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(135)
:
/

Properties of
Gases
(135)
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)(136

The Properties of Gases
)( :
)( )( .

.
.
) (
.
)
( .
.
)(136
)(137
/

) ( .

.

) (ice
) (water ) (steam ).(water vapor
(can exist in all
) .three states
. ) (fluid
) .(flow freely )(
) (condensed states .
) (
) (common substances .
)(137
)(138
/
:
)Gas (at 100 C
Density
Molar
)(g/ml
Volume
ml/mol
0.000588 30600
30600
0.00255
)Liquid (at 20 C
Density
Molar
)(g/ml
Volume
ml/mol
0.998
18.0
89.2
0.876
Solid
Density
Molar
)(g/ml
Volume
ml/mol
0.917 (0
19.6
)C
0.899 (0
86.9
)C
1.70 (- 25
90.5
)C
substances
)water (H2O
)Benzene (C6H6
Carbon
1.59
96.8
0.00503
30600
tetrachloride
)(CCl4
The molar volume of a substance is the volume occupied by one mole of that substance
.
) (
) (solids and liquids are many times denser than gases
) (very far
) .(much closer together
) (18 ml

) (30600 ml ) (100 C .

)
:
)(P = 0.006 atm (4.579 mmHg) , T = 0.01 C = 273.01 K
) (triple Point
)) (g ) (S ) ((L
)(1 atm
) (0 C .
)(138
)(139
/

:
) (T = 3096 C = 2823 K ).(1 atm
) (100 atm ) (3700 C
.3850 C CaCO3
) (
CaO CO2
.
) CaO(s) + CO2 (g
CaCO3 (s)

: .
) (

.
.
) (
.
) (1 atm, 25 C
.
) . (Bomb Calorimeter

.
)(139
)(140
/
:
) (1 atm, 25 C

) ( .
.
)) (NaCl(s ) (800 C
).(1000 C
) (
) (CO )(CO2
) (HCl ) (CH4
.

.
.

.
)
( : : H2
N2 O2 F2 .Cl2
)( ) : :(8 A
He Ne Ar Kr Xe Rn
)(140
)(141
/
) (O3
.
) (
.
) (HCN .deadly poison
) (CO ) (H2S
) (NO2 ) (SO2 ) (O3
. less toxic
) ( ) (colorless
F2 light yellow
Br2
) (NO2 ) ) (reddish brown

).(greenish yellow
) (He, Ne
.

.
25 C ) (1 atm .
) (
.
)(141
)(142
/
: )(1 atm, 25 C
)(
)(Diatomic Molecules
)(
Monatomic
Gases (Noble
)Gases
He
Helium
)(
)(
H2
Molecular
Hydrogen
Hydrogen
Fluoride
NO2

Ne
N2
HCl
Molecular
Neon
Nitrogen
Nitrogen
Hydrogen
Dioxide
Chloride
HBr
N2 O

Ar
O2

Nitrous Oxide
Argon
Molecular
Hydrogen
Oxygen
Bromide
HI
SO2

Kr
O3
Hydrogen
Krypton
Sulfur Dioxide
Ozone
Iodide

Xe
F2
CO H2S

Xenon
Hydrogen
Molecular
Carbon
Sulfide
Fluorine
Monoxide
CO2 * HCN

Rn
Cl2

Radon
Molecular
Hydrogen
Carbon
Chlorine
Cyanide
Dioxide
NH3
Ammonia
* HCN ) (26 C
NO
HF

Nitric Acid
)(142
(143)
/
4 : Table
Some Characteristic of Solids, Liquids, and Gases
Solids
Liquids
Have definite shape (resist Have

deformation)
no
Gases
definite
shape Have no definite shape (fill
(assume shapes of container)
containers completely).
Are nearly incompressible Have definite volume (are only
Are compressible
very slightly compressible).

Usually
have
higher
Have high density
Have low density
Are not fluids
Are fluid
Are fluid
Diffuse only very slowly
Diffuse through other liquids
Diffuse rapidly
density than liquids
through solids
Have
an
ordered Consist of disordered clusters Consist
of
extremely
arrangement of particles of particles that are quite close disordered particles with much
that
are
very
close together;
together, particles usually random

have
only
vibrational
particles
motion
in
have empty space between them;

three particles have rapid, random
dimensions
motion in three dimensions
motion.

