟐
W = 𝐤𝐠 = 𝐉
w= mxaxd 𝐬𝟐

• Kinetic Energy, eK
• The energy of motion.
𝟏 𝟐 𝐦𝟐
𝐞𝐤 = 𝐦𝐯 𝒆𝒌 = 𝐤𝐠 𝟐 = 𝐉
𝟐 𝐬
• Energy has the units of joules (J or kg m /s )
. 2 2

• Potential Energy
• Energy due to condition, position, or composition.
• Associated with forces of attraction or repulsion between objects.
Ep= mgh 5
6
 Potential energy (P.E.) and kinetic energy (K.E.)
• Energy can change from potential to kinetic.

• Potential energy is maximum at the top of each bounce.

• Kinetic energy is maximum at the moment of impact.

• Sum of the P.E. and K.E. decreases continuously as the

thermal energy of the ball and surroundings increase.

Thermal Energy
Kinetic energy associated with random molecular motion.

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• Thermal energy the temperature of a system
the hotter the sample the greater is
its thermal energy.

• The thermal energy on the number of particles present

• A small sample at a high temperature a cup of coffee at 75 ºC

a larger sample at a lower temperature
a swimming pool at 30 ºC

• Temperature thermal energy

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 7-2 Heat (q)
• Heat involves the transfer of thermal energy.

• Heat is energy transferred between a system and its surroundings as a result of a

temperature difference.

• Energy, as heat, passes from a warmer body (higher T) to a colder body (lower T)
until the average kinetic energies of the two bodies is equal (ie. until they have the
same T).

“flows” spontaneously from

higher T  lower T

“flow” ceases at thermal

equilibrium

9
 Phase Changes
• Heat transfer can also cause a change in matter; between solid, liquid
and gas. In this process, the transfer of energy does not cause a change in
temperature (the process is isothermal), but rather the energy overcomes
intermolecular forces.

• A process occurring at a constant temperature is said to be isothermal.

• Once a solid has melted completely, any further heat flow will raise the
temperature of the resulting liquid.

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• The quantity of heat (q) required to change the temperature of a substance
depends on:
1. How much the temperature is to be changed (DT).
2. The quantity of substance (m).
3. The nature of substance (type of atoms or molecules)(c).

• The quantity of heat required to change the temperature of one gram of water by
one degree Celsius has been called the calorie (cal).
• The calorie is a small unit of energy, and the unit kilocalorie (kcal) has also been
widely used.
• The kilocalorie is commonly used for measuring the energy content of foods.
• The SI unit for heat is simply the basic SI energy unit, the joule (J).

1 cal = 4.184 J

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 Heat Capacity
• Heat Capacity (C)
The quantity of heat required to change the temperature of a system by 1 oC,
usually expressed as J oC–1.

• Molar heat capacity

System is one mole of substance, JoC-1mol-1.

• Specific heat capacity or specific heat (c)

System is one gram of substance, JoC-1g-1.

• Specific heats of substances are temperature (phase) dependent. Over the

range from 0 to 100 oC, the specific heat of water (ie. H2O(l)) averages about

12
13
• The quantity of heat related to the mass of a substance, its specific heat,
and the temperature change.

• The temperature change is expressed as ∆T = Tf – Ti, where Tf is the final

temperature and Ti is the initial temperature.

If DT (Tf >Ti) > 0, then q > 0 and heat is gained by the system

If DT (Tf <Ti) < 0, then q < 0 and heat is lost by the system

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 Law of conservation of energy

• In interactions between a system and its surroundings the total

energy remains constant— energy is neither created nor destroyed.

qsystem + qsurroundings = 0

qsystem = -qsurroundings

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 Experimental Determination of Specific heats

a) 150.0 g sample of lead is heated to the temperature of

boiling water (100oC).

b) A 50.0 g sample of water is added to a thermally insulated

beaker, and its temperature is found to be 22oC.

c) The hot lead is dumped into the cold water, and the
temperature of the final lead–water mixture is 28.8oC.

