10/29/20

BKF1253 Physical Chemistry

Chapter 2: First Law of

Thermodynamic

Prof. Madya Dr. Syed Mohd Saufi

Dr SMS

Subtopics
• Introduction of First Law of Thermodynamics
• Form of Energy
• Internal
• Kinetic
• Potential
• Transfer of Energy
• Work
• Heat transfer
• Enthalpy
• Measurement of Heat and Specific Heat
• Thermochemistry

1
 Total energy Total energy Change in the total
fixed mass or closed system are heat transfer and work. a b #" a 0; thus $E " $U.b " a b
∆E = 8 kJ This relation isentering oftenthe system to as
referred leaving the system
the energy balanceenergy andofistheapplicable
system to
1. Heat Transfer, Q Heat transfer to a system (heat gain) increases the any kind of process. The successful use of
Wsh,any = 8 kind
kJ of
or system undergoing
energy of the molecules and thus the in internal energy of the system, and
72 2–41
FIGURE |heat transfer
Thermodynamics
from a system (heatthis loss)relation
decreasestoit solve since the engineering
energy Eproblems depends on understanding the
in # Eout " ¢Esystem

The work (shaft)transferred out as heat

done on an adiabatic
(Adiabatic)
comes from various
the energy
between This forms of
the totalof
the energy
molecules
relation energyis often
and of recognizing
the
entering
referredand to asthe
the
thetotal
forms
energy
of energy
energy
balance leaving transfer.
and isthe 10/29/20
system to
applicable
system. during thatany process.
kind of That
system is, undergoing any kind of process. The successful use of
system is2.equal to the increase in the
energy of the
Work Transfer, W An energy interaction thatthis
system.
FIGURE 2–41
perature difference between a system and itsTotal
Energy Change of a System, !E
is not causedtoby
relation
energy is work. A Total energy
surroundings
a tem-
solve engineering problems depends on understanding the
systemChange in the total
a various forms of b energy
# a and recognizing bthe"forms a of energy transfer.b
rising The work
piston, (shaft) done
a rotating shaft,onand an adiabatic
The
an determination
electrical
entering wirethe crossing
system ofthethe system energy
leaving the change
systemof a system energy ofduring
the system a process
∆E = system
8 kJ
boundaries areis equal
kJall to the increase
associated in theinteractions.
with involves
work the Work transfer
evaluation of to aenergy of the system at the beginning and at
the
Wb,in = 10
systemenergy of thedone
(i.e., work system.
Wsh,onin =a8 system)
or Energy
the energy Change of a System, !Esystem
kJ
theincreases
end ofThe the determination
process, of the system,
and oftaking their difference. That is,
and work transfer from a system (i.e., work done by the system) Einthe# Eenergy change of a system during a process
out " ¢Esystem
cen84959_ch02.qxd 3/31/05 decreases
5:02 PM Page it since
74 theb,in
W energy transferred out Energy
= 10 kJ involves
as workchange the evaluation
comes from " Energy of the energy of
the at final state # Energy at the system at initial
the beginning
state and at
energy contained in the system. CarThis relation
engines the
andend is oftenof the referred
hydraulic, process,
steam, or and the energy
to astaking balanceThat
their difference. andis, is applicable to

sume work.
The First Law of Thermodynamics
gas turbines produce work while compressors, orany kind of
this relation
pumps,
system
to
and
solve
Energy mixers
undergoing
change
engineering
con-" any Energy kind of process.
at final
problems
The atsuccessful
state # Energy
depends on
initial state use of
understanding the
FIGURE 2–41 or ¢Esystem " Efinal # Einitial " E2 # E1 (2–32)
3. Mass Flow, m Mass flow in and out variousof the forms system ofservesenergy as an and addi-recognizing the forms of energy transfer.
The work The
• (shaft)
tional First
done
mechanism
∆E = 10 kJ
law
on of of
anenergy thermodynamics
adiabatic transfer. When mass contributes
Note that energy is a property, enters a system,the law
the of
and"the
¢Esystem conservation
Efinalvalue of
of"aEproperty
# Einitial 2 # E1 does not change (2–32)
74 | Thermodynamics
system is equal
energy oftothe
energy, thesystem
increase
which thein the
increases
energy because cannot mass be carries
created energyor with it (in
destroyed duringTherefore,
a process;the energy change of a
energy of themass
fact, system.
it can
is energy). ∆ELikewise,
Energy
only within
change
= 10balance
kJ
from
when Energy
unless
for some
one any
form
the NoteChange
state
mass leaves
system that of
undergoing
to another.
the
energy of
the system, system
is a
any kind a System,
changes.
property, and !E
the
the of process can system value
be of a property does not change
Mass energy contained
W expressed themore
system system
decreases
The
compactly is unless
as zero
because
determination ifthe thestate
the state
leaving
of of of
the the
mass the
energy system
system change does
changes. of not change
Therefore,
a system during
theduring the
energy achange process.
process of a
in
takes(Adiabatic)
out some
Wb,in = 10 energy
kJ with it. For Also, example,
involves energy
E in # E out
system
when
the "
can is exist
some
evaluation zero
¢E system
hotifin thenumerous
water
of thestate
1kJ2
of theforms
isenergy system
of the such
does as
system
(2–35)
internal
notatchange
the (sensible,
during
beginning theand latent,
process.
at
Control taken out of a water (Adiabatic)heater and is chemical,
replaced by Also,
the
and sameenergy
nuclear),amount can kinetic,
exist
of cold in numerous
potential, forms such asand
electric, internal (sensible,
magnetic, and latent,
their
the end of the process, and taking their difference. That is,












volume
FIGURE 2–42 water, the Q energy content of the by
sum
Net energy
hot-water transfer
constitutes
heat, work, and masschemical,
tank Change
(the the and
control
potential, total
etc., nuclear),
in internal, kinetic,
volume)
energies energy kinetic,
E of potential,
a system. electric,
In theandabsence
magnetic,ofand their
electric,
decreasesFIGUREas a2–42
result of this mass interaction (Fig. sum
Energy constitutes
2–45). change " theEnergy at finalEstate
total energy of a#system.
EnergyIn the absence
at initial state of electric,
The work (boundary) done oninan done onmagnetic, and surface tensiontension effects (i.e.,(i.e.,
for for
simple
simplecompressible sys-
or, the rate form, as
The work
Mass (boundary) an. . magnetic, and surface effects compressible sys-
adiabatic Noting
systemthat energyto can
is out
equal
adiabatic the is
system
be transferred
equal to the Eor
tems), in the theforms
in # E out tems),
change
" dE
of heat,
the in the
>dt
change
system
work,total
in1kW
and2
theenergy of a of
total energy system
a system
(2–36) during
duringa aprocess
process is is the
thesum sum
increasemass,
in theand that the
energy net system.
ofinthe transfer of a quantity is equal to the difference
ofof netthe energychanges inchangeitscan internal, Ekinetic, and"and potential
E1 energies
energies and canbebe















FIGURE 2–45 increase the energy of the Rate system. of the
transfer Rate changes
of in¢E insystem
internal, its " internal,
final #kinetic,
Einitial E2 # potential and (2–32)
can
between the amounts transferred in andby out, theandenergy
heat, work, mass balance
kinetic, be writ-
potential, etc., energies
The energy contentten
of more
a control expressed expressed
as as
explicitly as Note that energy is a property, and the value of a property does not change
volume can be changed by mass∆Eflow= 10 kJ For constant rates, the total quantities during a time interval !t are related to
¢E
as well as heat andEwork
in ! E out " 1Q =Q
in !
Qout
interactions. out 2 #
the
3 kJ 1WQinout!= W
quantities 3 kJ 2 # 1E
per unless
out unit time the
as
mass,in ! Estate
mass,out 2of
" the ¢E
system
¢E system (2–34) ¢U"$¢U
"changes. $ ¢KE
¢KE $ ¢PE
$ ¢PE
Therefore, the energy change of(2–33)
a
(2–33)
# system # where if the state of the system does not change during the process.
" Q ¢t,
where the subscripts “in” and Q“out” W"
where
denote Wis¢t,zero
quantities and ¢E " and
that enter 1dE>dt2 ¢t
leave 1kJ 2 (2–37)
the system, respectively. All six quantities on the right can
(Adiabatic) Also, energy side exist
of the in numerous¢U
equation forms such
" m 1u
The energy balance can be expressed on a per unit mass basis as
∆E = (15 – 3) + 6
as internal (sensible, latent,
2 # u1 2
represent chemical, and nuclear), kinetic, ¢Upotential,
" m 1u2 1#electric,u1 2 and magnetic, and their
∆E
FIGURE (15 – “amounts,”
= 2–42 3) + 6 = and
18 kJ thus they are positive
ein #
quantities.
eout " ¢esystem
The direction
1kJ>kg 2
of ¢KE " 2 m(2–38) 1V 22 # V 12 2
any=energy
18 kJ transfer is described by the subscriptssum constitutes
“in” and “out.”the total energy E of 1 a system.
2 2 In the absence of electric,
¢KE " 2 m"1V 2 # V#1 z21simple
P The workThe heat transfer done
(boundary) is on
Qwhich zero for W bymagnetic,
adiabatic
isanobtained systems,
dividing
sh, in = 6 kJ
all and surface
the quantities
the work intension
transfer Eq.W2–35 by¢PE
is effectsthe mass mg
(i.e., m1z2offor 2 compressible sys-
zero for
adiabatic systems
system that the
is equal involve
the no Energy
tosystem. work interactions,
balance
tems), can and
also
theWhen
changethe
betheenergy
expressedthetransport
ininitial in
total
and the differential
energy
¢PE
final " of
mg
states aform
1z system
are # as
z 2
specified, during thea values
processofisthethespecific
sum
= 6 systems
Wsh, in for kJ 2 1
with mass
increase mass is zero
in theEenergy of the system. dEthat #ofinvolve
dE the " no
changes
dE massorin
internal flow its
energies
de across
#internal,
deu their
and
" de kinetic,
u can beand potential
determined
(2–39) energies
directly from andthecan be
property
in out system in out system
boundaries (i.e., closed systems). When
expressed thetables
initial
as or and final1 states
thermodynamic
2
are specified,
property relations. the values of the specific
= 15akJ
QinFor closed system undergoing a cycle, the initial and final states are iden-
Qnet = Wnet internal energies Most systemsu1 andencounteredu2 can beindetermined
practice directly from
are stationary, that is,the
theyproperty
do not
3 kJ and thus !Esystem " E2 # E1 " 0. Then the energy
Qout =tical, ¢E " balance
¢U $ ¢KE for a cycle
$ ¢PE (2–33)
Qin = 15 kJFIGURE 2–43 simplifies to Ein #tables Eout " or 0 orthermodynamic
involve
Ein " Eout any changes
. Noting property
thatin theirrelations.
a closed velocity
system does or elevation during a process (Fig.
3 The energy not involve
change of a any
systemmass where
Most
flow across
during 2–44).
systems its Thus,
encountered
boundaries, for stationary systems,
in practice
the energy balance are fortheastationary,
changes in that
kineticis,and potential
they do not
energies are workzero (that is, !KE as1u" # !PE " 0), andduring the totala energy change
FIGURE 2–43 a process iscycle equalcan be net
to the expressed
involve
work in terms
and any ofchanges
#
heat and in interactions
their ¢U velocity
# 2–33 reduces to !E2 " !U
" m or u elevation
1 2 process (Fig.
∆E = (15 V– 3)transfer
heat +6 between the system relation in Eq. for such systems. Also, the energy
Wnet,out " Qand
2–44).net,in Thus, for
or Wnet,out "stationary
Q net,in 1forsystems,
a cycle1 2 the changes
(2–40) in kinetic and potential
The energy change = 18its of a system during
kJsurroundings. ¢KE " 2 m 1V 2 # V 1 22 2
FIGURE 2–46
a process is equal to the netThat
work energies
andnet work
is, the are zero
output during (that
a cycle is, !KE
is equal to net" !PE
heat input" 0), and the total energy change
(Fig.
For a cycle
heat " 0, thusbetween
!Etransfer Q " W. the system
2–46).
W = and
6 kJ relation in Eq. 2–33 reduces¢PE
sh, in
to !E " 1z
" mg !U z1 2 such systems. Also, the energy
2 #for

