ANDERSON

JUNIORCOLLEGE
CHEMISTRY
JC1LECTURE

of the behaviorgases is an importantaspecttn chemist'.

.The understandirp
t ne ongtn ot wnat afe Rnowntodayas tha gas taws, stadedin 1M3 with the invenfi5n

oJ_!",_!"ro.y.d?1.by
Toniceili.
Gter,RonenBoytepu'tisnea
Ciye:s'ia:;.
lmOelisto
t n,sEw sratedthatat
constant

temperature
thewluine of a gasis inverselyproport:nnat
to thepressuro.Theobse'ationsby RobeftBoyleand otheiscientisfs
suchi"ir"q"";
charles andJohn Daltonled to thedevelopment
ot thegas,aws.ln the tateninetiiin
century,the kinetic-molecular
lheorywas thendevelopedby screnfr.sts.
rni" iiiorv'ii
basedon 3 fundamentatassumpfionsthatare usedto explaintheprop.ii"i iiii"J
gases'An tdea,gas is an imaginarygasthatperfecttyobeyslheseassumption"
,"/
as theBoyle's
LawandChartes'
Law.
""
AssessmentObiectives
o state lhe basicassumption
of the kinetictheory.asappriedto an idealgas
. Explainqualitatively
in termsof intermolecular
forcesand molecularsizi:
o The conditionnecessary
for a gasto approachidealbehaviour
o The limitationof idealityat very highpressureand very low
temperatures
.

o ptatg gno userhegenerargasequationpV= nRTin carcurationincruding

,
the deteimination
of Mr
. Describe,usinga kinetic-rnolecularmodel,the liquidstate;melting;
vaporizationandvapourpressure.

LectureOutline
.

Introduction

Summaryof the kineticconceptof the stateof matter

o The Gas Laws

o ldealgasesand the kinetic-molecular
theoryof gases
.

Maxwell-Boltzmann
distribution
of molecularspecies

Chemisrry2004

Mr Matthew Soh

Introduction
States of Matter
Manypuresubstancescan existin a[ of the threestatesof matten
sorid,
liquld andgas, dependingon conditionof temperatuieand pressure,
a
a

Eachstate can be classified by its particutarproperlies

Someof the bulk propertiesare

Solid

Liquid

Volume

Fixedvolume

Fixedvolume

Shape

Fixedshape

Compressibility

'

Gas

Nofh;a{ )oeurrrc Vltt/)

Notfixed;assurne Notfile<i;assumJ
shapeof
shape of
container
annlainar
Virtually
Virtually
Compressible
incompressible incompressible

Theseb,ulkpropertiescan be exprainedby the kineticconceptof the

three
statesof matteras brieflysummarizedbeiow.(ThekinetictheoryoiS""""
will be studiedin detaillaterin the lecture)

Chemistrv2004

Mr MatthewSoh

Gas

Liquid

Solid

Arrangement
of particles

.
Degreeof
movementof
particles

Processfor
changeof
state

.
Strongforces
betweenthe
.
partides
Particlesare
packedclosely
in a regular
arTangement

.
Strongforces
betweenthe particles
Particlesare not as
.
as in
close-packed
the solidstateand
not in an orderly
arrangement

Negligibleforces
betweenthe
particles.
Particlesare far
apart, and in
r:rndom
arangement.

Particlescan
onlyvibrate
androtate
abouta fixed
position.

Particleshavemore
energyihan in the
solidstate

Particleshave
more energy
thanin the sotid
or liquidstates

Partidescan vibrate, .
rotateand slideover
eachother(have
translational
movement)

Particleshave
unrestricted
movement;can
vibrate,rotate
and move
anywherewithin
the container

Particles
cannotmove
a
throughout
solid,i.e.,no
translational
movement.
. Merung
Particlesgain
energyto melt.
Energyrequiredto
overcomestrong
forcesholdingthe
partidesin fixed
positions

. Boiling
Occurswhenthe
saturatedvapour
pressureof the liquidis
equalto the
external(atmospheric)
pressure.
Energyrequiredto
overcomethe forces
betweenthe particlesin
the liquidand tc increase
the distancebetween
themso lhat more
moleculeshaveenergy
to escapeinto the vapour
ohaseThe averagekinetic
energyof the molecules
remaining
in the liquid
thus
doesnotincrease,
remains
the lemDerature
whenthe liquid
constant
boils.