• The transfer of energy, as heat, from the lead to the cooler water causes the
temperature of the lead to decrease and that of the water to increase, until the lead
and water are at the same temperature.
• Either the lead or the water can be considered the system. If we consider lead to
be the system, we can write qlead = qsystem. Then, qwater = qsurrundings.

• Thus, qlead = -qwater

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17
 Specific heats of Some Substances
TABLE 7.1 Some Specific Heat Values, J g-1 °C-1

• The relatively high specific heat of aluminum compared with other metals
helps to account for its use in “miracle thaw” products designed to thaw frozen
foods rapidly. The aluminum cools only slowly as it transfers heat to the frozen
food, and the food thaws more quickly than when simply exposed to air.

• Because of their greater complexity at the molecular level, compounds generally have
more ways of storing internal energy than do the elements; they tend to have higher
specific heats. Water, for example, has a specific heat that is more than 30 times as great
as that of lead. We need a much larger quantity of heat to change the temperature of a
sample of water than of an equal mass of a metal.

• An environmental consequence of the high specific heat of water is found in the effect of
large lakes on local climates. Because a lake takes much longer to heat up in summer and
cool down in winter than other types of terrain, lakeside communities tend to be cooler in
summer and warmer in winter than communities more distant from the lake. 18
 7-3 Heats of Reaction and Calorimetry
• Thermal energy
Kinetic energy associated with random molecular motion.

• Chemical energy
Associated with chemical bonds and intermolecular attractions.

• A chemical reaction is a process in which some chemical bonds are broken and
others are formed, then, the chemical energy of a system change as a result of
a reaction and appears as heat.

• Heat of reaction , qrxn

The quantity of heat exchanged between a system and its surroundings
when a chemical reaction occurs within the system at constant temperature.

• Heat of combustion
The heat released by a combustion reaction.

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• An exothermic reaction gives off heat

– In an isolated system, the temperature increases (T ↑) .

– The system goes from higher to lower energy; qrxn is negative (qrxn< 0).

• An endothermic reaction absorbs heat

– In an isolated system, the temperature decreases (T ↓).

– The system goes from lower to higher energy; qrxn is positive (qrxn > 0).

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 Conceptualizing a heat of reaction at constant temperature

CaO(s) + H2O(l) → Ca(OH)2(s) Ba(OH)2 8H2O(s) + 2 NH4Cl(s) → BaCl2 2H2O(s)

+ 2 NH3(aq) + 8 H2O(l)

Exothermic reaction Endothermic reaction 21

 Conceptualizing an Exothermic Reaction
Surroundings are at 25 °C

Typical situation: some

heat is released to the
surroundings, some heat
is absorbed by the 32.2 °C 35.4 °C
solution.
25 °C

Hypothetical situation: all heat is In an isolated system, all heat is

instantly released to the absorbed by the solution.
surroundings. Heat = qrxn Maximum temperature rise.
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 Calorimeter

• A calorimeter is a device used to measure the heat absorbed or evolved during a

chemical reaction.
• Two types of calorimeters (coffee-cup and bomb calorimeters) will be considered
and these will be treated as isolated systems.
• Some reactions, such as combustion, cannot be carried out in a coffee-cup
calorimeter.

heat

A bomb calorimeter assembly A “Coffee-Cup” Calorimeter

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 Bomb Calorimeter
• Bomb Calorimeter: a device used to measure the heat of a combustion reaction. The
quantity measured is the heat of reaction at constant temperature.
• In a bomb calorimeter, a sample of known mass is placed in a heavy-walled “bomb,”
which is then pressurized with oxygen.

A pulse of electric current heats and ignites the sample.

Temperature is measured before and

after detonation (ΔT).

Bomb immersed in H2O(l)

Filled with O2(g) at high pressure

heat

A bomb calorimeter
assembly 24
 Bomb Calorimeter
• The quantity of heat is just the negative of the thermal energy gained by the
calorimeter and its contents (qcalorimeter).
• qrxn = - qcalorimeter (qcalorimeter = q bomb + q water + q wires +…)

• Heat capacity of the calorimeter

The quantity of heat required to raise the temperature of the
calorimeter assembly by one degree Celsius.