its surroundings. When the initial and final states are specified, the values of the specific
internal
Coolingenergies
EXAMPLE 2–10 u1 and
of a Hot Fluid 2 can be determined directly from the property
in auTank
Qin = 15 kJ tables or thermodynamic property
A rigid tank contains a hot fluid that is cooled while being stirredrelations.
by a pad-
Most
dle wheel. Initially, the systems
internal energy encountered in practice
of the fluid is 800 kJ. Duringarethestationary, that is, they do not
FIGURE 2–43 cooling process, theinvolve any500changes
fluid loses kJ of heat,inand
their
the velocity
paddle wheelor does
elevation during a process (Fig.
100 kJ of work on the fluid. Determine the final internal energy of the fluid.
The
Qoutenergy
= 500 kJ change of a system 2–44). Thus, for stationary systems, the changes in kinetic and potential
Neglectduring
the energy stored in the paddle wheel.
a process is equal to the net work and energies are zero (that is, !KE " !PE " 0), and the total energy change
Solution and
heat transfer between the system relation
A fluid in in Eq.
a rigid tank 2–33
looses heatreduces to !E
while being " !U
stirred. The for
finalsuch systems. Also, the energy
U1 = 800its
kJ surroundings. internal energy of the fluid is to be determined.
Assumptions 1 The tank is stationary and thus the kinetic and potential
U2 = ?
energy changes are zero, !KE " !PE " 0. Therefore, !E " !U and internal
Wsh, in = 100 kJ energy is the only form of the system’s energy that may change during this
process. 2 Energy stored in the paddle wheel is negligible.
Fluid Analysis Take the contents of the tank as the system (Fig. 2–47). This is a
closed system since no mass crosses the boundary during the process. We

FIGURE 2–47 Form of Energy

observe that the volume of a rigid tank is constant, and thus there is no
moving boundary work. Also, heat is lost from the system and shaft work is
Schematic for Example 2–10. done on the system. Applying the energy balance on the system gives

Dr SMS

2
 10/29/20

Form of Energy
• In thermodynamics analysis, forms of energy can be divided
into two groups; macroscopic and microscopic energy.
• Microscopic energy
– The microscopic forms of energy are those related to the molecular
structure of a system and the molecular activity
– The sum of all the microscopic forms of energy is called the internal
energy of a system and is denoted by U.
• Macroscopic energy
– The macroscopic energy of a system is related to motion and the
influence of some external effects such as gravity, magnetism,
electricity and surface tension
– Magnetism, electricity and surface tension are usually ignored.
– We normally consider the kinetic energy and potential energy

Kinetic Energy
• Energy due to the translational motion of the system as a
whole relative to some frame of reference (usually the earth’s
surface) or to rotation of the system about some axis.
• Kinetic energy, △KE (J) of an object of mass m (kg) moving
with velocity u (m/s) relative to the surface of the earth is
1
𝐾𝐸 = 𝑚𝑢!
2

Dr SMS

3
 10/29/20

Potential Energy
• Energy due to the position of the system in a potential field
(such as a gravitational or electromagnetic field).

𝑃𝐸 = 𝑚𝑔𝑧
• Normally we are interested in the change of potential energy
during energy balance calculation
∆𝑃𝐸 = 𝑚𝑔(𝑧! − 𝑧")

Dr SMS

Kinetic and Potential Energy

https://www.youtube.com/watch?v=g7u6pIfUVy4
Dr SMS

4
 10/29/20

cen84959_ch02.qxd 3/31/05 5:02 PM Page 55

Internal Energy
Chapter 2 | 55
• Energy
Some due to to
Physical Insight translation,
Internal Energy rotation, vibration &
Internalelectromagnetic interactions of the molecules, atom and
4959_ch02.qxd 3/31/05 5:02 PM Page 55
energy is defined earlier as the sum of all the microscopic forms of
energy of a system. It is related to the molecular structure and the degree of
molecularsubatomic
activity and canparticle
be viewed aswithin
the sum of the system.
the kinetic and potential
energies of the molecules. Molecular Molecular
The
• have
To average
a better understandingvelocity and
of internal energy, let usthe
examinedegree
a system of translation
activity of the
rotation

