COU

URSE COD
DE
COU
URSE TITL
LE
HAN
ND-OUT NO. 1
Lectture Hours
s

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REF
FERENCE

CHPH
HY2 34P
PHYS
SICAL CHE
EMISTRY 2
FIRST
T LAW OF
F THERMO
ODYNAMIC
CS
1.50 h
hours
Funda
amentals of Physical Chemis
stry
Maron
n and Land
do

THE
ERMODYN
NAMICS

Is the study of in
nterrelation
n between vvarious forrms of energy in a syystem

ems or tho
ose of comparatively large and involving
Is based on the behaviour of macrosscopic syste
many moleculess

he initial and final

e element iin transform
mations bu
ut intereste
ed only in th
Does not consider the time
em
states of a syste

Basic forms of energy exissting in Natture:

C ENERGY
Y
1. KINETIC
Possessed
d by a systtem by virttue of its m
motion, be it molecula
ar or motion
n of the

body as a whole
TIAL ENERGY
2. POTENT
d by a systtem by virttue of its po
osition, or by virtue o
of the struccture of the
e
Possessed

body and its configuration with respect to

o other bod
dies

anical Equ
uivalent off Heat is th
he relation of the unitt of mecha
anical workk to the thermal units
Mecha
echanical E
Energy
Me
Ele
ectrical Ene
ergy
The
ermal Energy

cgs Units
e
erg
Jo
oule
Ca
alorie

ERMODYN
NAMIC SYS
STEM
THE

Syste
em is define
ed as any portion of tthe universse isolated
d in an inerrt containerr which ma
ay be real
or ima
aginary, forr purposes of study o
of the effecct of variouss variabless upon the contents o
of the
system
m

Surro
oundings iss the portio
on of the universe exxcluded from the systtem
em and Surrrounding
Figurre 1. Syste

m:
Typess of System
1. Open sy
ystems, w
which can e
exchange b
both matter and enerrgy with its surroundin
ngs
where no trransfer of m
matter to o
or from the surroundin
ngs is posssible, only
2. Closed System, w
energy
d systems
s, where no
o exchange
e of matterr and energ
gy with its surroundin
ngs is
3. Isolated
possible
e

e is defined
d as a hom
mogeneouss, physicallly distinct, and mecha
anically se
eparable po
ortion of a
Phase
system
m
1. Homoge
eneous sysstem conta
ains only on
ne phase
ains more than a sing
gle phase
2. Heterogeneous syystem conta

Phase
es present in a system
m may consist of:
1. Pure sub
bstance

An elemen
nt or compound whicch containss a fixed an
nd definite ratio amon
ng its
constituen
nts

ns
2. Solution

ned as a p
physically h
homogeneo
ous mixturre of two orr more
True Soluttion is defin
substance
es

May eitherr be gas, liquid or sollid and ma

ay vary in ccomposition
n within wide limits

Typess of Propertties of a Syystem:

1. Extensivve Propertyy

Magnitude
e depends on the am
mount of substance prresent

Includes m
mass, volum
me and en
nergy

2. Intensive
e Propertyy

Value is in
ndependen
nt of the tottal amount, but depends on the
e concentra
ation of
the substa
ance or sub
bstances in
n a system
m

Includes d
density, pre
essure, refrractive index, mass a
and volume
e per mole
e

Princiiple of Rep
producibillity of States suggessts that the
e State of a system ccan be reprroduced
by rep
producing tthe values of the variables

FIRS
ST LAW O
OF THERM
MODYNAM
MICS

First la
aw of Therrmodynamiics is mere
ely the law of conservvation of en
nergy, thatt is, energy
y can
neithe
er be created nor de
estroyed

For an
ny quantityy of a form of energy that disapp
pears, ano
other or oth
her forms o
of energy w
will have to
appea
ar in total quantity exa
actly equall to the am
mount that d
disappeare
ed.

