CHAPTER 5 - GASES

Properties of Gases
Gas has no fixed shape or volume;
It contains particles (atoms or molecules) separated by distances very much larger than
the particle size;
Gases are compressible and expandable due to plenty of empty spaces between
molecules;
Inter-particles attractions in gases are negligible;
Particles are constantly moving and colliding especially with container walls;
ollisions of particles with surfaces result in pressure!
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5.1 PRESSURE
Pressure is defined as force per unit area; Pressure =
Area
Force
; (P # $%&)
Force = mass x acceleration!
If mass in 'g and acceleration in m%s
(
) force # 'g!m%s
(
# *ewton (*)
Pressure #
2
meter
Newton
# *%m
(
# Pa (Pascal) +I unit for pressure)
Atmospheric Pressure or Barometric Pressure,
-he atmosphere contains a mixture of gases) mainly *( and .(! Gas molecules
constantly colliding with the /arth0s surface and results in the atmospheric pressure!
&tmospheric pressure is measured with a barometer) hence called barometric pressure! -he
first mercury barometer was invented in 1234 by an Italian scientist) /vangelista -orricelli
(1256 - 1237)!
-he first barometer was made of a meter-long glass tubing) closed at one end! -orricelli
filled the tubing with mercury and then inverted it into a bowl of mercury reservoir! 8e
found that the mercury column in the tubing only dropped to a level of about 45 inches
above the mercury reservoir! 8e explained that the mercury column is supported by the
air pressure that exerts on the surface of mercury in the bowl) thus preventing the
column from completely falling into the bowl! -orricelli mainly used his barometer to
determine the relationships between changes in the air pressure with the weather!
Pressure may be expressed in terms of the height of a li9uid column! Pressure exerted by a
li9uid column is directly proportional to the gravitional constant) g) the density of li9uid) d, and
the height of the column) h.
Pressure = g.d.h
+ince g and d are constant for a given li9uid) pressure is proportional only to the height of that
li9uid column! :ased on the mercury barometer) pressure is expressed in terms of the height of
mercury column supported by that pressure! &t sea level) the atmospheric pressure supports a
mercury column of 725 mm tall! -hus 1 atm = 760.0 mmHg = 760.0 torr!
(In honor of -orrichelli) 1 torr is defined to be e9uivalent to 1 mm8g!)
.ther pressure units are; 1 atm = 14.70 psi) and 1 atm = 101 325 Pa (1 Pa # 1 *%m
(
)!
Pascal (Pa) is the +I unit for pressure!
1
/xercise-1;
1! & car tire is inflated to a pressure of 4(!5 psi! onvert this pressure unit to atm) torr) and
'ilopascal ('Pa)! (&nswer; (!53 atm; 1<<5 torr; (57 'Pa)
(! -he osmotic pressure of an a9ueous solution is measured in terms of water column that
rises above the solution! If the osmotic pressure is 16!5 inches of water (density # 1!55
g%cm
4
)) what is the osmotic pressure in mm8g, (density of mercury # 14!2 g%cm
4
)
(&nswer; 44!2 mm8g)
4! If 1 atmospheric pressure supports a mercury column 72!5 cm tall) what height of water
column can be supported by the same pressure, (density of water # 1!55 g%cm
4
; density
of mercury # 14!2 g%cm
4
) (&nswer; 15!4 m or 44!= ft)
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Manometer or Pressure Gauge,
Manometer is a device used to measure gas pressure in a container! -here are two
types of manometers > opened-end and closed-end manometers! 8ow are these two
manometer different from each other and how are they ali'e, ?hich one gives the reading of
the gas pressure in the tan' directly, ?hich one re9uires you to 'now the air pressure in order
to determine the gas pressure in the gas tan',
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5. T!e Gas "a#s $ %o&le's( C!arles's( an) A*o+a)ro's "a#s
Gas behaviors are governed by the mathematical relationships between pressure) temperature)
volume) and the molar 9uantity of the gas! -hese relationships are summarized into various gas
laws) such as) Boyles law) which summarizes the inverse relationship between volume and
pressure of a gas sample at constant temperature; Charless law summarizes the direct
relationship between volume to temperature at constant pressure) and Ao!a"ros law relates
the gas volume to molar 9uantity of the gas at constant temperature and pressure!
Boyles !a";
&t constant temperature) !as olume is i#ersely proportio#al to its pressure!
V
P
1
; V =
P
b
; or PV = b (- is constant and b is a numerical constant)
$or a given 9uantity of gas at constant temperature) if the volume changes from @1 to @() then
the gas pressure will also change from P1 to P() such that)

P1,1 = P,; then) V2 #
2
1 1
P
V P
; and P2 #
2
1 1
V
V P
(8ow would the plots of @ ersus P and @ ersus 1%P loo' li'e,)
/xercise-(;
1! & gas is compressed from (3!< A to 1!<5 A at constant temperature! If the initial pressure
of the gas was 5!=62 atm) what is the final pressure, (&nswer; 12!1 atm)
(! -o what new volume should a 5!11(-A gas expands so that its pressure drops from 4<!5
psi to <!<5 psi, (&nswer; 5!714 A)
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2
#harless !a";
&t constant pressure) the olume o$ a !as sample is "irectly proportio#al to its
temperature i# %eli#!