at the molecular level. The molecules of a gas moveChapter through2 space | with 55
molecules
some velocity, are proportional
and thus possess some kinetic energy. This to istheknown temperature.
as the –Therefore, at
55
Some Physical Insight to Internal Energy
translational energy. The atoms of polyatomic molecules rotate about an
Internal energy is defined earlier as theaxis,
sum and
higher
thetheenergy
of all
temperatures,
associated
microscopic formswith the molecules
of this rotation is the rotational kinetic
possess +
higher kinetic
molecular activity and can be viewed as common energies,
energy. The
energy of a system. It is related to the molecular atoms of
structure
the sumcenter
and
of theofkinetic
and
a the
mass,and the as
polyatomic
degree of
andpotential
energya associated
resultwiththe system has aElectron
molecule may also vibrate about their
this back-and-forth higher internal
Molecular
energies of the molecules. motion energy.
is the vibrational kinetic energy. ForMolecular
gases, the kinetic energy is
Molecular
translation vibration
mostly due to translational and rotational motions,
To have a better understanding of internal energy, letChapter with vibrational
translation
us examine rotationmotion
2 a |system 55
at the molecular level. The moleculesbecoming of a gas significant
move through at higher
spacetemperatures.
with The electrons in an atom rotate
t to Internal
some velocity, Energy and thus possess some about kineticthe nucleus,
energy. Thisand thus possess
is known as the rotational kinetic energy. Electrons at
– also spin about their
– +
The atoms outer orbits have larger kinetic energies. Electrons
er as thetranslational
sum of all the energy.
microscopic formsofofpolyatomic molecules rotate about an +
axis, and the energyand associated with axes, and the energy associated with this motion is the spin energy. Other
d to the molecular structure the degree of this rotation is the rotational kinetic
The particles in the nucleus of an atom also possess spin energy. The portion of
viewed as energy.
the sum of atoms of a and
the kinetic polyatomic
potentialmolecule may also vibrate about their
common center of mass, and the energy theassociated
internal
Molecular
energy
with this of back-and-forth
a Molecular
system associated with the kinetic energies
Electron Molecularof the Electron Nuclear
motionenergy, is theletvibrational molecules is called
Fortranslation
gases, the the sensible
kinetic rotation
energyenergyis (Fig. 2–5). The average vibration
translation velocity and
ng of internal us examinekinetica system energy. spin spin
the degree of with
activity of the molecules
motion are proportional to the temperature of
oleculesmostly
of a gas duemoveto translational
through space and rotational
with motions, vibrational
the gas. TheTherefore, at anhigher
atom temperatures, the molecules possess higher FIGURE 2–5
ss some becoming
kinetic energy. significant
This is at known
higher temperatures.
as the electrons in
–
rotate
about the nucleus, kinetic energies, and as a Electrons
result the at system has a higher internal energy.
ms of polyatomic moleculesand thus about
rotate possess an rotational kinetic+
energy. – + The various forms of microscopic
outerrotation
orbits have TheElectrons
internal energy is also associated
their with various binding forces between energies that make up sensible energy.
d with this is thelarger kinetic
rotational energies.
kinetic also spin about
axes, and the energy associated with the molecules
this motion is of aspin
the substance,
energy. between the atoms within a molecule, and
Other
omic molecule may also vibrate about their
he energy particles
associated in the nucleus
with of an atom alsobetween
this back-and-forth
the
possessElectron
spinparticles
energy.within
The an atomofand its nucleus. The forces that bind the
portion
Molecular
the internal energy molecules to each other are, asofone the would expect, strongest in solids and
the of a system associated with the kinetic energies
9 weakest
tic energy. For gases, kinetic energy is translation vibration
molecules is called the sensiblemotionenergy (Fig. 2–5).in gases. If sufficient
The average energy
velocity and is added Electron
to the molecules of a solid or
Nuclear
d rotational motions, with vibrational spin spin
the degree of activityinofanthe molecules liquid, the molecules overcome these molecular forces and break away, turn-
temperatures. The electrons atom rotate are proportional to the temperature of
the gas. Therefore, at higher temperatures,ing the thesubstance
molecules into apossess
gas. This is a phase-change process. Because of this
higher
ossess rotational kinetic energy. Electrons at – + FIGURE 2–5 Sensible
kinetic energies,also and spin
as a result addedhas energy, a system
internalinenergy.
the gas phase is at a higher internal energy level
ic energies. Electrons about the theirsystem a higher and latent
than it is in the solid or the liquid phase.The Thevarious
internalforms of microscopic
energy associated with energy
d with thisThe internal
motion energy
is the spinisenergy.
also associated
Other with various binding forces between energies that make up sensible energy.
the phase of a system is called the latent energy. The phase-change process
tom alsothepossess
molecules of a substance,
spin energy. The portion between
of the atoms within a molecule, and
between can occur without a change in the chemical composition of a system. Most
m associated withthetheparticles
kineticwithin
energiesan atom
of theand its nucleus. The forces that bind the
practicalElectron
problems fall into this category,
inNuclear and one does not need to pay any
(Fig. 2–5).toThe
e energymolecules each other velocity
average are, as one and would expect, strongest solids and
attention to spinthe forces binding spin the atoms in a molecule to each other. Chemical
lecules weakest in gases.toIfthe
are proportional sufficient energy
temperature of is added to the molecules of a solid or
Internal Energy
An atom consists of neutrons and positively charged protons bound energy
liquid, the molecules
temperatures, moleculesovercome these molecular
possess higher FIGURE 2–5 forces and break away, turn-
ing the together by process.
very strong nuclear forces in the nucleus, and negatively
t the system hassubstance into a gas.
a higher internal This is a phase-change
energy. The various formsorbiting
Because
of microscopic
of this Sensible with the
charged
is at aelectrons aroundlevelit. The internal energy associated
ssociatedadded energy, binding
with various a systemforcesin thebetween
gas phase
energies
higher internal
that make up
energy
sensible energy. and latent
than atomic bonds in a molecule is called chemical energy. During
energya chemical
between theit atoms
is in the solid aormolecule,
within the liquid and phase. The internal energy associated with
theitsphase of aThesystem is called thethe reaction, such as a combustion
latent energy. The phase-change process process, some chemical bonds are destroyed Nuclear
atom and nucleus. forces that bind energy
can occur without a change in theand while composition
chemical others are formed. of a system. As aMost result, the internal energy changes. The
s one would expect, strongest in solids
nuclear forces arenotmuch
needlarger thananythe forces that bind the electrons to the
energy ispractical
added toproblems fall into
the molecules of this
a solidcategory,
or and one does to pay
attention to the forces binding theturn-
atoms nucleus. The tremendous
in a molecule amount of energy associated with the
to each other. strong bonds
these molecular forces and break away, Chemical
An atom consists of neutrons andwithin the nucleus
positively chargedof protons
the atombound itself is called nuclear energy energy(Fig. 2–6).
his is a phase-change process. Because of this FIGURE 2–6
together Obviously,
in the we need not be negatively
Sensible concerned with nuclear energy in thermodynam-
gas phase is at a by veryinternal
higher strongenergynuclear levelforces nucleus, and
and latent
charged electrons orbiting aroundwith it. Theicsinternal
unless, energy
of course, we deal with fusion or fission reactions. A chemical
associated
energy with the
The internal energy of a system is the
uid phase. The internal energy associated
atomic bonds reaction involves
called chemical energy.changesDuring ain chemical
the structure of the electrons of the atoms, but sum of all forms of the microscopic
the latent energy. Theinphase-change
a molecule isprocess
reaction, such as a of combustion a nuclear reaction involves changes in the core or nucleus.Nuclear Therefore, an energies.
the chemical composition a system. process,
Most some chemical bonds are destroyed
while energy
s category, andothers
one does are not
formed.
need to Aspay a result,
any the internal energy changes. The
he atoms nuclear forces are
in a molecule to much larger than the forces that bind the electrons
each other. Chemical to the
ons andnucleus.
positively The charged
tremendous amount
protons boundof energy associated with the strong bonds
energy
within
lear forces in thethe nucleus
nucleus,of and the atom itself is called nuclear energy (Fig. 2–6).
negatively
Obviously,
nd it. The we need
internal energy with the with nuclear energy in thermodynam- FIGURE 2–6
not be concerned
associated
ics unless,energy.
called chemical of course,Duringwe deal with fusion or fission reactions. A chemical The internal energy of a system is the
a chemical
process,reaction involves bonds
some chemical changes areindestroyed
the structure of the electrons ofNuclear the atoms, but sum of all forms of the microscopic
a nuclear
a result, the internal reaction
energyinvolves changes
changes. The in the core or nucleus.energy Therefore, an energies.
than the forces that bind the electrons to the
nt of energy associated with the strong bonds
m itself is called nuclear energy (Fig. 2–6).
cerned with nuclear energy in thermodynam- FIGURE 2–6
with fusion or fission reactions. A chemical The internal energy of a system is the
e structure of the electrons of the atoms, but sum of all forms of the microscopic
anges in the core or nucleus. Therefore, an energies.
https://www.youtube.com/watch?v=aDXQBE4r65Y

Dr SMS

10

5
 10/29/20

Transfer of Energy

Dr SMS

11

Transfer of Energy

heat work

Closed
system
3 forms energy
transfer
of energy
transfer
mass
flow work heat
energy

Dr SMS

12

6
cen84959_ch02.qxd 4/25/05 2:32 PM Page 60

10/29/20
60 | Thermodynamics

INTERACTIVE
2–3 ■
ENERGY TRANSFER BY HEAT
TUTORIAL Energy can cross the boundary of a closed system in two distinct forms:
SEE TUTORIAL CH. 2, SEC. 3 ON THE DVD. heat and work (Fig. 2–11). It is important to distinguish between these two
forms of energy. Therefore, they will be discussed first, to form a sound
basis for the development of the laws of thermodynamics.
We know from experience that a can of cold soda left on a table eventu-
ally warms up and that a hot baked potato on the same table cools down.
When a body is left in a medium that is at a different temperature, energy
System boundary
transfer takes place between the body and the surrounding medium until

Heat Transfer Heat

thermal equilibrium is established, that is, the body and the medium reach
the same temperature. The direction of energy transfer is always from the
higher temperature body to the lower temperature one. Once the tempera-
CLOSED
SYSTEM Work ture equality is established, energy transfer stops. In the processes described
• Energy that flows as a result of temperature difference between a system
(m = constant)
above, energy is said to be transferred in the form of heat.
Heat is defined as the form of energy that is transferred between two
and its surroundings. systems (or a system and its surroundings) by virtue of a temperature
difference (Fig. 2–12). That is, an energy interaction is heat only if it
• The direction of flow is always from a higher temperature to a low one.
FIGURE 2–11 takes place because of a temperature difference. Then it follows that there
cannot be any heat transfer between two systems that are at the same
Energy can cross the boundaries of a
temperature.
• No heat transfer between two systems that are at the same temperature.
closed system in the form of heat and
work. Several phrases in common use today—such as heat flow, heat addition,
heat rejection, heat absorption, heat removal, heat gain, heat loss, heat
• Heat is defined as positive when its enters/transfers to the system from
storage, heat generation, electrical heating, resistance heating, frictional
heating, gas heating, heat of reaction, liberation of heat, specific heat, sensi-
the surroundings. ble heat, latent heat, THE waste heat, body heat, process heat, heat sink, and heat
CONSERVATION OF ENERGY 45
source—are not consistent with the strict thermodynamic meaning of the
Room air term heat, which limits its use to the transfer of thermal energy during a
25°C
process. However, these w < 0 phrases are q < 0 deeply rooted in our vocabulary, and
No heat Heat Heat
transfer 8 J/s 16 J/s they are used by both ordinary people and scientists without causing any
misunderstanding since Work they are Heat
usually interpreted properly instead of
being taken literally. (Besides, no acceptable alternatives exist for some of
these phrases.) For example, the phrase body heat is understood to mean
Energy
the thermal energy content of a body. Likewise, heat flow is understood
Surroundings to mean the transfer wof > 0thermal energy, q > 0 not the flow of a fluidlike substance
25°C 15°C 5°C called heat, although the latter incorrect interpretation, which is based on
Work Heat
the caloric theory, is the origin of this phrase. Also, the transfer of heat
Energy as heat
into a system is frequently referred to as heat addition and the transfer of
heat out of a system as heat rejection. Perhaps there are thermodynamic rea-
sons Fig.
for2.8
being soconvention
The sign reluctant to replace heat
in thermodynamics: by thermal energy: It takes less
w and q
FIGURE 2–12
time are
and energy
positive toenters
if energy say,the write,
system and comprehend
(as work and heat, heat than it does thermal
Temperature difference is the driving energy.
respectively), but negative if energy leaves the system.
force for heat transfer. The larger the Heat is energy in transition. It is recognized only as it crosses the bound-
System
temperature difference, the higher is ary of a system. Consider the hot baked potato one more time. The potato
the rate of heat transfer. contains energy, but this energy is heat transfer only as it passes through
Fig. 2.7 Heat is the transfer of energy that causes or utilizes
THE
theCONSERVATION
skin of OF theENERGY
potato43 (the system boundary) to reach the air, as shown in
chaotic motion in the surroundings. When energy leaves the Fig. 2–13. Once in the surroundings, the transferred heat becomes part of
system (the green region), it generates chaotic motion the in internal energy of the surroundings. Thus, in thermodynamics, the term
the surroundings (shown magnified). When ameans
heat simply system does
heatwork, such as by raising a
transfer.
13 Closed
weight in the surroundings or forcing an electric
current through a circuit, the energy transferred, w,
is reported as a negative quantity. For instance, if
Energy

energy when a fire burns Openis a relatively unsophisticated

procedure because the energy emerges in a Low disordered a system
High raises a weight in the surroundings and in
fashion from the burning fuel. It was developed— temperature thetemperature
process does 100 J of work (that is, 100 J of
stumbled upon— early in the history of civilization. The energy leaves the system by doing work), then we
generation of work by a burning fuel, in contrast, relies write w = −100 J. When work is done on the sys-
on a carefully controlled transfer of energy so that vast
Isolated (a) (b) tem—for example, when we wind a spring inside a
numbers of molecules move in unison. Apart from
Fig. 2.2 A systemNature’s
is open if achievement
it can exchange energyof work
and mat-through theThe
Fig. 2.3 evolution
temperature
clockwork
ofis a parameter mechanism—w is reported as a positive
that indicates the
muscles,
ter with its surroundings, theiflarge-scale
closed it can exchangetransfer
energy butof energy
extent toby doing
which work
the exponentially quantity.
decaying Boltzmann write w = +100 J to signify that 100 J
We distri-