Properties of Gases

.
.
.
.(formed) ( consumed)
( in common) ( many properties)
:
(143)
)(144
/
( -

0.1 %
.
.

.
.
.

.

.
70 % )
(

.
.
.
.70 %
)(144
)(145
/
( )) (Gases are easily compressed
(
)(
.
)

( .
.
.
)(
) (N2 28 10-3 kg
273 K ) (1 atm = 1 105 N/m2
) (22.4 10-3 m3 )(0.441 10-3 m3
273 K ) (1 106 N/m2
.

)(0.0349 10-3 m3
) (1 105 N/m2 ) (0.0345 10-3 m3
) (5 106 N/m2
) (N2(S .
)(145
)(146
/
: ) (0 C
N/m2
1 105
1 106
5 106
)N2(g
m3
22.4 10-3
0.441 10-3
)N2(L
m3
0.0349 10-3
0.0345 10-3

.
5 %
.

(solids and liquids are almost
).incompressible
) ( :
( ) (expand
)
)(146
)(147
/

(
.

.
) (0.1 10-3 ) (1 10-3 m3

).(100 m3

.
. ) (Cu ) (Sn

.
.

.

.
)(147
)(148
/
)(
19 ml
) (30600 ml ) (100 C
).(Atmospheric Pressure
(
)
( )
(
.
.
Fig. 3 : Diffusion of bromine vapor in air. Some liquid (dark reddish

brown) was placed in the small inner bottle. As the liquid evaporated, the
resulting reddish brown gas diffused.
)(148
)(149
/

).(immiscible

.

.
)(
) (CO2
) (Br2

.
.

.
( .
( .
)(149
)(150
Fig. 4 : The pressure of a gas arises from the collisions that its molecules
make with the walls of the container. The storm of collisions exerts an
almost steady force on the walls.
( )(may be liquefied
) .(by cooling and compressing
) (Volatile liquids
).(or slightly above
( ) (can easily be altered
.
.
( ) (

)(150
)(151
/
.
:
(
( .
.
(
(

:
m
V
=d
)(
) (N2 kg/m3
) (
m3 :
))(V(N2)(g) = 2.400 10-3, V(N2)(L) = 0.0346, V(N2)(S) = 0.0272
).(N = 14
) (273 K (1
) atm :
= 1.25 kg/m3
28 10-3 kg
3
2.400 10 m
-3
m
V
)(g
dN
)(151
)(152
/
= 809.24 kg/m3
28 10-3 Kg
3
0.0346 10 m
-3
m
V
)(L
dN
:
= 1029.41 kg/m 3
28 10 -3 kg
3
0.0272 10 m
-3
m
V
)(S
dN

.
(
)
(
.
( ) F2
light yellow
greenish yellow Br2 NO2
reddish brown .violet
( )
( .
.
)(152
(153)
:
/
(153)
)(154
/

(
(
.
(
.
( .
( .
(
. .
( .
(
(
(
(
1. Gases can be compressed into smaller volumes, that is, their densities
can be increased by applying increased pressure.
2. Gases exert pressure on their surroundings.
3. Gases expand without limit so that gas samples completely and
uniformly occupy the volume of any container.
4. Gases diffuse into each other (mix) so that two samples of gas placed
in the same container mix completely almost immediately. Conversely,
different gases in a mixture like air do not separate on standing
Gases are described in terms of their temperature and pressure, the
volume occupied, and the amount (numbers of molecules or moles) of gas
present. For example, a hot gas occupies a greater volume and exerts a
greater pressure than does the sample of gas when it is cold.
)(154
)(155

)) .(atmosphere ) .((500 mil
.
) (beneficial
). (undesirable products
) ( ) (atmosphere total mass
5.3 1015 ) (metric tons
.
. .

.
)( (78 %
) N2 ) (unreactive gas ) (21 % O2
) (1 % ) (Ar
).(CO2
) (
.

. 30000
)(155
)(156
/
.
)
.(high altitudes
)( ) (50 % (6.4
) km ) (90 % ) (16 km )(99 %
).(32 km

.
) (
.

) (reduce the pressure
.
.

.