, T) or , = cT; (where c is a numerical constant and - is in Belvin!)
$or a given 9uantity of gas at constant pressure) if the temperature (in Belvin) changes from -1
to -() then the volume will change from @1 to @() such that)
2
2
T
V
=
1
1
T
V
; then) @( # @1(-(%-1) and -( # -1(@(%@1)
(8ow would the plot of @ versus - loo' li'e,)
If the temperature increases) but the volume remains unchange) then the gas pressure will
increase! -he pressure-temperature relationship at constant volume can be summarized by the
expression;

1
1
T
P
=
2
2
T
P
; and P( # P1(-(%-1) ; and -( # -1(P(%P1);
/xercise-4;
1! If a 43<-mA sample of gas at is heated from (5
o
to 155
o
at constant pressure) what is
its final volume, (&nswer; 34= mA)
(! & given gaseous sample is compressed at constant pressure to one-half its initial volume!
If the initial temperature is ((
o
) what is its final temperature, (&nswer; -1(2
o
)
4! & car tire is inflated to a pressure of (6!5 psi at ((
o
! &fter driving for 1 hr) the tire
pressure is found to have increased by 6!<C! ?hat is the new temperature (in
o
) of the
air inside the tire, (&nswer; 37
o
)
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A$ogadro%s !a"
&t constant temperature and pressure) the olume o$ a !as is "irectly proportio#al to
the #umber o$ moles o$ the !as!
, n; @%# # a ; (where a is a constant) and - D P are constant);
,-n = ,1-n1 ;
-he &vogadro0s law implies that e&ual olumes o$ !ases at the same temperature a#" pressure
co#tai# the same #umber o$ moles 'he#ce the same #umber o$ molecules(!
&tandard 'emperature and Pressure (&'P)
+ince gas volume is temperature and pressure dependent) it is necessary to defined a
sta#"ar" temperature and pressure condition when describing the molar volume of gas! -he
sta#"ar" temperature a#" pressure (or +-P) implies T # (74!1< B (5
o
) and P # 1!555 atm!
It was experimentally determined that) at +-P) 1!555 mol of ideal gases occupy a volume of
((!313 A) which is the molar olume of ideal gas at +-P!
3
/xercise-3;
1! ?hat is the volume of 5!264 mol of nitrogen gas at +-P, (&nswer; 1<!4 A)
(! 8ow many moles of helium gas would occupy a volume of 2!6 x 15
4
A at +-P,
(&nswer; 4!5 x 15
(
moles)
4! &n amount of ozone gas occupies a volume of (!53 A at 1 atm and (<
o
! If all of this gas
is converted to oxygen) what would be the volume of the oxygen gas under the same
temperature and pressure, -he reaction is; ( .4(g) 4 .((g)
(&nswer; 4!52 A)
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*.+ 'he ,deal Gas !a"
ombining :oyleEs) harlesEs and &vogadroEs Aaws we obtain the following expression;
V
P
T n
; or V =
P
T) R(n
; (where R is a universal gas constant!)
-his leads to the ideal gas e9uation; PV = nRT
+ince 1!555 mol of ideal gases has a volume of ((!313 A at +-P) R # .../.0
".atm
-mol.1.
If P is expressed in torr) R = 0.20
".torr
-mol.1
$or a fixed amount of gas) :oyle0s and harles0s laws may be combined to yield the following
relationships between volume) pressure and temperature;
, 3T-p4; @ # (a constant)(-%P)
?hich yields the expression;
1
1 1
T
V P
#
2
2 2
T
V P
;
Fe-arranging the above expression) we obtain other e9uations) such as;
V2 = V1.(
1
1
T
P
).(
2
2
P
T
); P2 = P1.(
1
1
T
V
).(
2
2
V
T
); T2 = T1.(
1 1
2 2
V P
V P
)
/xercise-<;
1! & sample of nitrogen gas has a volume of 1(!( A at (<
o
and 1!5 atm! ?hat is its volume
at -(5
o
and (6< torr, (&nswer; (7!2 A)
(! & sample of ideal gas has a volume of 1(5 mA at (<
o
and 7<5 torr! If the gas is
compressed to 72 mA and the pressure decreases to 256 torr) what is the new
temperature of the gas, (&nswer; -1(5!
o
or 1<4 B)
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)si#! *"eal +as ,&uatio#s to -ole .olar .ass a#" /e#sity o$ +as0
4
A. 5etermination of 6olar 6ass7
$or an ideal gas) P@ # nF-; P@ # (g%G)(F-);
where g is mass in grams) and G # molar mass of gas)
which yields PG # (g%@)(F-))
+ince density) " # g%@) PG # dF-) and 6 = dRT%P;
%. Gas 5ensit&( d =
RT
P
1! Gas densities vary greatly with temperature and pressure; it decreases as temperature rises
and increases as pressure increases!