Heat transfer
not matter, andwasisolated if it can exchange neither energy nor later bution reaches up into the higher energy levels of a system.
achieved thousands of years than the transfer ofonly
work has been
matter. (a) When the temperature is low, the lower energy done on the system (that is, 100 J
of energy by heating, as it had to await the
states aredevelopment
occupied (as indicated of energy had been transferred to the system by doing
by the green rectangles).
of the steam engine. (b) At higher temperatures, more higher states are occupied.
In each case, the populations decay work). The sign
exponentially withconvention is easy to follow if we
2.2 Work and heat increasing temperature, with the think
total of changes
population of all levels to the energy of the system: its
• exothermic
Energy can be exchanged between a closed system
vs. endothermic a constant.
energy decreases (w is negative) if energy leaves it
2.3 The measurement of work
– A process in a system that
and its surroundings by doing work or by the process
called ‘heating’. A system does work when it causes
releases energyand as heat
its energy
depend on the temperature: at low temperatures, most
is called exothermic.
increases (w is positive) if energy
We saw in Section 0.3 that the force molecules opposing the energy
are in the lowest enters
states;itas(Fig. 2.8).
the temper-
motion against an
when a system
–
raising A
opposing
does work
process
of a by
force. We
mass noting
in a
can system
identify
vertically
m whether that
the on energy,
absorbs
the surface of the
ature is raised, more energy
molecules as heat is called endothermic.
We use the same convention for energy transferred
occupy states of higher
so the population spreads into these upper states
as heat, We write q = −100 J if 100 J of energy
somewhere • inEarth
process can be used toischange
diathermic
the
mg, where
−2
surroundings. vs.
the heightg of
Heating
isa the
adiabatic
is
(9.81 m s ). Therefore, the work done to raise the
acceleration
weight
the this spread
of free fall
(Fig. 2.3). Temperature
of
is the parameter
populations.
that q.
summarizes
leaves the system as heat, so reducing the energy of
process of transferring energy as a result of a tem-
–
mass through
perature difference
Walls
between a
that
theheight
permit is its
systemh and
heating Wallsas a
that mode
permit of
heatingtransfer
as a mode of
the system, and of
of energy
transfer q =are
+100called diathermic.
J if 100 J of energy enters
energy are called diathermic (Fig. the 2.4).
system A metal con-
as heat.
surroundings. To– avoidWalls that
a lot of awkward do not
circumlocu- permit heating even though there is a difference in temperature are
Work = mgh tainer is diathermic.(2.1)
Walls that do not permit heating
tion, it is common to say that ‘energy is transferred Because
even though there is a difference in temperature are many chemical reactions produce gas,
as work’ when the system
It follows called doesadiabatic.
that work, and ‘energy
we have a simple way of measuring one very important type of work in chemistry is
is transferred as heat’ when the system heats or
is heated by the work done
its surroundings. by or we
However, onshould
a system: we measure the expansion work, the work done when a system
always remember height thatthrough
‘work’ andwhich a modes
‘heat’ are weight of is raised or lowered in expands against an opposing pressure. The action of
(a) Diathermic
transfer of energy, not forms of energy.
the surroundings and then use eqn 2.1. Cold acid on zinc illustrated in Fig. 2.5 is an example
Although in everyday language the terms ‘temper-
ature’ and ‘heat’ are sometimes not distinguished, of a reaction in which expansion work is done in
A briefentities:
they are entirely different illustration To raise a book like this one (of the process of making room for the gaseous product,
mass about 1.0 kg) from the floor to the table 75 cm
Heat, q, is energy in transit as a result of a temper- hydrogen
Hot in this case. We show in Derivation 2.1
ature difference. above requires that when a system expands through a volume ∆V
Temperature, T, Work is an = intensive Cold against a constant external pressure pex the work
(1.0 kg)property
× (9.81 m that
s−2is) × (0.75 m)
used to define the state of a system and determines done is
= 7.4 kg m2 s−2 = 7.4 J
the direction in which energy flows as heat.
(We
Later in the saw
text in Section
we shall discuss 0.4 that 1 J =
the molecular 1 kg m2 s−2 .) w = −pex ∆V
Hot (2.2)
interpretation of temperature. At this stage, all (b) Adiabatic
we need to appreciate is that the temperature is
the single parameter that tells us the relative
populations of the available energy levels in a system.
We need to recall from introductory chemistry courses
that molecules can possess only certain energies (the Fig. 2.4 (a) A diathermic wall permits the passage of energy
energy is ‘quantized’). At any given temperature, the num- as heat; (b) an adiabatic wall does not, even if there is a tem-
bers of molecules that occupy the available energy levels perature difference across the wall.

14

7
 10/29/20

Work
Work is the energy transfer associated with a44
CHAPTER 2: THERMODYNAMICS: THE FIRST LAW
•
force acting through a distance
• Or work is performed when the object moves
some distance z due to the application of a
force, F
• An energy interaction that is not caused by a
temperature difference between a system and Surroundings

its surroundings is work. Energy as work

• Process associated with work interactions: A
rising piston, a rotating shaft, and an electrical
wire crossing the system boundaries .
• produce work: Car engines and hydraulic, Fig. 2.5 When hydrochloric acid reacts with zinc, the hydro-
System

steam, or gas turbines gen gas produced must push back the surrounding atmo-
Fig. 2.6 Work is transfer of energy that causes or utiliz
sphere (represented by the weight resting on the piston), and
• consume work: compressors, pumps, and hence must do work on its surroundings. This is an example uniform motion of atoms in the surroundings. For examp

mixers.
• Because many chemical reactions produce gas,
one very important type of work in chemistry
is expansion work, the work done when a
system expands against an opposing pressure.
Dr SMS
of energy leaving a system as work.
called adiabatic (from the Greek words for ‘not pass-
ing through’). The double walls of a vacuum flask are
adiabatic to a good approximation.
As an example of the different ways of transferring
energy, consider a chemical reaction that produces
gases, such as the reaction of an acid with zinc:
Zn(s) + 2 HCl(aq) → ZnCl2(aq) + H2(g)
when a weight is raised, all the atoms of the weight (show
magnified) move in unison in the same direction.
much less common. The endothermic dissolution
ammonium nitrate in water is the basis of the insta
cold-packs that are included in some first-aid ki
They consist of a plastic envelope containing wat
dyed blue (for psychological reasons) and a sm
tube of ammonium nitrate, which is broken when t
pack is to be used.

15 Suppose first that the reaction takes place inside a
cylinder fitted with a piston, then the gas produced
drives out the piston and raises a weight in the sur-
roundings (Fig. 2.5). In this case, energy has mig-
rated to the surroundings as a result of the system
doing work because a weight has been raised in the
surroundings: that weight can now do more work, so
it possesses more energy. Some energy also migrates
into the surroundings as heat. We can detect that
transfer of energy by immersing the reaction vessel
The clue to the molecular nature of work com
from thinking about the motion of a weight
terms of its component atoms. When a weigh
raised, all its atoms move in the same directio
This observation suggests that work is the mode of tran
fer of energy that achieves or utilizes uniform motion
the surroundings (Fig. 2.6). Whenever we think of wo
we can always think of it in terms of uniform motion
some kind. Electrical work, for instance, corresponds
electrons being pushed in the same direction through
circuit. Mechanical work corresponds to atoms bei
pushed in the same direction against an opposing forc

Sign Convention of Work

in an ice bath and noting how much ice melts.
Alternatively, we could let the same reaction take
place in a vessel with a piston locked in position. No
work is done, because no weight is raised. However,
• -ve work (-W) because it is found that more ice melts than in the
P first experiment, we can conclude that more energy energy
ex has migrated to the surroundings as heat. THE CONSERVATION
– Work is done by a system are A process in a system that releases energy as heat is
Now consider the molecular nature of heat. When e
ergy is transferred as heat to the surroundings, the atom
and molecules oscillate more vigorously around th
positions or move more rapidly from place to place. T
key point is that the motion stimulated by the arrival
from the system as heat is disorderly, not unifo
as in the case of doing work. This observation sugge
OF ENERGY 45energy that achiev
that heat is the mode of transfer of
or utilizes disorderly motion in the surroundings (Fig. 2.

negative called exothermic. A process in a system that absorbs A fuel burning, for example, generates disorderly molec
w < 0 lar motion in its
q <vicinity.
0
energyzas heat is called endothermic. An example An interesting historical point is that the molecu
– energy leaves the system by of an exothermic reaction is any combustion Work
of Heat work and heat correlates with t
difference between
an organic compound. Endothermic reactions are
doing work (i.e. energy of Energy
chronological order of their application. The release

system decrease) Surroundings w>0 q>0

Work Heat
Energy as heat THE CONSERVATION OF ENERGY 45

Fig. 2.8 The sign convention in thermodynamics: w and q

w <0 q<0
are positive if energy enters the system (as work and heat,
respectively), but negative
Workif energy leaves the system.
• +ve work (W) System
Heat