The Gas Laws

o The behaviourof gasis describedby fhe Gaslaws:
o Boyle'slaw
o Chades'slaw
o Avogadro's law
o Dalton'slawof partialpressure
o Theidealgasequation
r The physicalcondirion,or stateof a gas is determinedby
threequantities:
o Pressure,p; volume,V; temperature,
T;
o Amountof gas;usuallyexpressedas nurhberof moles

Bovles'slaw
At constant temperature, the vorumeof a fixed mass of gas is inversery
proportional
to it pressure,i.e

Vcc L
P
Therefore,the lawsexpressedmathematically
V = constantX 1
P
PV = constant

Graphicalrepresentation
of the Boyle'slaw

Chemistry2004

Mr Matthew Soh

's LawQuick
A sampleof gasoccupiesa volumeof 7.50dm3 at 0.988atm and2B.O"C
(a) Calculatethe pressureof the gas if its volumeis decreasedto 4.89 dm3 while
the lemperatureis heldconstant? ( 'l atrn= 101 KPa)
Pd.f
P,V, : 91 V1
- 1 'l x 0 , 4 t ? - - ? L / '

Charles'law
.

) +, 2 0 1

rtr. t, 5t 7a
77

At constiantpressure, the volume of a fixed mass of gas is direcfly

proportional
to its absolutetemperature
ftemperalureexpressedin Kelvln)
V cc T at constantP
V =c ons tantX T

i.e

r/k)

Law Quick

Whatis the effecton lhe volumeof one moleof a gaswheneachof the following
happens
(i)

Thetemperature
changesfrom600Kto 300 K at constantpressure

(ii)

Thetemperature
changesfrom300 K to 600 K at constantpressure

t',t d

vol.lt'r bcrtmt

(;r) 0 nlqpf

Chemistry2004

^a
ir^ctat

"tl

t' lit"'l
h0

+.4

*s'/-tj'

Mr MatthewSoh

Avoqadro's
'
'
'

Law

Underthe same condition of temperatureand pressure,equarvorumes

of
all gasescontainlhe equalnumber of moleculei.
Th.evolumeoccupiedby one moreof gas is rhe same for a[ qases. rt is
cafled the gas molarvolumes.lt measuiesat22.4 dm3ats.t.pdJt;.o ;;:
at r.t.p.
Thereforethe morar mass of a gas can be determinedwhen the volume
occupiedby the gas is known.

ie

Vot

,rloU.t

"f3os

atconstantrandP

GaseswhichobeyBoyres'srawandcharres'rawundera[ conditionsare
calledidealgases
By CombiningBoyles'slaw(pV = constant)and Charles'law(V/T =
constant),one obtainthe relationship

'
.

PV=Constant
T

I
Prr
P,Vt .: (6416f
: rLv:
:

t,

This is oftenwrittenas

1;

PrVr = PrV"

Tr

Tz

The ldeal Gas Equation

.

The equationof statefor an idealgascan be expressed:

P X V = conslantfor a givenmassof gas

T
lt-follows
from
Avogadro's
law that the constantis the samefor one mole
'
of all gases. lt is calledthe universalgas constant,with symbol R. fhe
equationbecomes
P V =R T
This is called the idear gas equation.For n moresof gas the equation
becomes
Chemistry2004

Mr MatthewSoh

PV=n
Gas Constant. R
o Notethatthe valueof R dependson the unitsof P,V , T and n
Valueof R
8.314
0.08206
1.987

Units
qrl-'K'

S.l unit)