(! Gas density is directly proportional to its molar mass!
(/xplain how does a hot-air balloon wor'!)
/xercise-2;
1! & (!76-g sample of a gas occupies a volume of 3!(3 A at (4!2
o
and 7<< mm8g! ?hat is
the molar mass of the gas, (&nswer; 12!1 g%mol)
(! ?hat is the density (in g%A) of hydrogen chloride gas) 8l) at 1!55 atm and (<
o
,
(&nswer; 1!3= g%A)
4! If the average molar mass of air is (= g%mol) calculate the density of air at (<
o
and at
2<
o
) respectively! (&nswer; 1!1= g%A at (<
o
) and 1!5< g%A at 2<
o
)
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5.8 Gas Stoic!iometr&
If a reaction involves gaseous reactants and%or products) the molar 9uantities of such
substances can be calculated using the ideal gas e9uation (n # P@%F-)) provided their volumes
at a certain temperature and pressure is 'nown! $or example) the molar volume of ideal gas at
+-P (sta#"ar" temperature a#" pressure) is ((!3 A! -hus) the molar 9uantity of an ideal gas
can be calculated from its volume at +-P) such that) n # (@olume at +-P)%((!3
/xercise-7;
1! .xygen can be prepared in the laboratory by heating solid potassium chlorate) Bl.4)
which decomposes according to the e9uation;
( Bl.4(s) ( Bl(s) H 4 .((g)
alculate the volume (in liters) of oxygen gas produced if the temperature is (4!2
o
and
the pressure is 74< mm8g when 47!( g potassium chlorate is completely decomposed,
(&nswer; 11!< A of .( gas)
(! +odium azide (*a*4) decomposes when ignited according to the following e9uation;
!
( *a*4(s) ( *a(s) H 4 *((g)
8ow many grams of *a*4 must decompose to produce <<!5 A of *( gas at 41
o
and 615
mm8g of pressure, (&nswer; 15( g of *a*4)
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5.5 5alton9s "a# of Partial Pressure
Partial Pressure) Pi) is the pressure that a gas in a mixture would exert if it were to be
present alone in the same container! In a mixture containing non-reacting gases & and :) if the
partial pressure of gas & is P&) and that of : is P:) the total gas pressure is)
Ptotal # P& H P: ;
If P& # (n&)(F-%@)) and P: # (n:)(F-%@)
-hen) Ptotal # P& H P: # (n& H n: )(F-%@) # ntotal(F-%@)
IaltonEs Aaw states that) Jthe total pressure o$ a mi1ture o$ !ases is e&ual to the sum o$ the
partial pressures o$ i#"ii"ual !ases i# the mi1tureJ!
Ptotal # Pi # P1 H P( H P4 H!!!
(where) P1) P() P4) etc!) are partial pressures of individual gases in the mixture)
?hen a gas is collected over water) the gas contains water vapor) which also exerts pressure)
called the water vapor pressure) Pw! -he total pressure of the collected gas is the +KG of the
gas pressure and the water vapor pressure! If the atmospheric (or barometric) pressure and
the vapor pressure of water at a particular temperature are 'nown) the pressure of dry gas can
be calculated as follows;
P- # Pbar # Pgas H Pw; Pgas # Pbar > Pw;
/xercise-6;
1! & <!55-A container contains (<!5-g gaseous mixture of <5!5C *() 1<!5C .() and 4<!5C
8e) by mass! ?hat is the total gas pressure inside the container at (<
o
,
(&nswer; total gas pressure # 14!3 atm)
(! & <!55-A container contains 5!34 mol .( and 5!<7 mol *( gases at (<
o
! ?hat are the
partial pressure of each gas in the container and the total pressure of the mixture,
(&nswer; P.( # (!1 atm; P*( # (!6 atm; Ptotal # 3!= atm)
4! & piece of zinc metal is reacted with excess hydrochloric acid) 8l(a9)) and the hydrogen
gas produced is collected over water at (3!3
o
! (a) ?rite a balanced e9uation for the
reaction! (b) If the total pressure of the gas mixture (8( and water vapor) is 7<4!6 mm8g
and the total gas volume was 2<6 mA) calculate the moles of 8( produced!
(c) 8ow many grams of the zinc were reacted! (-he vapor pressure of water at (3!3
o
is
(4!5 mm8g!) (&nswer; (b) 5!5(<= mol of 8(; (c) 1!2= g of Ln reacted)
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5.0 T!e 1inetic 6olecular T!eor& of Gases
"
Ideal gas laws are derived from empirical data and observations of gas behavior! -hese
laws are summaries of physical characteristics of gases at relatively low pressures!
