Gases

PropertiesofGases
GasLaws(pressure,volume,temperature,
moles)
GasesinChemicalReactions
TheKineticModelofGases

Gaseouselements

Pressure=Force/Area

BoylesLaw

V~1/P
Ifafixedamountofgas
isreleasedintoalarger
container,
howmuchforcedoesit
exert?

Ifthevolumeofagasisconstrainedtoasmallercontainer,
howmuchforcedoesitexert?

P~1/V
BoylesLaw:
P1V1=P2V2

Relationship
between
volumeand
pressure.

V1

P1

P1V1=P2V2

Decreasevolume
morecollisions

V2

 Ex.1Asampleofgasoccupies21litersata
pressureof2.2atm.Whatwouldbethevolumeif
thepressurewasincreasedto6.2atm?

Ex.2AsampleofO2occupies10.0Lat785torr.
Atwhatpressurewoulditoccupy14.5L?

Ifthetemperatureofgasisincreased,howwillitsvolumerespond
(ifthepressureiskeptconstant)?

CharlesLaw:
V1/T1=V2/T2

Gas1
Gas2
Gas3
Gas4

Thepointwhereagas
wouldhavezerovolume!

Ifagasisheated,howmuchforcedoesitexert
(ifthevolumeiskeptconstant)?

P~T

CombinedGasLaw
(BoyleandCharles)
P1V1

=P2V2

T1

T2

RecapofGases:
BoylesLaw:
P1V1=P2V2

CharlessLaw:
V1/T1=V2/T2

P1V1=P2V2
T1

T2

1) Gasequationsshouldmakesense:volume,pressure,temperature
2) Watchyourunits!(K,L,atm)

Onestandardizedsetofconditions=
STP
0oC(273K)
1atm(760Torr)

 Ex.3AballoonfilledwithHeoccupies413mLat
100.oC.Atwhattemperaturewoulditoccupy577mLif
thepressurewasconstant?

Ex.4Asampleofhydrogensulfide(H2S)occupies210L
at27oCat1200T.WhatvolumewoulditoccupyatSTP?

Howmuchvolumedoes1moleofgasoccupy
at0oC,1atm?
IfonemoleofArgonoccupies22.1L,howmuchvolume
willbeoccupiedby:
onemoleCO2
onemoleN2
onemoleO2
onemoleH2

Howmuchvolumedoes1moleofgasoccupy
at0oC,1atm?

Liters

Idealgas:22.41Lpermole

Ex.5Whatisthedensityofagasthathasa
molarmassof44.01g/molatSTP?

IdealGasLaw:PV=nRT
(wheren=moles)

WhatisR?

STP=0oCand1atm

 Ex.6Whatisthevolumeofaballoonfilledwith32.02
gramsofHeliumwhentheatmosphericpressureis722
torrandthetemperatureis40oC?

Ex.7TheGoodyearblimpmustbeinflatedwithHelium
priortoafootballgame.Itsvolumeis7601ft3.How
manygramsofHeareneededforapressureof740torrat
22oC?
(1ft3=28.3L)

 Ex.9A0.723gsampleofagasoccupies
176mLat100.oCand750.torr.Whatisits
molarmass?

StoichiometricCalculationsInvolvingGases
C3H8+5O23CO2+4H2O
25.0gofpropaneproduceshowmanymolesofCO2?
25.0gofpropaneproduceshowmanylitersofCO2atSTP?
Howmanygramsofpropaneareneedtoreactwith
50.0LofO2at25oCand1.0atm?

KeyConcepts:
IdealGasLawPV=nRT
STP(0oCand1atm)
Standardmolarvolume:22.4L/moleatSTP
Gasesinstoichiometriccalculations

Anairbaginflatesinlessthan50msecbythereactionofNaN3
toproduceNaandnitrogengas:
NaN3Na+N2
Thevolumeoftheairbagisabout30Lwheninflated,anditis
filledtoapressureof1.4atm.HowmanygramsofNaN3must
beusedforeachairbag?ThemolarmassofNaN3is65.1
g/mole.Assumetheprocessoccursatroomtemperature.