L atm mol-1 K-1

Calmol-1K-1

WHY R = 8.314?
o The valueof R in S.l unitsis calculatedusingmolarvolumeof a gas at
s.t.pcondition
( s.t.pconditions
meansstandard
temperature
is 0 oCand1 atmospheric
pressure)
MolarVolume( Volumeof 1 mde of gas)at stp = 22.4dm'3= 2.24X'lO-2m3
= 1 atm= 101325Paor Nm-z
Pressure
= ooo = 273.15K
Temperature
UsingPV = nRT,

thus R = PV/nT

=1o1325-Pzz_2
-24_Xo2_st'
lmol X 273.'15
K

= 8.314 Jmol-lK

PV= m RT wherem = massof gasand[l = Molarmassof gas

PXMI=
m RT=p R T wherep = densityofgas

E-

Chemistry2004

Mr Matthew Soh

| ." -- tog6q
s
lr-1 -- 19 .^j
I drnt

?
I qro drn --

luorj

cl,3

lrnr

ldeal Gas Quick Check

9.2X 't0-'m

t,6t xt03

Solving aJinear equationwould tell you that there

can only be one
unknown in this linear equation.lf you had h"o ;il;"
in this equation,
eitheryou are wrongor lhe question.
RememberP V, T and n must be in their " correct"units.
^.

P'
Fl

I 9r xrot

<

8-r 19 x

' l P 6 x,o-l

jrb

-" o, o rPf,"o{

A volume485 cm3of a gasm-easured

at 40 'c of vapourmeasured
at 1.01x 105
Nm-'hasa massof 1.715g. Calculate
tnemotaimals ot gas

' - " q.i"*''

( ans = 4 omot '1)

Dalton'sLaw of partialpressure

{,. * *

= at I
ft".|-'l

ln a mixtureof gases(A, B, C and D), eachgas behaves

as if it werethe
onlygaspresent
This is basedon theassumptionthatthereare no chemicar
interactions
betweenthe gases.
The contribution
whicheachgas makesto the totarpressureis cated the
partial pressure.
ln a mixture,eachgas exertsits own pressure;independent
of the other
eachgasbehavesideally).
93:." t assuming
.lt is equalto the pressurewhichthe gas wouldexertif it aloneoccupied
the
container
The partialpressureof eachgas dependson the totar pressure
and on
the molefractionof thegas

Chemistry2004

Mr MatthewSoh

lllustration
Gas A alonoat tempt.T and \rolV

B at TemotT andwl V

oo
Ot

gas A molecule

gas B molecule

PressureofA, pA
= nARf

nA

no.o f molofA

Partial PressureofA , pA
= nART

. T.h" t99l pressu.e,

by a mixtureof gaseswhicfi do not react
chemicalry,
"r.f$
is the sum
of the partiarpd"uL'"r"rt"o
by the constituent
gases
i.e for a miliure of gasesA andB in a volumeV,
To tal pres s urep=P l +P g

when PAo portd pms$rr otA

PB r: perthl pnrrurc of A

Chemistry2004'

Mr MatthewSoh

Thislawassumeseachgas in the mixtureobeysthe idealgas equation,

Ptor.t =

naRT +nERT
VVV

= lltoufif

Mole Fraction
o Mole fractionis a dimensionress
numberthat expressesthe ratio of the
numberof molesof one componentgas lo the total numberof molesin
the mixture.
In a mixtureof gasA and gas B,
Molefractionof A =
Da__
Mole fraction of B =
r
.

ol + Fle
Ilg
ne * Ile

Sum of mol fraction= 1

Since nA is proportionalto VA ( Avogadro's law), mol fraction can also be
expressedas a ratio of volume.
Molefractionof A =
Vq_

Va+Ve

Relationshipbetweenmole frac-tionand partial pressure

PartialPressure
1. 3.00dm3nitrogenat a pressureof 101 Kpa and 7.00dm3of hydrogen
at a pressureof 101KPaarefed into a 10.0dm3conlainer.Wnit islne
partialpressureof eachgas?
Chemistry2004

l0

Mr Matthew Soh

x
Ptno =
/ 0, 5

?r"H,

#,

g,.ogrtot "

1 !'d5 xpr

'

x lnr 4r.tt :

t' Lo xlss P.7,

!. (l xlgr P11,
t.,to x tot

Pa//

2. A cylinderreceives2.50 dm3 of methane,7.S0 dm3 of ethane and

0.500dm" of propane,all at the same temperatureand pressure.The
pressureinsidethe cylinderis 5.0S X 105 pa. What is the partial
pressureof eachgas?