• qcalorimeter = heat capacity of calorimeter x ∆T

heat

A bomb calorimeter
assembly 25
26
27
 The “Coffee-Cup” Calorimeter
• A common general chemistry assembly used to measure the heat of an aqueous
reaction. The quantity measured is the heat of reaction at constant pressure.

Temperature is measured before

and after reaction (DT).
• A simple calorimeter.
• Well insulated and therefore isolated. Cork stopper

• Measure temperature change. Two cups for additional

thermal insulation
• The reaction mixture is in the inner cup.
• The outer cup provides additional thermal insulation from
the surrounding air.
A Styrofoam “coffee-cup”
• The cup is closed off with a cork stopper through which a calorimeter
thermometer and a stirrer are inserted and immersed into
the reaction mixture.
qrxn = - qcalorimeter
• The reaction in the calorimeter occurs under the constant
pressure of the atmosphere.
qcal = m CDT
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30
 7-4 Work
• In addition to heat effects, chemical reactions may also do work.
• Like heat, work is an energy transfer between a system and its surroundings.
• Unlike heat, work is caused by a force moving through a distance (heat is caused by a
temperature difference).
• A negative quantity of work signifies that the system loses energy.
• A positive quantity of work signifies that the system gains energy.

• The O2(g) which is formed pushes back the weight, and

does work on the surroundings.

• Gas formed pushes against the atmosphere.

• The volume changes.

Illustrating work (expansion)
• Work associated with the expansion or compression of during the chemical reaction
gases is called pressure–volume work.
2 KClO3(s) → 2 KCl(s) + 3 O2(g)

Pressure-volume work
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 Pressure Volume Work

work (w) = force (M x g) x distance (Δh)

= -M x g x Δh

𝑀𝑥𝑔
𝑤= − x ∆h x A
𝐴
w = -P x A x Δ h
𝐹
𝑤= − x ∆h x A w = -PDV
𝐴
w = -PextDV
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• Work w = -PextDV
• When a gas expands, △V is positive and the work is negative system loses energy.
• When a gas is compressed, △V is negative and w is positive, signifying that energy
(as work) enters the system.

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• If pressure is stated in atmospheres and volume in liters, the unit of work is the
liter-atmosphere, L atm; while the SI unit of work is the joule.
• The conversion factor between these two units of work can be obtained from the gas
constant, R.

8.3145 J mol−1 K−1 = 0.082057 L atm mol−1 K−1

8.3145 J mol−1 K−1

= 101.33 J/L atm
0.082057 L atm mol−1 K−1

1 L atm = 101.33 J

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Example
Example 7-57-3
Calculating Pressure-Volume Work.
Suppose the gas in the previous figure is 0.100 mol He at 298 K. How much
work, in Joules, is associated with its expansion at constant temperature.

Assume an ideal gas and calculate the volume change:

Vi = nRT/P
= (0.100 mol)(0.08201 L atm mol-1 K-1)(298K)/(2.40 atm)
= 1.02 L
Vf = (0.100 mol)(0.08201 L atm mol-1 K-1)(298K)/(1.30 atm)
=1.88 L

DV = Vi -Vf =1.88 L - 1.02 L = 0.86 L

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Example 7-3
7-5
Calculate the work done by the system:

w = -PextDV
101 J
= -(1.30 atm)(0.86 L)( )
1 L atm
= -1.1 x 102 J

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 7-5 The First Law of Thermodynamics

Internal Energy, U.
Total energy (potential and
kinetic) in a system.

• Translational kinetic energy.

• Molecular rotation.
• Bond vibration.
• Intermolecular attractions.
• Chemical bonds.
• Electrons.

FIGURE 7-9
•Some contributions to the internal energy of a system

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 The First Law of Thermodynamics

• A system contains only internal energy.

– A system does not contain heat or work.
– These only occur during a change in the system.
– The change in DU is related to the energy exchanges that occur as heat (q) and work (w).