– Work is done on a system are Energy

Fig. 2.7Surroundings
Heat is the transfer of energy that causes or utilizes w>0
positive chaotic motion in the surroundings. When energy leaves the
q>0
system (the green region), it generates chaotic motion in Work Heat
– energy is transferred/entered to(shown
the surroundings Energy as heat
magnified). When a system does work, such as by raising a
z weight in the surroundings or forcing an electric
the system by doing work (i.e. current through a circuit, the energy transferred, w,
Fig. 2.8 The sign convention in thermodynamics: w and q
energy of system increase)
energy when a fire burns is a relatively unsophisticated
isarereported
positive ifasenergy
a negative quantity.
enters the system For instance,
(as work if
and heat,
procedure because the energy emerges in a disordered arespectively),
system raises butanegative
weightifin the surroundings
energy and in
leaves the system.
fashionSystem
from the burning fuel. It was developed— the process does 100 J of work (that is, 100 J of
stumbled upon— early in the history of civilization. The energy leaves the system by doing work), then we
Dr SMS
generation of work by a burning fuel, in contrast, relies write w = −100 J. When work is done on the sys-
Fig.
on a 2.7 Heat iscontrolled
carefully the transfer of energy
transfer that causes
of energy or utilizes
so that vast
chaotic motion in
numbers of molecules the surroundings.
move in When energy
unison. leaves
Apart fromthe tem—for example, when we wind a spring inside a
16 system (the
Nature’s green region),
achievement
the surroundings
muscles,
it generates
of work
(showntransfer
the large-scale
chaotic
through the
magnified).
motionofin
evolution
of energy by doing work
clockwork mechanism—w is reported as a positive
When a system does work, such as by raising a
quantity. We write w = +100 J to signify that 100 J
was achieved thousands of years later than the transfer weight in the surroundings or forcing an electric
of work has been done on the system (that is, 100 J
of energy by heating, as it had to await the development current through a circuit, the energy transferred, w,
of energy had been transferred to the system by doing
of the steam engine. is reported as a negative quantity. For instance, if
energy when a fire burns is a relatively unsophisticated work). The sign convention is easy to follow if we
procedure because the energy emerges in a disordered a system raises a weight in the surroundings and in
think of changes to the energy of the system: its
fashion from the burning fuel. It was developed— the process does 100 J of work (that is, 100 J of
energy decreases (w is negative) if energy leaves it
2.3 The measurement
stumbled upon— early in theofhistory
workof civilization. The energy leaves the system by doing work), then we
generation of work by a burning fuel, in contrast, relies and its energy increases (w is positive) if energy
We
on asaw in Section
carefully 0.3 that
controlled the of
transfer force opposing
energy so that the
vast
write w = −100 J. When work is done on the sys-
enters it (Fig. 2.8).
tem—for example, when we wind a spring inside a
8
raising
numbers of aof mass m vertically
molecules move on the surface
in unison. Apartof from
the We use the same convention for energy transferred
clockwork mechanism—w is reported as a positive
Earth is mg, where g is the acceleration of free fallof
Nature’s achievement of work through the evolution as heat, q. We write q = −100 J if 100 J of energy
muscles, the large-scale transfer of energy by doing work quantity. We write w = +100 J to signify that 100 J
(9.81 m s−2). Therefore, the work done to raise the leaves the system as heat, so reducing the energy of
was achieved thousands of years later than the transfer of work has been done on the system (that is, 100 J
mass through
of energy a heightashitishad to await the development
by heating, the system, and q = +100 J if 100 J of energy enters
of energy had been transferred to the system by doing
of the steam engine. the system as heat.
Work = mgh (2.1) work). The sign convention is easy to follow if we

Expansion Work
• When a system expands through a volumeTo ΔV
calculate
external pressure pex, the work done is from an initial volume V to a final volume V , a change
𝑊 = −𝑝#$ ℎ𝐴 = −𝑝#$ ∆𝑉
• The external pressure determines how
much work a system does when it
expands through a given volume: the
greater the external pressure, the greater
the opposing force and the greater the
work that a system does.
• When the external pressure is zero, w = 0.
In this case, the system does no work as it
expands because it has nothing to push
against.
• Expansion against zero external pressure Fig.
is called free expansion.
17
Expansion Work
• A system does maximum expansion work when
equal to that of the system at every stage of the(when
• A system does maximum expansion work DV
equilibrium with its surroundings at every stageA of the
• Maximum expansion work is achieved in a reversible
Condition Equation
Expansion at constant pressure
Reversible expansion: P = Pex
Isothermal and reversible
expansion for ideal gas (PV=nRT)
18
10/29/20
46 CHAPTER 2: THERMODYNAMICS: THE FIRST LAW
Derivation 2.1
According to eqn 2.2, the extern
mines how much work a syste
Expansion work expands through a given volume
against
a constant
the work done when a system expands external pressure, the greater the o
i f the greater the work that a system
DV = Vf − Vi, we consider a piston of area A moving out external pressure is zero, w = 0. In
through a distance h (Fig. 2.9). There need not be an tem does no work as it expands be
actual piston: we can think of the piston as representing
the boundary between the expanding gas and the sur-
ing to push against. Expansion aga
pressure is called free expansion.
rounding atmosphere. However, there may be an actual
piston, such as when the expansion takes place inside
an internal combustion engine.
Self-test 2.1
Calculate the work done by a system
External results in the formation of 1.0 mol C
pressure, p ex
100 kPa. Hint. The increase in volum
h
under these conditions if the gas is
use the relations 1 dm3 = 10−3 m3 and
Area, A ∆V
Pressure, p
Equation 2.2 shows us how to g
sion work from a system: we just r
pressure to zero. But how can we a
work for a given change in volu
2.9 When a piston of area A moves out through
a distance h, it sweeps out a volume DV = Ah. The eqn 2.2, the system does maximu
external pressure p opposes the expansion with a
ex
external pressure has its maximum
force pexA. opposing the expansion is then th
Dr SMS
system must exert most effort to pu
The force opposing the expansion is the constant However, that external pressure
external pressure pex multiplied by the area of the piston than the pressure, p, of the gas ins
(because force is pressure times area, Section 0.5), so
F = pex A. The work done is therefore
otherwise the external pressure w
gas instead of allowing it to expand
Opposing force imum work is obtained when the e
Work done = h × (pex A ) = pex × hA only infinitesimally less than the p
in the system. In effect, the two
Distance moved Volume change
adjusted to be the same at all stages
= pex × DV In the Introduction we called this b
The last equality follows from the fact that hA is the a state of mechanical equilibrium.
volume of the cylinder swept out by the piston as the conclude that a system that rema
gas expands, so we can write hA = DV. That is, for ex- equilibrium with its surroundings
pansion work, expansion does maximum expansi
Work done = pexDV There is another way of express
Because the external pressure is i
the external
Now consider pressure
the sign. A system does workis
and thereby
than the pressure of the gas at s
loses energy (that is, w is negative) when it expands
expansion (pex
DV is positive). = p). we need a negative
Therefore,
expansion, the piston moves out. H
sign in the equation to ensure that w is negative when we increase the external pressure
when it soiswein
is positive), mechanical
obtain eqn 2.2. infinitesimally greater than the pr
now the piston moves in. That is,
note on expansion.
good practice Keep track of signs by
in a state of mechanical equilibrium
considering whether the stored energy has decreased
when the change
system does work (w is then negative) or has
change in the pressure results in o
increased when work has been done on the system
of motion. A process that can b
infinitesimal change in a variable
(w is then positive).
pressure—is said to be reversible
w = - Pex (V f - Vi )
Vf
w = - ò PdV
Vi
Vf
Vf dV
w = - nRT ò = - nRT ln
Vi V Vi
Dr SMS
9
 10/29/20

Exercise
Calculate the work done when 50 g of iron reacts with HCl in a
(a) Closed vessel for fixed volume ( 0 J)
(b) Open beaker at 25C (-2.218 kJ)

Dr SMS

19

Exercise
Consider an ideal gas in a piston chamber, where the initial volume is 2.00 L
and the initial pressure is 8.00 atm. Assume that the piston is moving up (that
is, the system is expanding) to a final volume of 5.50 L against a constant
external pressure of 1.75 atm. Also assume constant temperature of 25C for
the process.

A) Calculate the work for the process (ans: 620.61 J)

B) Calculate the final pressure of the gas (ans: 2.91 atm)

20

10
 10/29/20

Energy Balance
• Most systems encountered in practice are stationary, that is, they do not involve
any changes in their velocity or elevation during a process. Thus, for stationary
systems, the changes in kinetic and potential energies are zero.

• Closed System EB ∆𝑼 = 𝑸 + 𝑾

• Open System EB ∆𝑯 = 𝑸 + 𝑾

Work can be combination of any work such as expansion work, electrical work, shaft
work, etc.