The ideal gas equaliondescribestwo gases behave,but it does not

explainwhy theybehaveas theydo, eg. Why doesa gasexpandwhen
heatedunderconstantpressure?
An idealgas is a hypothetical
gas that obeysBoyles's
lawand Charles'
'
lawat all temperature
and pressureconditions.
The kinetic-rnolecular
theorywas developedto explainthe properties
andbehaviourof idealgasesdescribedby the gas laws.

The kinetictheory of gases was put forward by RJ Clausiusand JC

Maxwell in 1857 and 1859 respectively.The theory tackles these
questionsby makingthreefundamentalassumptions
.

Gasescpnsistof moleculesthat are in a constantstate of random

motion;movingin a straightline. The moleculesmovein straightline
until they collidewith each other or with the walls of the container.
These collisions are perfec y elastic; this means that molecules
bouncesapartwith no net lossof energy.

The volume of all moleculesof the gas is negligiblecomparedto

the total volume in which the gas occupies. The moleculesare far
apart

The moleculeshave a range of speeds.The speed of a molecule

dependson its kineticenergy.As the temperatureincreasesthe kinetic
energyincreasesas, as a result,the averagespeed increases.The
averag kinetic energy is proportional to the absolute
temperature;thereforea certaintemperatureall gaseshavethe same
averagekineticenergy.

Srrrr h.,rc neglrfttc &r.r * .*zc{rbrt.

Chemistry2004

ll

Mr MatthewSoh

behaviourof gases
- Wtrenmovingobjectcollideswith a surfaceit exert
lS""T".
I ne colrslonof gas moleculeswith the wallsof the ontainer exerta force.
a force
which-results
in a pressure.The greaterthe numberof mole"ur"" ano in"
morefrequentand the pressurethly coltidewith thewatts t e gr""t
r ih"
,
pressureis.
Boyle's Law (V o 'rtp)- A decreasein the volumeof gaseswiil
cause
distance between the moleculeesand the *"if" if the containerthe
to
decrease.coflisionsare more frequentand the pressureexerted
by
the
gas thereforeincreases.
charles' Law (V o T) - As the temperatureincreases,both the
energy and the averagemolecularspeed increases.Molecule kinetic
hits the
wall.morefreguenflyand with moreforce,increasingthe pressureexerted
by the gas. As a resultthe wall movesoutwards:"thevolumeincreases
untila constantpressureis restored.

a
a

ldealgasesdo notexistin practice

Accuratemeasurementshow that all real gasesdo not obey the
ideal
gas equation(or Boyles'Lawand charles'Law)undercertain
conditions
of temperatureor pressure
The extentto whicha realgas departsfromidealbehaviourcan be
seen
from the PVIRT plots beljw ( Fi! 1 and Zl . fnese pfotsare obtained
from resullsofBoyles'Lawexperiments foi.t molof eachgas.

Chemistry2004

l2

Mr Matthew Soh

)J/cn,
,'

{----yrtur-

1000K

il
800

P (atm)
rrgure

1000
a

pv/ RT versusn..t<<,
r.. r^. 1 -^,

J-

Figure

z'

PVlRTwc;

:i::*,::*:,i;ift
*,Ttrff:.,,j:rtr#:i:i:i'r:ffif"l.;tr'[[r:
.

( So....c

Note: PV = nRT

.- Tvr Ce.^I'-,l(
c_
scn o.^4)

ideal gas equation

p V =n
RT
For

one mole of ideal oas

u""run.iio'.ioi'di"i1'#i:,"{*Hl,:,r1!Ti":lll,i;,l,l1liry
'

lmportant features from pV/RT plot

Fig 1- Pressure condition

'

ffiJr':lt f,ffiiln;"*"

deviation
fromidealbehaviour
is rarseandis

o At lowerpressure( usually
. Deviationfor gasessuch below10 atm),the deviationis small
r.rH:;;;
o Deviationfor H2 gasis relativellisrn"li."
"s.co, "no ' . "'" '';.n".
Fig 2 - Temperaturecondition .