The First Law:

DU = q + w

• Law of Conservation of Energy

– The energy of an isolated system is constant.

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 The First Law of Thermodynamics

• An isolated system is unable to exchange either heat or work with its

surroundings, so that DUisolated system = 0, and we can say:

The energy of an isolated system is constant.

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• Energy entering a system carries a positive sign:
– heat absorbed by the system, q or
– work done on the system, w
• Energy leaving a system carries a negative sign:
– heat given off by the system, q
– work done by the system, w

• If, on balance, more energy enters the system than leaves, ∆U is positive.

• If more energy leaves than enters, ∆U is negative.

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41
 Functions of State
• Any property that has a unique value for a specified state of a system is said to
be a function of state or a state function.

• Water at 293.15 K and 1.00 atm is in a specified state.

• d = 0.99820 g/mL
• This density is the state function.
• It does not matter how the state was established.

Obtain three different samples of water:

1. one purified by extensive distillation of groundwater;
2. one synthesized by burning pure H2(g) in pure O2(g) and
3. one prepared by driving off the water of hydration from CuSO4•5H2O and condensing the gaseous
water to a liquid.

• The densities of the three different samples for the state that we specified will be the same: 0.99820.
• The value of a function of state depends on the state of the system, and not on how that state was
established.
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 Functions of State

• U is a function of state.
– Not easily measured.

• DU has a unique value between two states.

– Is easily measured.

DU -DU
State 1(U1) → State 2(U2) → State 1(U1)

ΔUoverall =ΔU + (-ΔU = U2 - U1 U2 - U1

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 Path Dependent Functions
• Changes in heat (q) and work (w) are not functions of state.

• Their values depend on the path followed when a system undergoes a change.
–Remember example 7-5,
w = -1.1 x 102 J in a one step expansion of gas:

• Let us consider a two step process from 2.40 atm to 1.80 atm, and finally to 1.30 atm.

1.30 atm
2.40 atm 1.80 atm w = (-1.80 atm)(1.36-1.02)L + (-1.30 atm)(1.88-1.36)L
= (-0.61) L atm + (- 0.68) L atm
= (-1.3) L atm (101J/ 1L atm)
= -1.3 x 102 J

1.02 L 1.36 L 1.88 L

Compared -1.1  102 J for the one stage process.
Intermediate state
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 Path Dependent Functions

• The value of DU is the same for the single- and two-stage expansion processes
because internal energy is a function of state.

• Slightly more work is done in the two-stage expansion. Work is path dependent.

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 7-6 Heats of Reaction: DU and DH
• Constant Volume Reactions
Reactants → Products
Ui Uf
DU = Uf - Ui

DU = qrxn + w

• In a system at constant volume (bomb calorimeter):

The original reactants and products are confined within the bomb, and the
reaction occurs at constant volume. Because the volume is constant, DV = 0,
and no work is done, w = -PDV = 0.

DU = qrxn + w = qrxn + 0 = qrxn = qv

The heat of reaction measured in a bomb calorimeter is equal to DU.

46
 Two different paths leading to the same internal
energy change in a system

• In path (a)

• In path (b)

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 Heats of Reaction
• Constant Pressure Reactions: carried out open to the constant pressure of the
atmosphere. Here, PV work is done as the system expands or contracts.

qV = qP + w

We know that w = - PDV and DU = qv, therefore:

DU = qP - PDV
qP = DU + PDV
These are all state functions, so define a new function.
Let enthalpy be H = U + PV
Then DH = Hf – Hi = DU + DPV

If we work at constant pressure and temperature:

DH = DU + PDV = qP
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 ENTHALPY (DH ) AND INTERNAL ENERGY (DU) CHANGES
IN A CHEMICAL REACTION
Comparing heats of reaction at constant volume and constant pressure
for a reaction
• The heat of reaction at constant pressure, DH, and the heat of reaction
at constant volume, DU are related by the expression, DU = DH -PDV.
• The PDV term is the energy associated with the change in volume of
the system under a constant external pressure.
• To assess just how significant pressure–volume work is, consider
the following reaction,
2 CO(g) + O2(g) → 2 CO2(g)
a) No work is performed at constant volume because the piston
cannot move.
qV = DU = DH - PDV = -563.5 kJ/mol
b) The reaction is carried out at constant pressure, the piston allowed
to move and the surroundings do work on the system. More heat is
evolved than in the constant-volume reaction.
qp = DU + PDV qp = qV + PDV
-w = PDV = P(Vf – Vi) = RT(nf – ni) = -2.5 kJ
qp = -563.5 kJ + (-2.5 kJ)
qp = -566.0 kJ
49
C12H22O11(s) + 12 O2(g) → 12 CO2(g) + 11 H2O(l) DH = -5.65x103 kJ

50
 Enthalpy Change (DH) Accompanying a Change in
State of Matter

• Molar enthalpy of vaporization:

The heat required to vaporize a fixed quantity (1 mole) of liquid is called the
enthalpy (or heat) of vaporization.

H2O (l) → H2O(g) DH = 44.0 kJ at 298 K

• Molar enthalpy of fusion:

The heat required to melt a fixed quantity (1 mole) of solid is called the enthalpy
(or heat) of fusion

H2O (s) → H2O(l) DH = 6.01 kJ at 273.15 K

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52
 Standard States and Standard Enthalpy Changes

• The measured enthalpy change for a reaction has a unique value only if the initial state
(reactants) and final state (products) are precisely described.

• Standard enthalpy of reaction, DH°

– The enthalpy change of a reaction in which all reactants and products are in their
standard states.

• Standard State
– The standard state of a solid or liquid substance is the pure element or compound at 1 bar
pressure and the temperature of interest (usually 25 oC).

– Gaseous standard state is the “ideal gas” at 1 bar pressure and the temperature of
interest (usually 25 oC).

– e.g., at 1 bar, 25 oC standard state for Hg is liquid, C is solid, H2O is liquid, He is gas.

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 Enthalpy Diagrams
• The negative sign of DH in the combustion of sucrose means that reaction is exothermic.

C12H22O11(s) + 12 O2(g) → 12 CO2(g) + 11 H2O(l) DH = -5.65x103 kJ

• The positive sign of DH in the reaction of nitrogen with oxgen means that reaction is endothermic.

N2(g) + O2(g) → 2 NO(g) DH° = +180.50 kJ

• An enthalpy diagram is a diagrammatic representation

of enthalpy changes in a process.

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 7-7 Indirect Determination of DH: Hess’s Law
• DH is an extensive property.
– Enthalpy change is directly proportional to the amount of substance in a system.
– The standard enthalpy change in the formation of NO(g) from its elements at 25°C.

N2(g) + O2(g) → 2 NO(g) DH° = +180.50 kJ

To express the enthalpy change in terms of one mole of NO(g), all coefficients and DHº
the value are dived by 2.

½N2(g) + ½O2(g) → NO(g) DH° = +90.25 kJ

• DH changes sign when a process is reversed

NO(g) → ½N2(g) + ½O2(g) DH° = -90.25 kJ

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• Hess’s law of constant heat summation

– If a process occurs in stages or steps, the enthalpy change for the overall process is
the sum of the enthalpy changes for the individual steps.

– Describe the standard enthalpy change for the formation of NO2(g) from N2(g) and O2(g).

½N2(g) + O2(g) → NO2(g) DH° = ?

½N2(g) + ½ O2(g) → NO(g) DH° = +90.25 kJ

NO(g) + ½O2(g) → NO2(g) DH° = -57.07 kJ
½N2(g) + O2(g) → NO2(g) DH° = +33.18 kJ

56
57
58
 7-8 Standard Enthalpies of Formation DHf°

• The enthalpy change that occurs in the formation of one mole of a substance
in the standard state from the reference forms of the elements in their
standard states.

• The reference forms of the elements are their most stable forms at the
given temperature and 1 bar pressure.

The standard enthalpy of formation of a pure element in its reference state is 0.