Dr SMS

21

Exercise
Suppose in the course of an experiment someone does 622 kJ of
work on an exercise bicycle and loses 82 kJ of energy as heat.
What is the change in internal energy of the person?
Answer: -704 kJ

22

11
 10/29/20

Enthalpy
Specific Heat

Dr SMS

23

Enthalpy
• Enthalpy of a system is defined as
H = U + PV

• A change in enthalpy arises from a change in the internal

energy and a change in the product PV.
DH = DU + D(PV )

• If the changes takes place at constant pressure,

DH = DU + PDV

24

12
 10/29/20
PM Page 179

Enthalpy of Ideal Gases

Chapter 4 | 179
ressure is maintained constant • Molar
is the enthalpy,
specific heatHat m = U m + PVm

– For perfect gas, heat (2)

This is illustrated in Fig. 4 –19. The specific PVm = RT
is always greater than cv because• Therefore,
at constant pressure
H m = U m + RT
d to expand and the energy for this expansion work (1)
to the system.
• Where, Enthalpy, H mV == constant
express the specific heats in terms of other Molar thermody- H /n P = constant
t, consider a fixed mass in a stationary closed Molar volume, Vm m= =V 1/ nkg
system m = 1 kg
Chapter 4 | 179 T = 1°C
volume process (and thus no expansion or compression T = 1 °C
e isconservation
the specificofheat at principle ein ! eout " #esystem
energy kJ kJ
c = 3.12 .
(2) v
cp = 5.19 .
kg °C kg °C
–19. The specific
expressed heat
in the differential form as
use at constant pressure
dein ! deout
r this expansion " du
work (1) 3.12 kJ 5.19 kJ
this equation represents the net amount of energy
rms
tem.ofFrom
other the
thermody-
definition ofV =cconstant P = constant
v, this energy must be
FIGURE 4 –19
ationary closed system m = 1 kg
dT is the differential change in temperature. Thus, m = 1 kg Constant-volume and constant-
pansion or compression T = 1°C T = 1 °C
pressure specific heats cv and cp
cv deT "
ple du at constant volume kJ kJ
in ! eout " #esystem cv = 3.12 . cp = 5.19 .
kg °C (values given are for helium gas).
˛

25 kg °C
m as
0u 3.12 kJ 5.19 kJ
cv " a
b (4 –19)
0T
net amount of energyv
v, this energy must be FIGURE 4 –19
on for the specific heat at constant pressure cp can be
temperature. Thus, Constant-volume and constant-
ing a constant-pressurepressure
expansion or compression
e Measurement
v of Heat
specific heats c and c
p
(values given are for helium gas).
0h • Energy absorbed or released by a system as heat:
cp " a b (4 –20) 𝑞 = 𝑐∆𝑇
0T p
(4 –19) • Specific heat (c):
–20 are the defining equations for
in Fig.
tant 4 –20.cp can be
pressure
cv andrequired
– Energy
degree.
cp, andtotheir
( (
cv = ofu a unit mass substance by one
raise the temperature
T v
nsion or compression
are expressed in terms of other –properties; thus, they = the change in internal energy
Common unit; kJ/kg.K or kJ/kg.℃
with temperature at
mselves. Like any other property, • Twothe specific
kinds heats
of specific heat;of constant volume
the state that, in general, is specified by heat
– Specific two atindepen-
constant volume, cv
(4 –20) required –toSpecific
ies. That is, the energy raise heat
the attempera-
constant pressure, cp
y one degree is different at different temperatures and
for anddifference
Butcvthis cp, and theiris usually not
can be made from Eqs. 4 –19 and
( (
cv = veryu large.
T v
4change
–20. First, these
( (
cp = h
T p
= the in internal energy = the change in enthalpy with
yr relations
properties;and thus,
as they
such are independent of the type
with temperature at of temperature at constant
ty, the specific heats of constant
valid for any substance undergoing any volume
process. The pressure
ecified by two indepen-
to a constant-volume process is that cv happens to be
d to raise the tempera-
to a system
erent duringand
temperatures a constant-volume process per unit
risevery
not
lso
in temperature.
how
large.
the name
and 4 –20. First, these 26
This is how
specific heat
( (
cp = theh values of cv are
atT constant
p volume
= the change in enthalpy with FIGURE 4 –20
the energy
ependent of transferred
the type of to a systemtemperature
per unitatmassconstantper
during a constant-pressure
oing any process. The process happens
pressure to be equal Formal definitions of cv and cp.
values of c
s that cv happens
p can be
to bedetermined and also explains the
ecific heat
volume at constant
process per unit pressure.
wthat
thecan be made
values of cv from
are Eqs. 4 –19 and 4 –20 is that cv 13
nges in internal
at at constant energy and cp to the changes in
volume
ould per
be more proper FIGUREc4 –20
perto define
stem unit mass v as the change in the
 10/29/20

Specific Heat

Dr SMS

27

Specific Heat Relation of Ideal Gases

• For a perfect gas,

ℎ = 𝑢 + 𝑅𝑇

𝑐" 𝑑𝑇 = 𝑐# 𝑑𝑇 + 𝑅𝑑𝑇

𝑐" = 𝑐# + 𝑅

𝑐" − 𝑐# = 𝑅

5 3
𝑐" = 𝑅 𝑐# = 𝑅
2 2

Dr SMS

28

14
 10/29/20

Exercise
Q2 Test 1 2018-2019-II:
An ideal gas expands adiabatically against a pressure 0.435 atm
until its volume double; which in considering one mole of an
ideal gas at initial pressure of 1.00 atm and temperature of 25 °C,
respectively. Given Cv = 12.47 J/mol K.

i) Calculate work, W (Answer: -987 J)

ii) Internal energy, ∆U (Answer: -987 J)
iii) Final temperature, Tf (Answer: 352.1K)

Dr SMS

29

Thermochemistry

Dr SMS

30

15
 10/29/20

Thermochemistry
• Thermochemistry is the study of heat change in chemical
reactions.
• A reaction vessel and its content form a system, and chemical
reaction result in the exchange of energy between the system
and the surrounding
• The application of enthalpy in chemistry.
• The thermochemistry processes contributing enthalpies are as
follows:
– Phase changes (vaporization, fusion, freezing, sublimation etc)
– Chemical changes (combustion, formation and reaction)

Dr SMS

31

Thermochemistry

Dr SMS

32

16
 10/29/20

Enthalpy in Phase Changes

• The conversion of one phase of a substance to another phase
is called phase transition.
• Most phase transitions are accompanied by a change of
enthalpy.
• Standard enthalpy of vaporization (∆-./ 𝐻 ° ) is the energy that
must be supplied as heat at constant pressure per mole of
molecules that are vaporized under standard conditions (1
bar).
𝐻! 𝑂 𝑙 → 𝐻! 𝑂 𝑔 ∆𝐻° = 40.7 𝑘𝐽⁄𝑚𝑜𝑙

• Depend on the stoichiometric coefficient in the chemical

reaction
2𝐻! 𝑂 𝑙 → 2𝐻! 𝑂 𝑔 ∆𝐻° = 81.4 𝑘𝐽⁄𝑚𝑜𝑙

Dr SMS

33

Enthalpy in Phase Changes

• Standard enthalpy of fusion(melting) (∆123 𝐻 ° ) is the change in
molar enthalpy that accompanies fusion under standard
conditions.
𝐻! 𝑂 𝑠 → 𝐻! 𝑂 𝑙 ∆𝐻° = 6.01 𝑘𝐽⁄𝑚𝑜𝑙
• The reverse of vaporization is condensation and the reverse of
fusion (melting) is freezing.
• The enthalpy change of a reverse transition is the negative of
the enthalpy change of forward transition
𝐻! 𝑂 𝑙 → 𝐻! 𝑂 𝑠 ∆𝐻° = −6.01 𝑘𝐽⁄𝑚𝑜𝑙

Dr SMS

34

17

Enthalpy in Phase Changes
• Standard enthalpy of sublimation (∆324 𝐻 ° ) is the amount of
energy required for direct conversion of a solid to a vapor. The
reverse process is called vapor deposition
Vaporization
Sublimation
∆subH
∆%&' 𝐻° = ∆(&% 𝐻° + ∆#)" 𝐻°
Enthalpy
∆vapH
Fusion
∆fusH
Fig. 3.3 The enthalpy of sublimation at a given temperature
is the sum of the enthalpies of fusion and vaporization at that
temperature. Another implication of the First Law is that
the enthalpy change of an overall process is the sum of the
enthalpy changes for the possibly hypothetical steps into
which it may be divided.
the enthalpies of fusion and vaporization for this
Dr SMS temperature. Adding together enthalpies of transition
for different temperatures gives a meaningless result.
35 Self-test 3.2
Calculate the standard enthalpy of sublimation of ice at
0°C from its standard enthalpy of fusion at 0°C (6.01 kJ
mol−1) and the standard enthalpy of vaporization of water
at 0°C (45.07 kJ mol−1).
[Answer: 51.08 kJ mol−1]
The result expressed by eqn 3.2 is an example of a
Heat of Fusion and Vaporization
more general statement that will prove useful time
and again during our study of thermochemistry:
The enthalpy change of an overall process is the sum
of the enthalpy changes for the steps (observed or
hypothetical) into which it may be divided.
3.2 Atomic and molecular change
A group of enthalpy changes we employ quite
often in the following pages are those accom-
panying changes to individual atoms and
molecules. Among the most important is the
standard enthalpy of ionization, D ion H -, the standard
molar enthalpy change accompanying the removal of
an electron from a gas-phase atom (or ion). For example,
because
H(g) → H +(g) + e−(g) DH = = +1312 kJ
the standard enthalpy of ionization of hydrogen atoms is
reported as 1312 kJ mol−1. This value signifies that 1312 kJ
of energy must be supplied as heat to ionize 1 mol H(g)
at 1 bar (and 298.15 K). Table 3.2 gives values of the
ionization enthalpies for a number of elements; note that
all enthalpies of ionization are positive.
Dr SMS
36
10/29/20
PHYSICAL CH
A brief comment The enthalpy of ionization is c
related to—but is not identical to—the ionization e
Briefly, the ionization energy corresponds to the standa
ization enthalpy at T = 0. The ionization enthalpy at a dif
temperature can be calculated from the ionization ene
using the concepts developed in Section 3.7.
We often need to consider a succession of io
tions, such as the conversion of magnesium ato
Mg+ ions, the ionization of these Mg+ ions to
ions, and so on. The successive molar enthalpy ch
are called, respectively, the first ionization enth
the second ionization enthalpy, and so on. For
nesium, these enthalpies refer to the processes
Mg(g) → Mg+(g) + e−(g) ∆H = +738 k
Mg +(g) → Mg2+(g) + e−(g) ∆H = +1451
Note that the second ionization enthalpy is
than the first: more energy is needed to separa
electron from a positively charged ion than fro
neutral atom. Note also that enthalpies of ioniz
refer to the ionization of the gas phase atom o
not to the ionization of an atom or ion in a
To determine the latter, we need to combine tw
more enthalpy changes.
Example 3.2
Combining enthalpy changes
The standard enthalpy of sublimation of magnes
at 25°C is 148 kJ mol−1. How much energy as hea
constant temperature and pressure) must be supp
to 1.00 g of solid magnesium metal to produce a
composed of Mg2+ ions and electrons?
Strategy The enthalpy change for the overall proces
a sum of the steps, sublimation followed by the
stages of ionization, into which it can be divided. T
the heat required for the specified process is the pro
of the overall molar enthalpy change and the amoun
atoms; the latter is calculated from the given mass
the molar mass of the substance.
Solution The overall process is
Mg(s) → Mg2+(g) + 2 e−(g)
The thermochemical equation for this process is
sum of the following thermochemical equations:
DH -
Sublimation: Mg(s) → Mg(g) +1
First ionization: Mg(g) → Mg+(g) + e−(g) +7
Second ionization: Mg+(g) → Mg2+(g) + e−(g) +14
Overall (sum): Mg(s) → Mg2+(g) + 2 e−(g) +23
18
 10/29/20