Gasmixtures
DaltonsLawofpartialpressures
Thetotalpressureofamixtureofgasesequalsthe
sumofthepressuresthateachwouldexertifit
werepresentalone
PT=P1+P2+P3+.Pn
Exercise:
A gaseous mixture is made from 6.00g oxygen and
9.00g methane placed in a 15L vessel at 0oC. What is the partial
pressure of each gas and the total pressure in the vessel?

Daltonslawof
partialpressures
PT=Pa+Pb+Pc+Pd=
Rememberthateachpressure
isalsoequalto:nXRT/V

MoleFractions
Theration1/nTiscalledthemolefraction(denotedx1),a
dimensionlessnumberbetween0and1.

P1 n1RT / V
n1

PT nT RT / V nT
n1
P1
nT

PT

Mole fraction of N2 in air is 0.78, therefore if the total

barometric pressure is 760 torr, the partial pressure of N2 is
(0.78)(760) = 590 torr.

KineticMolecularTheory
Theorydescribingwhygaslawsareobeyed(explainsbothpressureand
temperatureofgasesonamolecularlevel).
Completeformoftheory,developedover100yearsorso,publishedby
Clausiusin1857.
Gasesconsistoflargenumbersofmoleculesthatareincontinuous,
randommotion
Volumeofallmoleculesofthegasisnegligible,asare
attractive/repulsiveinteractions
Interactionsarebrief,throughelasticcollisions(averagekineticenergy
doesnotchange)
AveragekineticenergyofmoleculesisproportionaltoT,andallgases
havethesameaveragekineticenergyatanygivenT.
Because each molecule of gas will have an individual kinetic energy, and thus
individual speed, the speed of molecules in the gas phase is usually characterised
by the root-mean-squared (rms) speed, u,(not the same though similar to the
average speed). Average kinetic energy = mu2

ApplicationtoGasLaws
IncreasingVatconstantT:
ConstantTmeansthatuisunchanged.
ButifVisincreasedthelikelihoodof
collisionwiththewallsdecreases,
thusthepressuredecreases(Boyles
Law)
IncreasingTatconstantV:
IncreasingTincreasesu,increasing
collisionalfrequencywiththewalls,
thusthepressureincreases(IdealGas
Equation).

 Ex.10A20.5Lbulbcontains0.200molesofmethane,
0.300molesofhydrogen,and0.400molesofnitrogenat
20.0oC.Itisstinkyandexplosive.Whatisthepressure
insidethebulb?Howmuchpressureiscontributedby
eachofthethreegases?

Ex.12Onetankofgascontains5.00LofN2at32.0atm.
Asecondtankcontains3.00LofO2at24.0atm.What
pressureisattainedwhenthevalvebetweenthetanksis
opened?

Molefraction:theportionofaspecificsubstance
withinamixture

Whatistheportion(molefraction)ofredspheres?

Kineticmodelofgases

eachdotis
onegas
molecule

TheKineticMolecularTheory
Thebasicassumptionsofkineticmoleculartheoryare:
Postulate1
Gasesconsistofdiscretemoleculesthatarerelativelyfar
apart.
Gaseshavefewintermolecularattractions.
Thevolumeofindividualmoleculesisverysmallcompared
tothegassvolume.

ProofGasesareeasilycompressible.

TheKineticMolecularTheory
Postulate2
Gasmoleculesareinconstant,random,straight
linemotionwithvaryingvelocities.

ProofBrownianmotiondisplays
molecularmotion.

TheKineticMolecularTheory
Postulate3
Gasmoleculeshaveelasticcollisionswith
themselvesandthecontainer.
Totalenergyisconservedduringacollision.

ProofAsealed,confinedgasexhibitsno
pressuredropovertime.

TheKineticMolecularTheory
Postulate4
Thekineticenergyofthemoleculesis
proportionaltotheabsolutetemperature.
Theaveragekineticenergiesofmoleculesof
differentgasesareequalatagiven
temperature.

ProofBrownianmotionincreasesas
temperatureincreases.

TheKineticMolecularTheory
Thekineticenergyofthemoleculesisproportionalto
theabsolutetemperature.Thekineticenergyofthe
moleculesisproportionaltotheabsolutetemperature.
DisplayedinaMaxwelliandistribution.