.
)(156
(157)
:
/
( Homogeneous mixing)
( compressibility)
.
.
(packed closely
together)
.
:
composition of dry air at sea level
% by volume
% Mass
Constituent
(percentage by
volume)
Nitrogen
N2
78.084
75.52
Oxygen
O2
20.948
23.14
Argon
Ar
0.934
1.29
Carbon dioxide*
CO2
0.033 (variable)
0.05
Neon
Ne
0.00182
1.27 10-3
Hydrogen
H2
0.0010 (0.00005)
Helium
He
0.000524
7.24 10-5
Methane*
CH4
1.7 10-4 (variable))
9.4 10-5
Krypton
Kr
0.000114
3.3 10-4
+
Carbon monoxide
CO
0.00001
Xenon
Xe
0.000008
Ozone+
O3
0.000002
Ammonia
NH3
0.000001
Nitrogen dioxide+
NO2
0.0000001
Sulfur dioxide
SO2
0.00000002
The greenhouse gases carbon dioxide and methane relate to fuels and
the burning of fuels for energy production.
+ Trace gases of environmental importance.
(157)
)(158
/
) (0.1%

(normal
) circumstances ) (99.9% ) .(empty space

) (70 % .
.
.

. ) (pumping up ) (inflating
) (hardness .
) (P ) (force = f
) .(area = a ) (mass
) (acceleration = a ).(a = 9.81 m/s2
F
m a
=
A
A
=P
) (N ) (1 N = 1 kg m/s2
) (SI ) (Pa )(1 Pa = 1 N/m2 = 1 kg/ms2

) (10.2 mg ).(1.00 cm2
:
)(158
)(159
m
-6 kg
kg.m
10.2 mg 10 mg 9.80665 s 2 1.00 10-4
ma

s 2 = 1.00 Pa
=P
=
=
-4
2
A
1.00 10 m 2
2
-4 m
1.00 cm 10
cm 2
)
( ).(250 Pa

.
) (1.00 m2
) (10300 kg
) (atmospheric pressure ) (101000 Pa ) (101 kPa
:
) 10300 103g (9.80665 m/s 2

ma
=P
=
= 101008 Pa = 101 kPa
A
1.00 m 2

)mercury
(mm Hg = millimeter of
) .(atm = atmosphere (1 mm Hg = 1
) torr ) Evangelista Torricelli (1608 1647

.
)(159
)(160
/

Standard State of Matter
) (
)(1 atm
) (25 C ) (298 K
.

)Standard (Normal) Conditions (SC
)Standard Temperature Pressure (STP
) (0 C = 273 K ).(1 atm

:
:
) (n ) (V ) (P ) .(T

.
( : (Temperature) T

.
.

.
.
. :
)(160
)(161
/

.

) ( .
:
( Celsius Temperature Scale
) (100 C
) (0 C ) (100 C
) (Centigrade Scale
).(C
( Fahrenheit Temperature Scale

. ) (180

) (32
) (.
212
)(161
)(162
/
( Kelven Temperature Scale

.(Kelvin) K ) (- 273.15 C
) (

)
( .
" " .
) (273.16 K
H2O ) (
) : ( .
H2O ) (0.01 K
H2O H2O )(273.15 K
) (273.15
373.15
).(0.15
) (200 K .
.

) (5/9 :
)(162
(163)
C = ( F - 32)
K = C + 273.15
5
9
F - 32
1.8
or K = C + 273
or
C=
K = ( F - 32) + 273.15
9
(163)
(164)
:
/
Fig. 7 : Temperature scales. Zero on the absolute scale is the lowest

possible temperature (0 K or 273.15 C).
(164)
)(165
/
( Mass )(Quantity

) (SI kg
).(mol
) (n )
( )
( ) (Mw ) (N ): (M
m
Mw
N
=n
) where ( N A = 6.023 1023
NA
=n
)n = MV(L
.
( : (Volume) V
.
.

.
. m3

0.001 m3 = 10-6 m3
= 0.001 m3
)(165
)(166
/
:
( 1 L = 1 dm3 = 1000 ml = 1000 cm3 = 0.001 m3), (1 m3 = 1000 L = 1000
)dm3

.
.

.

.
.
. ) (1 ml

) (1 ml .

.

. .

)(166
)(167
/
.
.
( : (Pressure) P

.
.

.

.

.

.

.
.
) .(straw ) (sucking

.
)(167
)(168
/
) (F
).(A

.