At a highertemperatllg,tfle.leyia-tion
is smater . Behaviourof a rearqas
approachesmorecloselyto ttratoi
an'io:e"l.gl"""tnignu,temperature
Chemistry
2004
|1
Mr MatrhewSoh
'

'

In generar'the deviations.from
idearbehaviour
increaseas temperature
decrease.The deviation.lecomgs
.ig;in;ni'neir tne temperature
at
whichthegasis converted
intoa liouid

Hence,deviationfrom ideality is greatestat these conditions:

]wo..b3si9assumptionsof the kinetic_ moleculartheory for ideal gases are

invalid at these conditions- the iaear gas ;oi;ri""
assumedto have
negligiblevolumes,and haveno or negligibleintermolecutar
"r"attractions.
Real gases molecules do have finite volume, ancl
they have significant
intermolecular
attraction.

Averagedistancebetweenmorecures
is smal ( morecures
are very crose
together)
o Intermolecular
attractiondevelop,and
. Volume gas moleculebecomesignificant
comparedto the volume
.of
occupiedby the gas
'

lmpact on PV/RT (referto Fig .t)

'

At hrgh pnessure,the attractiveforcesreducethe force

with which gas
moleculeshit the container

Thisimplieslhat pressureof realgas is lessthanthatof

an idealgas
Therefore PV/RT< 1

Chemistry2004

l4

Mr Matthew Soh

Al vry high pressure, lhe volume of gas molectles become more

significantand tends to-be greaterthan that predictedby the idearjas
equation.The volumeeffectsdominateat veryhighpressures.

This impliesthat volumeof gas molecrlesbecomesignificantand tendsto be

greaterthanthat predictedby the idealgas equalion
The volumeeffects dominateat veryhighpressures
Therefore PV/RT> 1

The moleculeshave low averagekineticenergy.This reducesthe energy

neededto overcomeintermolecularattractiveforces. Thus, intermolecuLi
attractionare significant.

lmpact on PV/RT(referto Fig 2)

.

significantintermolecular
attractionat low temperaturereducesthe force
withwhichgas moleculeshit the container

PV/RT<1 (negativedeviation)
o Finitevolumeof gas morecures
causesthe positivedeviation(pv/RT >1)
at lowtemperature
or hightemperature
with highpressurecondition.
(Noticethat as temperatureincreases,the negativedeviation(PV/RT < 1)
decreases.This is dueto lessintermolecular
attractionat highertemperature.

NH3, Cq and other polar' moleculeshave significantintermolecular

attractions
These moleculesare also relativelylarge, thus lhe volume of the gas
moleculesis not negligible.
(* This term will be studied under chemical boding lecture)

Chemistrv2004

t5

Mr Matthew Soh

deviation?
Hz,Ar andNe are nonpolar-moleorles,thustheyhaverelati\retyweak
intermolectrlar
forces,almostlikeldealgass.
Theseare alsorelatvelysmallmolecules.

NOTE
Manygasesapprcximateto ideal behaviourat lorivpressurc(usually<10
atm)
andat hightemperatures
(temperature
welt auovetire ooilinspolil 6f the;;si
Mosrgasesat np or stp behavelike ideal gasesfor prac{icafpurposes
PV =nR Tc anbeus ed.

Chemistry2004

l6

Mr MatthewSoh

Basedon the kinetictheory,the absolutetemperature

of a gas is a measure
of the averagekineticenergyof it molecules
For example,increasingthe temperature
of a gas by 10 'C will doubtethe
.aveEge kineticenergyof its molecules.Thus, molecularspeed increases
withincreasing
temperature.
At conslanttemperature,the molectlesin a sampleof gas have avemge
kineticenergy,thusan averagespeed;butthe individualmoleculesmoveat a
varyingspeeds.At anyinstant,somearemovingrapidly,othersmoreslowly
This distributionof molecularspeedor energyis summarizedgraphicay in
the Maxwell- Boltzmann
distribution
curve

fraction
of
molecules
with
speedx

A typicat M-B
curye at a
particular
temperature

molecularspeed, x

The curve showsthe fractionof moteculesmovingat each speed.