• The most stable forms of some common elements at 298.15 K (common T

for tabulated values) is:
Na(s) H2(g) N2(g) O2(g) C(graphite) Br2(l)

59
• Carbon can exist as both diamond and graphite, however, there is a measurable
enthalpy difference between the two forms:

C(graphite) → C(diamond) DHo = 1.9 kJ

DHfo C (graphite) = 0

DHfo C (diamond) = 1.9 kJ/mol

Diamond and graphite

60
• Although we can obtain bromine in either the gaseous or liquid state at 298.15 K,
Br2 (l) is the most stable form.

Br2 (l) → Br2 (g) DHf° = 30.91 kJ

DHfo [Br2 (l)] = 0 DHfo [Br2 (g)] = 30.91 kJ/mol

Liquid bromine vaporizing

• The reference form of phosphorus is white phosphorus.

P(s, white) → P(s, red) ∆Ho= -17.6 kJ

DHfo [P(s, white)] = 0 DHfo [P(s, red)] = -17.6 kJ/mol

61
62
 number of carbons

Some standard enthalpies of formation at 298.15 K

63
64
 Standard Enthalpies of Reaction
• If the reactants and products of a reaction are in their standard states, the
enthalpy change is a standard enthalpy change, DHº.

65
∆H° = ∑np∆Hf°(products) - ∑nr∆Hf°(reactants) (7.21)

66
67
68
Ionic Reactions in Solutions

69
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72
 7-9 Fuels as
Sources of Energy

• Fossil fuels
– Combustion is exothermic.
– Non-renewable resource.
– Environmental impact.

73
Global Warming – An Environmental Issue Involving Carbon Dioxide

nuclear

FIGURE 7-22
•World primary energy consumption by energy source

74
The “greenhouse” effect
FIGURE 7-23

75
Global average atmospheric Actual and predicted CO2
carbon dioxide level emissions

76
 Coal and Other Energy Sources
•Gasification of Coal: steam and heated coal
•Liquifaction of Coal: convert coal gas to long chain hydrocarbons
using catalysis
•Methanol: prepared from coal or thermal decomposition of various
organic materials
•Ethanol: mostly from ethylene but also by fermentation
•Biofuels: biodiesel is composed of methyl esters of fatty acids
•Hydrogen: excellent fuel but requires a good production method

77
 7-2 Heat
• Thermal Energy
• Kinetic energy associated with random molecular motion.
• In general, proportional to temperature.
• An intensive property.

• Heat and Work

• q and w.
• Energy changes.

Heat (q): transfer of thermal energy as a result of a temperature difference.

Heat passes from a warmer body (higher T) to a colder body (lower T) until the
average kinetic energies of the two bodies is equal (ie. until they have the
same T).

78
 Internal Energy (U)

• Internal energy (U) is the total energy contained within a

system
• Part of U is kinetic energy (from molecular motion)
• Translational motion, rotational motion, vibrational motion.
• Collectively, these are sometimes called thermal energy

• Part of U is potential energy

• Intermolecular and intramolecular forces of attraction,
locations of atoms and of bonds.
• Collectively these are sometimes called chemical energy

79
 Heat (q)

• Technically speaking, heat is not

“energy.”
• Heat is energy transfer between a
system and its surroundings, caused
by a temperature difference.
• Thermal equilibrium occurs when More energetic … transfer energy to
the system and surroundings reach molecules … less energetic
the same temperature and heat molecules.
transfer stops.
How do the root-mean-square
speeds of the Ar atoms and the N2
molecules compare at the point of
thermal equilibrium?

80
 Work (w)
• Like heat, work is an energy transfer between a system and its
surroundings.
• Unlike heat, work is caused by a force moving through a distance
(heat is caused by a temperature difference).
• A negative quantity of work signifies that the system loses energy.
• A positive quantity of work signifies that the system gains energy.
• There is no such thing as “negative energy” nor “positive energy”; the
sign of work (or heat) signifies the direction of energy flow.

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• Internal energy is transferred between a system and its
surroundings as a result of a temperature difference.

• Heat “flows” from hotter to colder.

• Temperature may change.
• Phase may change (an isothermal process).

82