-he -inetic Molecular 'heory (BG-) of gases consists of a set of postulates) which try to
explain this behavior of gases! -he theory is summarized as follows;
1. +ases co#tai# particles 'molecules or atoms( that are poi#t masses 2 their total molecular
olume is #e!li!ible compare" with the olume occupie" by the !as.
2. .olecules are i# co#sta#t3 ra#"om motio#s; molecular collisio#s are completely elastic
3. *#termolecular $orces are #e!li!ible 4 particles #either attract #or repel each other.
4. 5he aera!e 6i#etic e#er!y o$ a !as sample is "irectly "epe#"e#t o#ly o# the temperature
i# %eli#!
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Usin+ t!e 16T of +ases to e:plain +as la#s7
Pressure-.olume /elationship
&t constant temperature) gas molecules travel with a constant average speed! Feducing
the volume results in shorter distances traveled by molecules) which leads to a higher
fre9uency of molecular collisions! -his leads to a higher gas pressure) as stated by :oyle0s law!
Pressure and 'emperature
Faising the temperature causes an increase in the average molecular speed! -his causes
the fre9uency of molecular collision to increase and leads to a higher gas pressure! Gay-Aussac
law states that gas pressure will increase proportionally with temperature at constant volume!
.olume and 'emperature
-o maintain a constant pressure when the temperature increrases) the volume of the gas
must increase) so that the fre9uency of collisions is reduced! harles0s law states that gas
volume will increase proportionally as the temperature is increased at constant pressure!
011ect o1 ,ncreasing the 2um3er o1 Molecules on Gas .olume
?hen more molecules are added to the same volume at constant temperature) the
number of molecular collisions will increase) which leads to an increase in pressure! If the
pressure were to be constant) the volume must increase) in accordance with &vogadro0s law!
'emperature and /oot-Mean-&4uare &peed
-he root4mea#4s&uare spee" of gas molecules at a given temperature is given by the
following expression;
urms = (2RT-6)
where F # 6!413 M%mol!B # 6!413 'g!m%(s
(
!mol!B)! -herefore) the molar mass G must be given
in 'g%mol! (M # 'g!m
(
%s
(
)! $or example) the root-mean-s9uare speeds for 8( and .( at 5
o
are;

urms for 8( # (4 x 6!413 'g!m
(
!s
-(
!mol
-1
!B
-1
x (74 B) # 1!63 x 15
4
m%s
((!512 x 15
-4
'g!mol
-1
)
urms for .( # (4 x 6!413 'g!m
(
!s
-(
!mol
-1
!B
-1
x (74 B) # 321 m%s
(4(!55 x 15
-4
'g!mol
-1
)
-he urms of 8elium gas at (<
o
is;
#
urms # (4 x 6!413 'g!m
(
!s
-(
!mol
-1
!B
-1
x (=6 B) # 1!42 x 15
4
m%s!
(3!5 x 15
-4
'g!mol
-1
)
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5.< Effusions an) 5iffusion
5i11usion is the term used to describe the mixing process of gases or when a gas spread
out from a source; while e11usion is the passage of gas through a tiny opening! -he rate of
effusion implies how fast gas escapes through this opening!
-homas Graham (165< > 162=)) a +cottish chemist) found that the rate o$ e$$usio# o$ a
!as is i#ersely proportio#al to the s&uare root o$ its molar mass!
Fate of effusion 1""
G
-he relative rates of effusion of two gases at the same temperature and pressure are e9ual to
the inverse ratio of the s9uare root of their molar mass! :ased on the 'inetic molecular theory)
rate o$ e$$usio# is "irectly proportio#al to the root4mea#4s&uare spee") urms) of the gas
molecules! -he relative rates of two gases can be expressed as follows;
$ gas o% e%%&sion o% Rate
A gas o% e%%&sion o% Rate
#
$ gas o%
A gas o%
rms
rms
u
u
#
) (3RT'
) (3RT'
$
A
#
A
$

$or a given period) the relative number of moles of gas & and : effused is;
e%%&sed $ gas o% o(
e%%&sed A gas o% o(
#
A
B
M
M
+ince effusion time is the inverse of rate) if ta is the effusion time for an amount of gas &) and tb
is the effusion time for the same amount of gas :) then)
$ gas o% ime )%%&sion t
A gas o% ime )%%&sion t
#
B
A
t
t
#
B
A
M
M
-he relative rate of diffusion of two gases may be expressed in terms of the relative distance
traveled by these gases for a given period of time such that)
$ mo(ec&(e *+ tra,e(ed distance
A mo(ec&(e *+ tra,e(ed distance
#
A
B
M
M
/xercise-=;
1! ?hat is the average 'inetic energy and urms of *( molecules at +-P, -he molar mass of *(
is (!6 x 15
-(
'g%mol! (F # 6!413 M%mol!B; M # 'g!m
(
!s
-(
) (&nswer; urms # 3=4 m%s)
(! &t a certain temperature and pressure) 2!( mg of *( gas effuses through an opening in =5!
seconds! 8ow much of 8( gas would effuse through the same opening in =5! seconds
under the same condition, (&nswer; 1!7 mg of 8()
-
4! alculate the relative distance traveled by; (i) *84 and 8l gases; (ii) *84 and 8(+ gases)
under the same temperature and pressure!