At any instant, a small number of moleculeswitl be almost stationary
and a small numberwill be movingat very high speeds. However,the
majoritywill have speedsbetweenthesetwo extremes.
The largestnumberhas a speed conespondingto the maximumof the
curve,that is , more moleculespossessthis speed than any other. This
is the most probablespeed.
The area under the curve reflectsthe total number of moleculesin the
sample
Chemistry2004

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Mr MatthewSoh

ra

As the temperatureof the

lhe averagekineticenergy ;
g:"^1"_r:,_r."d,
thus the averagespeedof the
gasmoleculeincreasJJproportionaily.
At high temperarure,
the curveis shiftedt";il;dh:,
speed as the
withrow

"p;; ;;;;;;;#'

;i#3::g#ijr:j::

fraction
of
molecules
with
speed x

ll num
" berwnh

M-B curvcs ofa gas at two different

Iemperatures:
at lower tempcrature,
Tl
at highcr tempcrahuc,T2
-

molecularspeed x

fractionof moleculeswithspeedX1 or greater,

at Tl
fractionof moleculeswithspeedX1 or greater,
at T2
Note lhat the fractionor numberof molecutes
with speedX1 or greater
is considerably
largerat highertemperature
T2

Chemistry2004

l8

Mr MatthewSoh

fur"t l^ 0*d, ch"cfce$

.'.rV.cq'\

P{ +
? PM=P"\

=
d'm
0.q88
Y J'tnn
+.8qdr3
x
1.s0.1,,'3
g .l.b| trr.

1.4 {b" ,\^0P,eso

'J.

'
Tof" nol,e' tldls h.lgtbe cq'slsl'nl

P.c! d P oz V

Ctott"i lo,^rQur&ctpcl'
\--l

S,tr. V of T.

rf te Vd,n'e
{}"t
U Tgrpl,rt uog\es
rou.ldmeooe
Cil he ftngtderrooee
\
b alrrnesr hu Ptusurq,
) \r^o.

(tD ft.\p} tnl tnoroAb3 'ltto ltmos.

Pa*olpr6son4flS\D

Iie{hod1- .

vd,nat

Rv,- P,V,

trFH"P'V,=PrV,

P"=no*g,esrvX,

Pr'* xl o l K P c r

P"-' xrolKPq
*
P,-= fo.+kPq

B- = jo 3(.?t,
Ur

l.
ft\nhDd

Tftl wiorna
4- Vfttl Vq,ulurbe fo rnuno4 ftnh'ner
n

/i,

Viri. rr&-f*.h*,.,-,'Ifl'
,LH)Jt\Lrnil".o'-

Vir," Vrr-Cca,t,'nd
s'o|

= 1'o
[0 t-t

.ffrd p0{(<u\P

hih pr\rsru&s
,r.etoikPC
-,->
.: tofiU.ncr p{\Ssrrv-{
uc".ld }.9
X l0 | lsPq
i 0'd
l0l kfa

7 fidni dhano.

-lutot
pllsst$e

Jlooxot?"

J.odnr3
Fdl'*ne

PT''"

snoq.Vrd I

=
t'
Po.tlnt
ywcu*n
ft;.n, tr;
.Voir,rne
.

fr"*

h*.\-- J.5drn3'f
tr-54'n3+o5drn3
=

\O'5'Itn3

'

\--l

Pa*otp.^n.rrre
(popnne) x I Doxi0uPa
ft:f

-).+o x\o *P Q
=4.Lxb oSxr0ePcr
prrssurc(wltnt4
Po.t,,J
=)

J.O

i t| Y t A 5 f " | v
/\ [V
(t

pnss,'*6ufht,
!nn+,n.l

=J 5 X5.05Ii0'Krr
i05
-

. I Jo x tDtPrn,*,
= 5 05110%
vrr\r,t
Cho.Llutcr\odclec\