Enthalpy in Phase Changes

PHYSICAL CHANGE 65

Table 3.1
Standard enthalpies of transition at the transition temperature*

Substance Freezing point, T f /K D fus H - /(kJ mol−1) Boiling point, T b /K D vap H -/(kJ mol −1)

Ammonia, NH3 195.4 5.65 239.7 23.4

Argon, Ar 83.8 1.2 87.3 6.5
Benzene, C6H6 278.6 10.59 353.2 30.8
Ethanol, C2H5OH 158.7 4.60 351.5 43.5
Helium, He 3.5 0.02 4.22 0.08
Mercury, Hg 234.3 2.292 629.7 59.30
Methane, CH4 90.7 0.94 111.7 8.2
Methanol, CH3OH 175.2 3.16 337.2 35.3
Propanone, CH3COCH3 177.8 5.72 329.4 29.1
Water, H2O 273.15 6.01 373.2 40.7

* For values at 298.15 K, use the information in the Data section. The text’s website also contains links to online databases of
thermochemical data.

Example 3.1
Determining the enthalpy of vaporization of
a liquid
Ethanol, C2H5OH, is brought to the boil at 1 atm. When an
electric current of 0.682 A from a 12.0 V supply is passed
37 for 500 s through a heating coil immersed in the boiling
liquid, it is found that the temperature remains constant
but 4.33 g of ethanol is vaporized. What is the enthalpy
of vaporization of ethanol at its boiling point at 1 atm?
Strategy Because the heat is supplied at constant pres-
sure, we can identify the heat supplied, q, with the
change in enthalpy of the ethanol when it vaporizes.
We need to calculate the heat supplied and the amount
of ethanol molecules vaporized. Then the enthalpy of
vaporization is the heat supplied divided by the amount.
The heat supplied is given by eqn 2.5 (q = I !t ; recall that
1 A V s = 1 J). The amount of ethanol molecules is deter-
mined by dividing the mass of ethanol vaporized by its
molar mass (n = m / M ).
Solution The energy supplied by heating is
q = I !t = (0.682 A) × (12.0 V) × (500 s)
= 0.682 × 12.0 × 500 J
This value is the change in enthalpy of the sample. The
amount of ethanol molecules (of molar mass 46.07 g
Because the pressure is 1 atm, not 1 bar, the enthalpy
of vaporization calculated here is not the standard value.
However, 1 atm differs only slightly from 1 bar, so we
Dr SMS
can expect the standard enthalpy of vaporization to be
very close to the value found here. Note also that the
value calculated here is for the boiling point of ethanol,
which is 78°C (351 K): we convey this information by
writing D vapH - (351 K) = 43.5 kJ mol−1.
A note on good practice Molar quantities are ex-
pressed as a quantity per mole (as in kilojoules per mole,
kJ mol−1). Distinguish them from the magnitude of a
property for 1 mol of substance, which is expressed as
the quantity itself (as in kilojoules, kJ). All enthalpies of
transition, denoted DtrsH, are molar quantities.
Self-test 3.1
In a similar experiment, it was found that 1.36 g of
boiling benzene, C6H6, is vaporized when a current
of 0.835 A from a 12.0 V source is passed for 53.5 s.
What is the enthalpy of vaporization of benzene at
its boiling point?
[Answer: 30.8 kJ mol−1]

m
Enthalpy in Chemical Changes
mol−1) vaporized is
4.33 g 4.33
n= =
- Enthalpy of combustion
=
M 46.07 g mol−1 46.07
mol There are some striking differences in standard
enthalpies of vaporization: although the value
−1

- Enthalpy of formationatforitswater
The molar enthalpy change is therefore
0.682 × 12.0 × 500 J
is 44 kJ mol , that for methane, CH ,
boiling point is only 8 kJ mol . Even −1
4

D H= = 4.35 × 10 J mol4 allowing for the fact that vaporization is taking place
−1
vap
- Enthalpy
(4.33/46.07) mol
corresponding to 43.5 kJ mol . −1
or reaction
at different temperatures, the difference between the
enthalpies of vaporization signifies that water molecules
are held together in the bulk liquid much more tightly

Dr SMS

38

19
 10/29/20

Enthalpy in Chemical Changes

• Some enthalpy relate to the enthalpy in chemical changes are
enthalpy of combustion, enthalpy of formation and enthalpy
or reaction.
• Enthalpy of combustion, ∆5 𝐻 °
– The standard enthalpy of combustion is the change in standard
enthalpy per mole of combustible substance.

𝐶𝐻* 𝑔 + 2𝑂! 𝑔 → 𝐶𝑂! 𝑔 + 𝐻! 𝑂 𝑙 ∆𝐻° = −890 𝑘𝐽⁄𝑚𝑜𝑙

– Commonly measured using bomb calorimeter (energy transfer as heat

at constant volume).
– Gas phase

∆𝐻+ = ∆𝑈+ + ∆𝑣,)% 𝑅𝑇

Dr SMS

39

Standard Enthalpy of Combustion

72 CHAPTER 3: THERMODYNAMICS: APPLICATIONS OF THE FIRST LAW

pVm = (1.0 × 105 Pa) × (18 × 10−6 m3 mol−1)

Table 3.6 = 1.8 Pa m3 mol−1 = 1.8 J mol−1
Standard enthalpies of combustion
= 1.8 × 10−3 kJ mol−1
Substance D c H -/(kJ mol−1) However, the molar volume of a gas, and therefore
the value of pVm, is about 1000 times greater and
Benzene, C6H6(l) −3268 cannot be ignored. For gases treated as perfect, pVm
Carbon monoxide, CO(g) −394 may be replaced by RT. Therefore, if in the chemical
Carbon, C(s,graphite) −394 equation the difference (products – reactants) in the
Ethanol, C2H5OH(l) −1368 stoichiometric coeAcients of gas phase species is
Ethyne, C2H2(g) −1300 ∆vgas, we can write
Glucose, C6H12O6(s) −2808
Hydrogen, H2(g) −286 ∆cH = ∆cU + ∆v gas RT (3.3)
iso-Octane, *C8H18(l) −5461 Note that ∆v gas (where v is nu) is a dimensionless
Methane, CH4(g) −890 quantity.
Methanol, CH3OH(l) −726
Methylbenzene, C6H5CH3(l) −3910 A brief illustration The energy released as heat when
Octane, C8H18(l) −5471 glycine is burned in a bomb calorimeter is 969.6 kJ mol−1
Propane, C3H8(g) −2220 at 298.15 K, so DcU = −969.6 kJ mol−1. From the chemical
Sucrose, C12H22O11(s) −5645 equation
Urea, CO(NH2)2(s) −632
NH2CH2COOH(s) + 94 O2(g) → 2 CO2(g) + 52 H2O(l) + 12 N2(g)

* 2,2,4-Trimethylpentane. we find that Dvgas = (2 + 12) − 94 = 14 . Therefore, assuming that

Dr SMS
By convention, combustion of an organic compound
40 results in the formation of carbon dioxide gas, liquid
water, and—if the compound contains nitrogen—
nitrogen gas. The standard enthalpy of combustion,
∆cH , is the change in standard enthalpy per mole of
combustible substance. In this example, we would
write ∆ c H (CH4, g) = −890 kJ mol−1. Some typical
values are given in Table 3.6. Note that ∆ c H is a
molar quantity, and is obtained from the value of
∆H by dividing by the amount of organic reactant
consumed (in this case, by 1 mol CH4). We see in
Box 3.1 that the enthalpy of combustion is a useful
measure of the eAciency of fuels.
Enthalpies of combustion are commonly measured
the difference between DcU and DcH is due to contribu-
tions from reactants and products in the gas phase, we
use eqn 3.3 to obtain
DcH = DcU + 14 RT
= −969.6 kJ mol−1 + 14 × (8.3145 × 10−3 kJ K−1 mol−1)
× (298.15 K)
= −969.6 kJ mol−1 + 0.62 kJ mol−1
= −969.0 kJ mol−1
3.4 The combination of reaction enthalpies
The reaction enthalpy (or the ‘enthalpy of reaction’),
∆rH, is the change in enthalpy that accompanies a
chemical reaction: the enthalpy of combustion is just 20
a special case. The reaction enthalpy is the difference
between the molar enthalpies of the reactants and the
products, with each term weighted by the stoichio-
metric coeAcient, v (nu), in the chemical equation:
 the enthalpy density is Dc H -/Vm , where Vm is the molar that is oxidized. Now consider the oxidation of 1 mol
volume of the material. CH3OH(g):
The table lists the specific enthalpies and enthalpy densi- 3
CH3OH(g) + O2(g) → CO2(g) + 2 H2O(l) DH - = −764 kJ
ties of several fuels. The most suitable fuels are those with 2

high specific enthalpies, as the advantage of a high molar
enthalpy of combustion may be eliminated if a large mass of
fuel is to be transported. We see that H2 gas compares very
well with more traditional fuels such as methane (natural
gas), iso-octane (gasoline), and methanol. Furthermore, the
combustion of H2 gas does not generate CO2 gas, a pollut-
ant implicated in the mechanism of global warming. As
a result, H2 gas has been proposed as an efficient, clean
alternative to fossil fuels, such as natural gas and petroleum.
However, we also see that H2 gas has a very low enthalpy
density, which arises from the fact that hydrogen is a very
light gas. So, the advantage of a high specific enthalpy is
This reaction is also exothermic, but now only 764 kJ of
energy is released as heat per mole of carbon that under-
goes oxidation. Much of the observed change in energy
10/29/20
output between the reactions can be explained by noting
that the carbon in methanol has an oxidation number of −2,
and not −4 as in methane. That is, the replacement of a
C—H bond by a C—O bond renders the carbon in methanol
more oxidized than the carbon in methane, so it is reason-
able to expect that less energy is released to complete the
oxidation of carbon to CO2 in methanol. In general, we find
that the presence of partially oxidized carbon atoms (that is,
carbon atoms bonded to oxygen atoms) in a material makes