(&nswer; *84 travels 32!3C farther than 8l; *84 travels 31!<C farther than 8(+)
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5./ Real Gases
-he ideal gas e9uation represents an approximation of the behavior of real gases at high
temperature and low pressure! $or ideal gases) P@ # nF-; where the compressibility $actor) z #
P@%nF- # 1! $or a mole of ideal gas) n # 1; z # P@%F- # 1! $or real gases) the
compressibility factor) z # P@%nF- 1!
-wo factors cause the deviation from ideal behavior! $irstly) intermolecular forces exist in
real gases) which become very significant at high pressure and low temperature when
molecules are closer together! &ttractive forces tend to reduce the effective gas pressure; the
pressure of a real gas is lower than that expected for an ideal gas under the same condition!
+econdly) gas molecules are not point masses; they occupy a finite space in the container! -he
space occupied by gas molecules are not compressible) which reduces the compressibility factor
of the gas! Knder moderate pressure) both intermolecular forces and molecular volume lead to
a compressibility factor of less that 1!
-he mathematical e9uation that represents the behavior of real gases is very
complicated! 8owever) a simplified version of the van der ?aals e9uation for real gases) which
ta'es into account intermolecular forces and molecular volume of gas particles) provides an
approximation of the behavior of real gases! -he van der ?aals e9uation for the pressure of
real gases is;
P =
) . (V
RT
nb
n
-
2
2
V
a n
;
?hen re-arranged) it yields the following e9uation;
(P H n
(
a ) x (@ - nb) # nF-; a # factor due to intermolecular forces
@
(
b # molecular volume
$or a given gas) the weighting factors a and b are determined by iteration method until one that
gives the best fit of the observed pressure is obtained under all conditions!
&t low pressure there are fewer gas molecules and the total molecular volume (#b) is
negligible relative to the volume @ occupied by the gas! Knder this condition) the free (space)
volume available to the gas molecules is essentially e9ual to the volume of the container! &t
high pressure) @ is small and the molecular volume of the gas becomes significant and the free
volume available becomes significantly less than the volume of the container!
?hile at high temperature) molecules are moving very fast and interparticle interactions
become insignificant and the term (P H n
(
a'@) P! -hus) real gases approach ideal behavior
under low pressure and high temperature conditions!
/xercise-15;
/
1! Kse (a) the ideal gas e9uation) and (b) the van der ?aals e9uation) to calculate the
pressure exerted by the following gases when the volume and temperature are <!55 A and
(=6 B) respectively;
(i) 1!55 mol of l((g) (a # 2!3= A
(
!atm!mol
-(
; b # 5!5<2( A!mol
-1
);
(ii) 1!55 mol of .((g) (a # 4!<= A
(
!atm!mol
-(
; b # 5!53(7 A!mol
-1
);
(c) ?hich gas shows the greater departure from ideal behavior,
(&nswers; (i) (a) 3!6= atm) (b) 3!2= atm; (ii) (a) 3!6= atm) (b) 3!7= atm; (c) hlorine)
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5.= C!emistr& of t!e Atmosp!ere
-he principal components of the atmosphere are nitrogen and oxygen gases) but .(
and 8(. are important atmospheric gases that 'eep the /arth0s climate moderately warm! -he
atmosphere is divided into different strata) based on how the temperature changes with
altitude! In order of increasing altitude) they are; the troposphere) stratosphere3
mesosphere3 thermosphere) and e6osphere! &bout ==C of the atmosphere0s mass lies
within 45 'm from the /arth0s surface) and 7<C lies within the lowest 11 'm) which covers the
entire troposphere) where climatic changes occur! -he four maNor components of a clean) dry
air in the troposphere are *( (76!56C)) .( ((5!=<C)) &r (5!=4C)) and .( (5!54C)) (all
percentages are by volume)!
Pressure and 'emperature $ariations o1 the Atmosphere
-he mass of the atmosphere is the highest at sea level and decreases with altitudes)
which results in the decrease of pressure! ?ithin the troposphere) atmospheric pressure
decreases from 725 torr at sea level to about 1<5 torr at the upper boundary! -his rapid
decrease in pressure is also the result of a gradual decrease in temperature! ?ithin the
troposphere) temperature drops by about 7
o
per 'ilometer until ><<
o
((16 B)! 8owever) in
the stratosphere temperature increases from about (16 B (-<<
o
) to (65 B (7
o
) at <5 'm!