TheKineticMolecularTheory
Thegaslawsthatwehavelookedatearlierinthischapterare
proofsthatkineticmoleculartheoryisthebasisofgaseous
behavior.
BoylesLaw
P1/V
AstheVincreasesthemolecularcollisionswithcontainer
wallsdecreaseandthePdecreases.
DaltonsLaw
Ptotal=PA+PB+PC+.....
Becausegaseshavefewintermolecularattractions,their
pressuresareindependentofothergasesinthecontainer.

 CharlesLaw
VT
Anincreaseintemperatureraisesthemolecularvelocities,
thustheVincreasestokeepthePconstant.

TheKineticMolecularTheory
Therootmeansquarevelocityofgasesisavery
closeapproximationtotheaveragegasvelocity.
Calculatingtherootmeansquarevelocityis
simple:

u rms

3RT
Mm

Tocalculatethiscorrectly:
ThevalueofR=8.314kgm2/s2Kmol
AndMmustbeinkg/mol.

TheKineticMolecularTheory
Example1217:Whatistherootmeansquare
velocityofN2moleculesatroomT,25.0oC?

u rms

kg m 2
3 8.314 2
298 K
sec K mol

0.028 kg / mol
515 m / s = 1159 mi / hr

TheKineticMolecularTheory
Whatistherootmeansquarevelocityof
HeatomsatroomT,25.0oC?

TheKineticMolecularTheory
u rms

kg m
3 8.314 2
298 K
sec K mol

0.004 kg / mol

1363 m / s = 3067 mi / hr
CanyouthinkofaphysicalsituationthatprovesHe
moleculeshaveavelocitythatissomuchgreater
thanN2molecules?
WhathappenstoyourvoicewhenyoubreatheHe?

DiffusionandEffusionofGases
Diffusionistheinterminglingofgases.
Effusionistheescapeofgasesthrough
tinyholes.

DiffusionandEffusionofGases
Thisisademonstrationofdiffusion.

DiffusionandEffusionof
Gases

Therateofeffusionisinverselyproportional
tothesquarerootsofthemolecularweights
ordensities.
R1

R2

M2
M1
or

R1

R2

D2
D1

DiffusionandEffusionofGases
CalculatetheratiooftherateofeffusionofHe
tothatofsulfurdioxide,SO2,atthesame
temperatureandpressure.

R He

R SO 2

M SO 2
M He

641
. g / mol

4.0 g / mol
16 4 R He 4 R SO 2

DiffusionandEffusionofGases
Example1216:Asampleofhydrogen,H2,wasfoundto
effusethroughapinhole5.2timesasrapidlyasthesame
volumeofunknowngas(atthesametemperatureand
pressure).Whatisthemolecularweightoftheunknown
gas?
R H2

R unk

5 .2

M unk
2.0 g/mol

M unk
2.0 g/mol
27( 2.0 g/mol) = 54 g/mol

27
M unk

M unk
M H2

RealGases:
DeviationsfromIdeality
Realgasesbehaveideallyatordinary
temperaturesandpressures.
Atlowtemperaturesandhighpressuresreal
gasesdonotbehaveideally.
Thereasonsforthedeviationsfromidealityare:
1. Themoleculesareveryclosetooneanother,thus
theirvolumeisimportant.
2. Themolecularinteractionsalsobecomeimportant.

RealGases:
DeviationsfromIdeality
vanderWaalsequationaccountsforthebehaviorof
realgasesatlowtemperaturesandhighpressures.

n 2a
V nb nRT
P +
2
V

The van der Waals constants a and b take into

account two things:
1. a accounts for intermolecular attraction
2. b accounts for volume of gas molecules
At large volumes a and b are relatively small
and van der Waals equation reduces to ideal
gas law at high temperatures and low
pressures.

RealGases:
DeviationsfromIdeality

Whataretheintermolecularforcesingases
thatcausethemtodeviatefromideality?
1. Fornonpolargasestheattractiveforcesare
LondonForces
2. Forpolargasestheattractiveforcesare
dipoledipoleattractionsorhydrogen
bonds.