Standard Enthalpy of Combustion

undermined by the large volume of fuel to be transported
and stored. Strategies are being developed to solve the
storage problem. For example, the small H2 molecules can
travel through holes in the crystalline lattice of a sample of
it a less suitable fuel than a similar material containing more
highly reduced carbon atoms.
Another factor that determines the heat output of
combustion reactions is the number of carbon atoms in

Box 3.1
Thermochemical properties of some fuels

Fuel Combustion equation D c H -/ Specific Enthalpy

(kJ mol−1) enthalpy/ density*/
(kJ g−1) (kJ dm−3)

Hydrogen 2 H2(g) + O2(g) → 2 H2O(l) −286 142 13

Methane CH4(g) + 2 O2(g) → CO2(g) + 2 H2O(l) −890 55 40
iso-Octane 2 C8H18(l) + 25 O2(g) → 16 CO2(g) + 18 H2O(l) −5471 48 3.8 × 104
Methanol 2 CH3OH(l) + 3 O2(g) → 2 CO2(g) + 4 H2O(l) −726 23 1.8 × 104

* At atmospheric pressures and room temperature.

† 2,2,4-Trimethylpentane.

Dr SMS

41

Enthalpy in Chemical Changes

• Standard enthalpies of formation (∆1 𝐻 ° ) is standard enthalpy
for substances formation from its element at references state.
𝐻! 𝑔 + 1/2𝑂! 𝑔 → 𝐻! 𝑂 𝑙 ∆𝐻° = −286 𝑘𝐽⁄𝑚𝑜𝑙

• Standard enthalpies of reaction, ( ∆6 𝐻 ° ) is standard of

enthalpy can accompanies a chemical reaction
• Can be calculate from enthalpy of formation which is the
differences between enthalpies of formations the products
and reactants.

∆- 𝐻 ° = 8 𝑣∆( 𝐻 ° 𝑝𝑟𝑜𝑑𝑢𝑐𝑡 − 8 𝑣∆( 𝐻 ° 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡

42

21
 Table 3.8 Endothermic compounds
Standard enthalpies of formation at 298.15 K *
∆fH° > 0

Enthalpy
Substance D f H °/(kJ mol−1)

Inorganic compounds
10/29/20
Elements

Ammonia, NH3(g) −46.11 ∆fH° < 0

Ammonium nitrate, NH4NO3(s) −365.56
Carbon monoxide, CO(g) −110.53
Exothermic compounds
Carbon disulfide, CS2(l) +89.70
Carbon dioxide, CO2(g) −393.51
Dinitrogen tetroxide, N2O4(g) +9.16 Fig. 3.8 The enthalpy of formation acts as a kind of ther
Dinitrogen monoxide, N2O(g) +82.05 chemical ‘altitude’ of a compound with respect to the ‘sea le
Hydrogen chloride, HCl(g) −92.31 defined by the elements from which it is made. Endother
Hydrogen fluoride, HF(g) −271.1 compounds have positive enthalpies of formation; exot
mic compounds have negative energies of formation.
Hydrogen sulfide, H2S(g) −20.63
Nitric acid, HNO3(l) −174.10
Standard Enthalpy of Formation Nitrogen dioxide, NO2(g)
Nitrogen monoxide, NO(g)
+33.18
CHEMICAL CHANGE 77 Computer-aided molecular modelling using co
+90.25
mercially available software is now widely used
Sodium chloride, NaCl(s) − 411.15
Sulfur dioxide, SO2(g) −296.83
estimate standard enthalpies of formation of m
Table 3.8 Sulfur trioxide, SO3(g) Endothermic−395.72
compounds cules with complex three-dimensional structures,
Standard enthalpies of formation at 298.15 K * Sulfuric acid, H2SO4(l) −813.99 can distinguish between different conformations
Water, H2O(l) ∆fH° > 0 −285.83 the same molecule. In the case of methylcyclohexa
−241.82 for instance, the calculated difference in enthalpy

Enthalpy
Substance D f H °/(kJ mol−1) H2O(g)
Elements formation ranges from 5.9 to 7.9 kJ mol−1, wh
Inorganic compounds Organic compounds compares favourably with the experimental valu
Ammonia, NH3(g) −46.11 ∆fH°C6<H06(l)
Benzene, +49.0 7.5 kJ mol−1. However, good agreement betw
Ammonium nitrate, NH4NO3(s) −365.56 Ethane, C2H6(g) −84.68 calculated and experimental values is relatively r
Carbon monoxide, CO(g) −110.53 Ethanol, C2H5OH(l) −277.69 Computational methods almost always predict c
Exothermic compounds
Carbon disulfide, CS2(l) +89.70 Ethene, C2H4(g) +52.26
rectly which conformation of a molecule is most sta
Carbon dioxide, CO2(g) −393.51 Ethyne, C2H2(g) +226.73
but do not always predict the correct numerical val
Dinitrogen tetroxide, N2O4(g) +9.16 Fig. 3.8 TheCenthalpy
Glucose, 6H12O6(s)of formation acts as −1268
a kind of thermo-
Dinitrogen monoxide, N2O(g) +82.05 chemical ‘altitude’
Methane, CH4(g)of a compound with respect to the ‘sea level’
−74.81
of the difference in enthalpies of formation.
Hydrogen chloride, HCl(g) −92.31 defined by the
Methanol, CHelements
OH(l) from which it is made. Endothermic
−238.86 A calculation performed in the absence of solv
3
Hydrogen fluoride, HF(g) −271.1 compounds
Sucrose, Chave positive enthalpies of −2222.86
12H22O11(s)
formation; exother- molecules estimates the properties of the molecul
mic compounds have negative energies of formation. interest in the gas phase. Computational methods
Hydrogen sulfide, H2S(g) −20.63
Nitric acid, HNO3(l) −174.10 * A longer list is given in the Data section at the end of the available that allow for the inclusion of sev
Nitrogen dioxide, NO2(g) +33.18 book. The text’s website also contains links to additional data.
Computer-aided molecular modelling using com- solvent molecules around a solute molecule, ther
Nitrogen monoxide, NO(g) +90.25 taking into account the effect of molecular in
mercially available software is now widely used to
Sodium chloride, NaCl(s) − 411.15 actions with the solvent on the enthalpy of format
Sulfur dioxide, SO2(g) −296.83
estimate standard enthalpies of formation of mole-
molecules
cules in these two
with complex conformationsstructures,
three-dimensional have different
and of the solute. Again, the numerical results are o
Sulfur trioxide, SO3(g) −395.72
standard
can enthalpies
distinguish of formation
between different as a result of the
conformations of estimates and the primary purpose of the calculat
Sulfuric acid, H2SO4(l) −813.99
greater
the samesteric repulsion
molecule. In thewhen themethylcyclohexane,
case of methyl group is in is to predict whether interactions with the solv
Water, H2O(l) −285.83
H2O(g) −241.82 an axial
for position
instance, than whendifference
the calculated it is equatorial.
in enthalpy of increase or decrease the enthalpy of formati
formation ranges from 5.9 to 7.9 kJ mol−1, which As an example, consider the amino acid glyc
compares favourably with the experimental value of which can exist in a neutral or zwitterionic fo
Organic compounds
Benzene, C6H6(l) +49.0 Dr SMS
7.5 kJ mol−1. However, good agreement between H2NHCH2COOH and +H3NCH2CO 2− , respectiv
Ethane, C2H6(g) −84.68 calculated and experimental values is relatively rare. in which in the latter the amino group is protona
Ethanol, C2H5OH(l) −277.69 Computational methods almost always predict cor- and the carboxyl group is deprotonated. Molecu
43 Ethene, C2H4(g) +52.26
rectly which conformation of a molecule is most stable modelling shows that in the gas phase the neu
Ethyne, C2H2(g) +226.73 form has a lower enthalpy of formation than
but do not always predict the correct numerical values
Glucose, C6H12O6(s) −1268 zwitterionic form. However, in water the opposit
Methane, CH4(g) −74.81
of the difference in enthalpies of formation.
A calculation performed in the absence of solvent true on account of the strong interactions betw
Methanol, CH3OH(l) −238.86
molecules1 Equatorial
estimates the properties of the 2 Axial
molecule of the polar solvent and the charges on the zwitter io
Sucrose, C12H22O11(s) −2222.86
interest in the gas phase. Computational methods are
* A longer list is given in the Data section at the end of the available that allow for the inclusion of several
book. The text’s website also contains links to additional data. solvent molecules around a solute molecule, thereby
taking into account the effect of molecular inter-

Hess’s Law and Heat of Formation

molecules in these two conformations have different
standard enthalpies of formation as a result of the
greater steric repulsion when the methyl group is in
an axial position than when it is equatorial.
1 Equatorial
actions with the solvent on the enthalpy of formation
of the solute. Again, the numerical results are only
estimates and the primary purpose of the calculation
is to predict whether interactions with the solvent
increase or decrease the enthalpy of formation.
As an example, consider the amino acid glycine,
which can exist in a neutral or zwitterionic form,
H2NHCH2COOH and +H3NCH2CO 2− , respectively,
in which in the latter the amino group is protonated
and the carboxyl group is deprotonated. Molecular
modelling shows that in the gas phase the neutral
form has a lower enthalpy of formation than the
zwitterionic form. However, in water the opposite is
true on account of the strong interactions between
2 Axial the polar solvent and the charges on the zwitter ion.

Dr SMS

44

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