The in
nternal ene
ergy of a syystem can be change
ed by a flow
w of work, heat or bo
oth:

E rep
presents th
he change in the inte
ernal energ
gy of the syystem, q re
epresents h
heat, and w
repressents work

Therm
modynamicc quantitiess always co
onsist of tw
wo parts: a number, g
giving the m
magnitude of the
chang
ge; and a siign, indicating the dirrection of tthe flow. Th
he sign re
eflects the
e systems
s point of
view:

sign indica
ates that th
he systemss energy iss increasin
ng
where the positive s

ndicates that the systtems energ

rgy is decre
easing
the negatiive sign in

That iss, in this co

onvention tthe signs o
of both q and w reflecct what hap
ppens to th
he system;; thus we
use:
E = q + w

E de
epends onlyy in the inittial and final states o
of the syste
em, and no
ot at all on tthe manne
er in which
the ch
hange is acccomplishe
ed

n distance, if the pisto

on moves a distance h, work
Work is defined as a force applied ovver a given
is:
Worrk

= Forcce x distance

dw

=Fxd
dh

or F = P x A
A, then
Since P = F/A, o
dw

= p x A x dh

Since volume off the cylinder equals tthe area off the piston
n times the
e height of the cylinde
er:
dV

= finall volume initial volu

ume
=Axd
dh

And:
dw

= p x A x dh
= p dV
V

gure 2. Pre
essure V
Volume or M
Mechanica
al Work
Fig

ent thermodynamic cconditions:

Differe
1. Constan
nt Volume
e, where dV
V = 0, dw = 0, hence:
E = q
ng Pressu
ure Zero o
or Free Exp
pansion, w
where p = 0
0, dw = 0 a
and hence:
2. Opposin
E = q
ng pressu
ure consta
ant:
3. Opposin
dw

V
= p dV

= p (V
V2 V1)

ng Pressu
ure Variable, when p is variable
e, then p m
must be known as a ffunction of
4. Opposin
V for the
e work equ
uation to be
e integrated
d. If no ana
alytic functtion is avaiilable, the integration
n
can be p
performed graphicallyy by plottin
ng p vs. V a
and determ
mining the area under the
curve.

RTANT!
IMPOR
1. The presssure whicch determin
nes the am
mount of wo
ork done iss not the prressure of the gas
but the p
pressure against which the gass is working
g
pansion, w is negative
e, and worrk is done b
by the gas on its
2. If V2 > V1, the proccess is exp
surround
ding
pansion, w is positive
e, and workk is done by the surro
ounding
3. If V2 < V1, the proccess is exp
on the g
gas
hich work iss performe
ed, and, he
ence, w is
4. Magnitude of workk depends on the manner in wh
ate function
n
not a sta
E is fixed, q must varry with w, a
and thus dependent upon the p
path followe
ed by the
5. Since E
process

REV
VERSIBILITY AND M
MAXIMUM WORK

Reverrsible Proce
ess is any process w
which is con
nducted that at everyy stage the
e driving force is only
infinite
esimally greater than the oppossing force, and which
h can be re
eversed by increasing
g the
oppossing force b
by an infinittesimal am
mount

Reverrsible proce
ess are imp
possible in
n nature, an
nd hence a
all naturallyy occurring
g processe
es are
irreverrsible in na
ature

The w
work obtainable from a given pro
ocess unde
er reversib
ble conditio
ons is the m
maximum p
possible,
and th
hat this worrk is the minimum req
quired to re
everse the
e process:
The maximum
m work is o
obtainable
e from a sy
ystem when any ch
hange takiing place iis entirely
y
reve
ersible.

Underr reversible
e conditions, the exte
ernal pressure p differs only by an infinitessimal amou
unt from
the pre
essure of tthe gas itse
elf, P, hencce:
Maximum W
Work (wm)

= P dV

If the d
driving pressure is m
made greate
er the P + dP, the pro
ocess beco
ome irreve
ersible and more
work tthan PdV w
will be requ
uired to acccomplish th
he compre
ession.

THALPY O
OF THE SY
YSTEM
ENT

Enthalpy or heatt content o

of the syste
em is define
ed as:

where
e E is the in
nternal ene
ergy of the system, P is the presssure of th
he system, and V is th
he volume
of the system

energy, pre
essure, an
nd volume
e are all sstate functiions, enthalpy is alsso a state
e
Since internal e
on
functio

consid
der a proce
ess carried
d out at co
onstant prressure, where the o
only work allowed is pressure-volume work (w = PV). Under these
e condition
ns the exprression: E
E = qP + w, becomes:

V:
Since H = E + PV

Since P is constant:

e:
Hence

At con
nstant presssure (whe
ere only PV
V work is a
allowed) the change in enthalpyy (H) of tthe system
m
is equ
ual to the e
energy flow
w as heat. This mean
ns that for a reaction
n studied a
at constantt pressure,,
the flo
ow of heat is a measu
ure of the cchange in enthalpy fo
for the systtem. For th
his reason,, the termss
heat o
of reaction
n and cha
ange in en
nthalpy arre used in
nterchange
eably for rreactions studied att
consta
ant pressurre.