RealGases:
DeviationsfromIdeality
Example1219:Calculatethepressureexertedby
84.0gofammonia,NH3,ina5.00Lcontainerat
200.oCusingtheidealgaslaw.
1 mol
n = 84.0 g NH 3
4.94 mol
17.0 g

L atm
4.94 mol 0.0821
473 K
nRT
mol K

P=

V
5.00 L
P 38.4 atm

RealGases:
DeviationsfromIdeality
SolveExample1219usingthevander
Waalsequation.
L2 atm
n = 4.94 mol a = 4.17
b = 0.0371 L
2
mol
mol

n 2a
P + 2 V - nb nRT
V

nRT
n 2a
P=
2
V - nb V

RealGases:
DeviationsfromIdeality

473K 4.94 mol 4.17

P

2
L
5.00 L (4.94 mol)(0.0371 mol )
5.00 L
4.94 mol 0.0821

L atm
mol K

L2 atm
mol 2

191.8 L atm
P
4.07 atm (39.8 atm 4.1 atm)
4.817 L
P 35.7 atm which is a 7.6% difference from ideal

Realgases
Deviationsfromidealbehaviorasgasesare
exposedto:
highpressures
lowtemperatures
(Whathappensathighpressuresandlow
temperatures???)

Themolarvolumeisnotconstantasisexpectedforidealgases.
Thesedeviationsduetoanattractionbetweensomemolecules.
Finitemolarmolecularvolume.
For compounds that deviate from ideality the van der Waals
equationisused:

2a

n
P+
(V - nb) = nRT
whereaandbareconstantsthatarecharacteristicofthegas.

2
V

Applicableathighpressuresandlowtemperatures.

Ideal:PV=nRT
Real:(P+an2/V2)(Vnb)=nRT
aisamolecularattractivityfactor
bisamolecularvolumefactor

Ideal:P=nRT/V
Real:
P=nRT/(Vnb)an2/V2

Realgases

Ex.13Calculatethepressureexertedby5.00moles
ofNH3ina1.00Lvesselat25.0oCassumingideal
andnonidealbehavior.

CompressionFactor

Variation of Z with Pressure

At 0 C

molar volume
molar volume perfect gas

pV
RT

Low pressures, Z=1, all gases ideal

At high pressures, Vreal >Videal ; Z>1
repulsive forces dominate
Low pressure, Vreal <Videal, Z< 1
attractive forces dominate
Low temperatures -> molecules moving
less rapidly more influenced by
attractive forces

VanderWaalsEquation(1873)
RT
a
p
2
Vm b Vm

nRT
n
p
a
V nb
V

a reflects how strongly molecules attract each other

b corrects for the molecules size

DerivationofvdwEq.State
Repulsiveinteractionscausemoleculestobehaveas
impenetrablespheres
MoleculesrestrictedtosmallervolumeVnb,wherenbis
volumemoleculestakeup
Pressuredependsonfrequencyofcollisionswithwallsand
forceofeachcollisionbothreducedbyattractiveforces
proportionaltomolarconcentration(n/V)
Pressureisthenreducedaccordingtoa(n/V)2

PhaseTransition:Condensation
Imagine you are compressing gas with piston
At C, piston slides without further change in
pressure
Liquid begins to appear Two phases coexist
Going to E amount of liquid increases
Pressure along CDE is vapour pressure
At E, sample is liquid now the compressibility
changes .
Similar behave happens in lipidic or polymeric
systems, which exhibit a rich variety of phase
transitions
Experimental isotherms of
CO2 at several temperatures.

CriticalConstants
The `critical isotherm', the isotherm
at the critical temperature Tc, is at
31.04 C. The critical point is
marked with a star.
Critical pressure

Pc

Critical molar volume Vc

Tc, Pc,Vc critical constants

If you compress along Tc, liquid

does not appear these highly
dense materials are called
supercritical fluids and their
properties are a subject of intense
current research

VirialEquationofState
Most fundamental and theoretically sound
Polynomial expansion Viral Expansion

PV
1 B2 P ( P ) P B3 P ( P ) P 2 ...
RT

PV
B (T ) B3V (T )
1 2V

...
2
RT
V
V

B2V (T =) 0 at Boyle temperature

Used to summarize P, V, T data
Also allow derivation of exact correspondence between
virial coefficients and intermolecular interactions