?hile in the mesosphere) temperature drops smoothly again to about 165 B (-=4
o
) at around
65 'm! ?ithin the thermosphere) which extends to approximately <55 'm) temperature rises
again) but varies between 755 and (555 B) depending on the intensity of solar radiation and
sunspot activity! -he e1osphere) which is the outermost region) maintains these temperatures
and merges with the outer space!
.ariation in #omposition
:ased on the chemical compositions) the atmosphere is usually divided into two maNor
regions) homosphere and heterosphere! -he homosphere includes the troposphere)
stratosphere) and mesosphere) and the heterosphere covers the thermosphere and exosphere!
-he homosphere has a relatively constant composition) containing (by volume)
approximately 76C *() (1C .() and 1C mixture of other gases (mostly &rgon)! -he
composition of the homosphere is relatively uniform due to co#ectie mi1i#!! &ir directly in
contact with land is warmer than the air above it! -he warmer air expands) its density
decreases) and rises through the cooler) denser air) and mixing occurs! -he cooler air sin's and
comes in contact with lands) which eventually becomes warm and rises) and the convection
process continues! +oaring birds and glider pilots use this convection air current to stay aloft!
-he heterosphere contains regions that are dominated by few atomic or molecular species!
onvective heating does not reach these heights) so the gas particles become layered according
to molecular mass; nitrogen and oxygen molecules in the lower levels) oxygen atoms in the
next) followed by helium and hydrogen atoms!
10
/mbedded within the lower heterosphere is the ionosphere) containing species such as
.
H
) *.
H
) .(
H
) *(
H
) and free electrons! Ionospheric chemistry involves numerous light-induced
bond brea'ing (photo4"issociatio#) and light-induced electron removal (photo4io#i7atio#)
processes! $or example) the formation of oxygen atoms occurs by the following steps;
*( *(
H
H e
-
(photo-ionization)
*(
H
H e
-
* H *
* H .( *. H .
* H *. *( H .
111111111111111111111111111
.( . H . Ooverall photo-dissociation of .(P
111111111111111111111111111
>?one in T!e Stratosp!ere
Gost of the high-energy solar radiation is absorbed by the thermosphere! 8owever) a
small amount reaches the stratosphere causing photo-dissociation) which brea's .( to . atoms!
-he energetic . atoms collide with other .( molecules to form ozone (.4);
.((g) ( .(g); (photo-dissociation)
.((g) H .(g) H *((g) .4(g) H *(
Q
8ere) *( serves as an energy sin' to absorb excess energy produced by the exothermic reaction
of .4 formation! +tratospheric temperature increases with altitude due to this exothermic
reaction!
-he ozone layer in the stratosphere is vital to live on /arth because it absorbs a great
portion of solar ultraviolet (K@) radiation) which causes its decomposition;
.4(g) H K@ .((g) H .(g)
K@ radiation is extremely harmful because it can cause bond dissociations and) thus) interrupt
normal biological processes! ?ithout the stratospheric ozone) much more of this radiation would
reach the /arth surface) resulting in increased mutation and cancer incidence!
5epletion o1 'he 78one !ayer
Knder normal conditions) the stratospheric ozone concentration varies seasonally but
remains fairly constant annually through the complex series of atmospheric reactions! -wo
reactions that maintain a balance in ozone concentration are the following;
.((g) H .(g) .4(g) OformationP
.4(g) H .(g) ( .((g) Obrea'downP
8owever) based on the ground-brea'ing research by Paul rutzen) Gario M! Golina) and $!
+herwood Fowland) for which they received the *obel Prize in 1==<) we now 'now that the
release of industrially produced chlorofluorocarbons ($s) has shifted the balance by
catalyzing the brea'down reaction!
$s are used as air-conditioning refrigerants) plastic foam reagents) and aerosol
propellants! -hese lead to large 9uantities of this product being released into the atmosphere!
$s are chemically inert near the /arth0s surface) but once they reach the stratosphere) the
high-energy K@-radiation causes them to dissociate and release l atom (reactive free
radicals);
$(l((g) H K@-radiation $(l(g) H l(g)
11
hlorine atomic is very reactive) which readily attac's ozone molecules and brea'ing it down to
oxygen gas;
.4(g) H l(g) .((g) H l.(g)
l.(g) H .(g) .((g) H l(g)
RRRRRRRRRRRRRRRRRRRR
*et reaction; .4(g) H .(g) ( .((g)
RRRRRRRRRRRRRRRRRRRRRRRRRRR
-herefore) chlorine atoms produced by the photodissociation of $s) acts as a homogeneous
catalyst in the brea'down reaction of the ozone gas!
Eart!'s Primiti*e Atmosp!ere
+cientists agree that the primitive /arth0s atmosphere did not contain oxygen gas! -he
origin-of>life models propose that about 1 billion years after the earliest organism appeared)
blue-green algae evolved! -hese on-celled organisms used solar energy to produce glucose by
photosynthesis;
2.((g) H 28(.(l) H h 281(.2(a9) H 2.((g)
&s a result of this reaction) the .( content of the atmosphere increased and .( decreased! -he
increase in .( allowed more oxidation reactions to occur) which changed the geological and
biological ma'eup of the early /arth! Iron(II) minerals changed to iron(III) minerals) sulfites
changed to sulfates) and eventually organisms evolved that could oxidize other organisms to
obtained energy! It has been estimated that the level of .( may have increased to the current
level of about (5C approximately 1!< billion years ago!