THE
ERMODYN
NAMICS OF IDEAL G
GASES

For an
n Ideal Gass: PV = nR
RT, and:

where
e (KE)avg re
epresents tthe averag
ge, random
m, translatio
onal energ
gy for 1 mo
ole of gas at a given
n
tempe
erature T (in kelvins). The only w
way to cha
ange the kiinetic enerrgy of an id
deal gas is to change
e
its tem
mperature. The energ
gy (heat) required tto change the energy of 1 molle of an ide
eal gas byy
T is:

pacity of a substance
e is defined
d as the en
nergy required to raisse the temp
perature off
Molarr Heat Cap
1 mole
e of that su
ubstance b
by 1 K.
C

= dq / dT

dq

= dE + p dV

= dE + p dV
d
dT

Hea
ating a Gas
s at Consttant Volum
me:

when volume is held consttant, dV = 0

0:
CV

=( E / T)V

al energy w
with tempe
erature at cconstant vo
olume
Cv is the rate of cchange of the interna

gas is heatted in a rig

gid containe
er in which
h no chang
ge in volum
me occurs,, there can
n
When an ideal g
Under thesse conditio
ons all the energy tha
at flows intto the gas is used to
o
be no PV work ((V = 0). U
ase the tran
nslational e
energies off the gas m
molecules
increa

ating a Gas
s at Consttant Press
sure:
Hea

when pressure iss held constant, p = P

P:
CP

=( E / T)P + P ( V / T)P\

CP

=( H / T)P

mperature at constan
nt pressure
e
CP is tthe rate of change off the enthallpy with tem

When an ideal g
gas is hea
ated at constant pre
essure, its volume in
ncreases a
and PV wo
ork occurs..
gy must be supplied
d both to cchange the
e
Thus, when a gas is heated at consstant presssure, energ
ational en
nergy of tthe gas a
and to prrovide the
e work th
he gas do
oes as itt expandss
transla

The qu
uantity of w
work done as the gass expands by V is P V

Hea
ating a Pollyatomic G
Gas:

Monattomic real gases, succh as heliu

um, have m
measured vvalues of Cv very closse to 3/2R.. However,,
gases such as S
SO2 and C
CHCl3 that contain p
polyatomic moleculess have obsserved values for Cv
antly greate
er than 3/2
2R.
that arre significa

ules absorrb energy tto increase

As a p
polyatomicc gas is heated, the g
gas molecu
e their rota
ational and
d
vibrational motio
ons as well as to movve through space (tra
anslate) at higher spe
eeds

erature of a monatom
mic ideal g
gas is an in
ndex of the
e average random tra
anslationall energy off
Tempe
the ga
as. Thus, when a g
gas is hea
ated, the te
emperature only inccreases to the exten
nt that the
e
transla
ational ene
ergies of tthe molecu
ules increa
ase. Any e
energy tha
at is absorrbed to inccrease the
e
vibrational and ro
otational e
energies do
oes not con
ntribute dirrectly to the
e translatio
onal kineticc energy

alue of Cv for a gass whose pa

articles are
e molecule
es is not ccaused byy
Note tthat the ellevated va
nonide
eal behavior. That iss, it does not depen
nd on whe
ether the gas obeyss the idea
al gas law..
Rather, it is simp
ply that the
e internal sstructure o
of the molecules enab
bles them to absorb energy forr
processses other than transslational motions.

Thus, if a given p
polyatomicc gas obeyys ideal gass law, the e
equation b
below can b
be used:

also that ass the molecules beco

ome more complex (m
ms), Cv incrreases. Th
his result iss
Note a
more atom
expeccted because the pre
esence of more atom
ms means that more
e nontransslational m
motions are
e
orb energyy
available to abso
THE
ERMMODY
YNAMIC PR
ROPERTIE
ES OF IDE
EAL GAS

For calculation of the heat flow for an ideal gas:

q = nC T
where CV or CP is used depending on the conditions

For a temperature change of ideal gas regardless of whether pressure or volume (or neither) is
constant:
H = n CP T
E = n CV T

Heat flow at constant volume equals E; (E = qV)

Heat flow at constant pressure equals H; (H = qP)

CARNOT CYCLE
Observations from Carnot Process:
1. Absorption of heat takes place at the higher temperature
2. Heat passes from higher to lower temperature
3. Thermodynamic efficiency must be the same for all processes operating under a given
temperature