Atmospheric Pollutants
-he chemistry of the troposphere is strongly influenced by human activities! Aarge amount
of gases and particulates are released into the troposphere by our highly industrial civilization!
+evere air pollution occurs especially around many large and industrial cities! -he two maNor
sources of air pollution are transportation and processing plants that use petroleum and coal as
fuel sources! -he combustion of petroleum in vehicles produces .) .() *.) and *.() along
with unburned molecules from petroleum! ?hen this mixture is trapped close to the ground in
stagnant air) reactions occur producing chemicals that are potentially irritating and harmful!
-he complex chemistry of air pollution seems to center around the nitrogen oxides (*.x)!
&t the internal combustion engines of cars and truc's) where temperatures are high) *( and .(
(from air) react to form *. that is released into the air with other exhaust gases! *. is then
immediately oxidized to *.() which absorbs K@-radiation and brea's up into *. molecules and
oxygen atoms (.);
*((g) H .((g) ( *.(g)
( *.(g) H .((g) ( *.((g)
*.((g) H K@ *.(g) H .(g)
.xygen atoms may combine with .( to form ozone;
.(g) H .((g) .4(g)
.zone is a very strong oxidizing reagent) which attac's other pollutants as well as materials)
causing the latter to be degraded at a faster rate! .zone on the /arth0s surface also undergoes
photo-dissociation) producing energetically excited .( molecules (.(
Q
) and oxygen atom (.
Q
)!
-he latter readily react with water molecule to form hydroxyl radicals (.8)) which is strong
oxidizing agent!
12
.
Q
H 8(. ( .8
.8 radical can oxidize *.( to form nitric acid; .8 H *.( 8*.4!
-he free radical .8 can also react with unburned hydrocarbons in the polluted air to produce
other chemical that are irritating and harmful to the respiratory system! -he end product of this
complex processes is often referred to as p!otoc!emical smo+) so called because light is
re9uired to initiate some of the reactions! O*ote that) while ozone layer is desirable in the
stratosphere to bloc' most of the uv-radiation from the sun) it is highly harmful on the /arth0s
surface because of its strong oxidizing property!P
-he other maNor source of pollution results from burning coal power plants! Guch of the
coal found in the Gidwest contains significant amount of sulfur) which) when burned) produces
sulfur dioxide;
+(in coal) H .((g) +.((g)
Feaction of +.( with oxygen in the air produces +.4) which readily dissolves in rainwater to
form sulfuric acid;
+.((g) H 2.((g) +.4(g)
+.4(g) H 8(.(l) 8(+.3(a9)
+ulfuric acid is highly corrosive to both living things and building materials; its present in acid
rain has resulted in damaging effects on the environments! In many parts of the northeastern
Knited +tates and southeastern anada) acid rain has caused some freshwater la'es to become
too acidic to support a9uatic life!
-he use of high-sulfur coal by power plants further aggravates the pollution problems! &n
industrial method to reduce the amount of +.( released into the atmosphere is by using a
system called a scrubber before it is emitted into the power plant stac'! & common method of
scrubbing is to blow powdered limestone (a.4) into the combustion chamber) where it is
decomposed to lime and carbon dioxide;
a.4(s) a.(s) H .((g)
-he lime then combines with +.( to form calcium sulfite;
a.(s) H +.((g) a+.4(s)
-o remove the calcium sulfite and any remaining unreacted +.( gas) an a9ueous suspension of
lime is inNected into the exhaust gases to produce slurry of a+.4!
Knfortunately) there are many problems associated with scrubbing! -he systems are
complicated) expensive and consume a great deal of energy! -he large 9uantities of calcium
sulfite produced in the process present a disposal problem! ?ith a typical scrubber)
approximately 1 ton of a+.4 per year is produced per person served by the power plant! +ince
no use has been found for this compound) it is buried in a landfill! -hus) air pollution by sulfur
dioxide will continue to be a maNor problem) one that is expensive in terms of damage to the
environment and human health as well as in monetary terms!
13
Appen)i:
'emperature and /oot-Mean-&4uare &peed
-he goals of BG- of gas are to provide plausible explanations of the molecular behavior
of gases that are related to pressure and temperature of the gas! -he 'inetic energy of a
molecule of mass m and traveling at speed ux in x-direction is ex # Smux
(
!
+imilarly) the 'inetic energy of an identical molecule traveling in the y- and z-direction is
ey # Smuy
(
and ez # Smuz
(
) respectively!
-he average 'inetic energy of a molecule traveling in any direction is) ek #
1
%4(
4
%( mu
(
)
-hen) the average 'inetic energy of a mole of gas particles is
,k # 8&(Smu
(
) # SGu
(
where 8& is the &vogadro0s number!
+ince molar mass G # 8&m, ,k # SGu
(
$orce is the change in momentum per unit time! ?hen a molecule traveling with speed u
collides with the wall head-on and bounces in the opposite direction with the same speed) the
change in its momentum # (mu per collision.
If the molecule is in a cubic box of length 9) the distance traveled by molecule between collision
is 9) and the time ta'en between collision is t # 9'u! onse9uently)
$orce # ( mu # ( mu = ( mu
(
!
t 9'u 9
If this force were concentrated on one face of the wall of area 9
(
) the pressure exerted on that
face of the wall is $orce # ( mu
(
% 9
area 9
(

If the same force is applied on all the six faces of the cubic box) the average pressure exerted
on each wall is P # ( mu
(
% 9 # mu
(
29
(
4@
In a mole of gas) the average pressure exerted by the &vogadro0s number of molecules in @
volume is
P #
3V
) (
2
A
mu N
#
3V
) ( 2
2
2
1
A
mu N
#
V
) )( (
2
2
1
3
2
Mu
:ut) for one mole of gas) the pressure P =
V
RT
=
V
) )( (
2
2
1
3
2
u
= (

-2)0k
-his implies that the average molar 'inetic energy of gas is 0k =
1
-6u

# (
2
-)RT!
-hat is) the average molecular 'inetic energy of a gas is dependent only on the temperature (in
Belvin)) but is independent of the 9uantity or the molar mass of the gas!
+ince molar mass is G # 8&m) then *&(
1
%( mu
(
) #
1
%(Gu
(
#
4
%(F- )
+ince
1
%(Gu
(
#
4
%(F- u
(
# 4F-%G) and urms = (u

) = (2RT-6))
where F # 6!413 M%mol!B # 6!413 'g!m%(s
(
!mol!B) and urms is called the root4mea#4s&uare
spee"!
14
&t constant temperature) the root-mean-s9uare speed urms is i#ersely proportio#al to the
s&uare root o$ the molecular mass! &t constant temperature) the ratio of the root4mea#4s&uare
spee" of two gases with molar masses G& and G: is given as)
(urms of gas &) # (4F-%G&) # (G:%G&)
(urms of gas :) (4F-%G:)
$or example) under the same temperature) the urms of 8( is about 3 times that of .(;
(urms of 8() # (Golar mass of .() # (4(!5 g%mol) # 3
(urms of .() (Golar mass of 8() ((!5( g%mol)
""""""""""""""""""""""""""""""""""""""""""""""""""""""""""""""""""""""""""
A))itional E:ercises
1! &n aerosol-spray can contains a gas at 1!6( atm when the temperature is ((!5
o
! ?hat
is the pressure inside the can when it is placed in a boiling water at 155!
o
! (&ssume gas
temperature e9uals that of boiling water) (&nswer; (!45 atm)
(! ?hat volume of *() measured at 74< torr and 35
o
) is produced when <5!5 g of sodium
azide) *a*4) decomposes according to e9uation; (&nswer; 45!2 A)
( *a*4(s) ( *a(s) H 4 *((g)
4! 8ow many grams of methane gas (83) would consume 7!3< A of .((g) at (7
o
and 7<1
mm 8g when the former reactant is completely combusted, (&nswer; (!4= g of 83)
3! If 5!5541( mol *(. effuses through an orifice over a period) how much *.( would effuse
in the same period of time under the same conditions, (&nswer; 5!5545< mol)
<! -he density of oxygen) .() is 1!3(=53 g%A at +-P! ?hat is the molecular mass of a gas
whose density is 5!6=4(5 g%A at +-P, (&nswer; (5!551 u)
2! & sample of gas that occupies (75 mA at 735 torr and =6
o
weighs 5!465 g! ?hat is its
molar mass, (&nswer; 33!5 g%mol)
7! If the density of acetone vapor is (!5= g%A at 1!55 atm and 2<
o
) calculate the molar mass
of acetone! (&nswer; <6!5 g%mol)
6! & small bubble with a volume of (!1 mA rises from the bottom of a la'e) where the
temperature and pressure are 6
o
and 2!3 atm) respectively! If the temperature and
pressure on the surface are (<
o
and 1!5 atm) respectively) what is the final volume (in
mA) of the bubble if its initial volume was (!1 mA! (&nswer; 13!4 mA)
=! & 6!47-g sample that is =(!5C Bl.4) by mass) is decomposed and the .( gas produced is
collected over water at (4!5
o
and 726!< mm 8g pressure! -he decomposition proceeds as
follows;
( Bl.4(s) ( Bl(s) H 4 .((g)!
?hat is the volume of gas collected, (@apor pressure at (4!5
o
is (1!1 mm8g!)
(&nswer; (!44 A of .()
1!