) (velocity ).(acceleration
) (change in distance
) (elapsed time :
distance moved
elapsed time
= velocity
) (SI unit ) (m/s )(cm/s

): (acceleration
:
change in velocity m s-1
= m/s2
elapsed time s
= acceleration
) (m/s2 ).(cm/s2

:
force = mass of object acceleration
)(168
(169)
:
/
: ( N) ( SI unit)
1 N = 1 kg m/s 2
:
pressure =
force N
= N/m2 = Pa
2
area m
( pa)
1 Pa = 1 N/m2
:
a summary of the four properties of a gas are given in the following
table.
property
Pressure (P)
Volume (V)
Temperature (T)
Amount (n)
Properties that describe a Gas

description
unit(s) of measurement
The force exerted by gas against atmosphere (atm); mm Hg; torr
the walls of the container.
The space occupied by the gas
liter (L); milliliter (mL)
Determine the kinetic energy and Celsius (C); Kelvin (K) required
rate of motion of the gas particles.
in calculations.
The quantity of gas present in a grams (g); moles (n) required in
container.
calculations.

.

.
(169)
)(170
/

. .

.
.
.
.
.

) = (N/m2
N
2
m
)Force F(N
=P
=
= N/m 2 = Nm -2 = Pa
2
) Area A(m
) (Intensive
) (Extensive . ) (SI
)) (N/m2( .

) (cmHg
).(mmHg
)(170
)(171
/
=
) )
(
P=h.d.g
13595.1 Kg
9.806665 m
P = 0.760 m
= 101325.2 kg. m /m 2 s 2 = 101325.2 N/m 2
m3
s2
13.5951 g
980.6665 cm
= 1 .013252 10 6 g. cm /cm 2 s 2 = 1.013 10 6 dyne/cm 2

P = 76 cm
cm 3
s2
2
2
dyne = g. cm/s
where : N = kg . m/s ,
) (atm .
.
.
:
:
Pressure Units
)SI Unit : pascal (Pa
1 Pa = 1 kg /m.s2 = 1 N/m2
other common units
1 bar = 100000 Pa = 100 kPa
1 atm = 101325 N/m2 = 101325 Pa = 101.325 kPa = 1.01325 bar = 1.013 x 106 dyne/cm2
1 atm = 0.76 mHg = 76 cmHg = 760 torr = 760 mm Hg
1 atm = 14.7 lb/inch2 (psi) = 1.01325 bar
: ) (atm
units of measuring pressure
unit
abbreviations
unit equivalent to 1 atm
atmosphere
atm
)1 atm (exact
millimeters of mercury
mm Hg
760 mm Hg
torr
torr
760 torr
inches of mercury
in. Hg
29.9 in. Hg
pounds per square inch
)lb/in.2 (psi
14.7 ib/in.2
pascal
Pa
101325 Pa
) (torr ) (Torricelli) (Pa

) .(Pascal
)(Manometer
)(171
)(172
/
) (Barometer
Evanglista
.Torrcelli

. )(
760 mm .0 C

) (.
.

) (45
760 mm
).(0 C
)(
) (71 cm Hg :
( )(
( ).(atm
( 71 cm Hg )( :
:
)(172
)(173
/
76 cm Hg = 101325 Pa
71 cm Hg = P
71 cmHg
P =101325 Pa
76 cmHg
P = 94658.88 Pa
( 71 cm Hg atm
:
1 atm = 76 cmHg
Patm = 71cmHg
71 cmHg
P = 1atm
76 cmHg
P = 0.934 atm
)(
) (F = 100 N
) (100 m2
100 N
= 1N/m 2 = 1 Pascal
2
100 m
=P
1 Pa
.
)(
) (100 N
)(1 m2
)(173
)(174
100 N
= 100 N/m 2 = 100 Pa
2
1.0 m
=P
)(
50.0 Kg (1.0
) mm2( )
(g = 9.81 m/s2
( .
( :
) F = m (kg) g (m s-2
F = ( 50 kg ) ( 9.81 m/s2 ) = 490 kg.m/s2 = 490 N
( :
F
490 N
=
)= 490 000 000 Nm -2 (Pa) = 490 megapascals (MPa
-6
2
A
1.0 10 m
=P
.

.
200 kPa
.
)(174
)(175
/
( : .
(
.
Atmospheric Pressure
:
) (
.
) (location
) (temperature ).(weather conditions

) (
.
. ) (fluid

.
.

.
)(175
)(176
/
(
:
( :
) ( .
.

.
) (1 atm
.
) (10 %
.
( :
.
.

) ( ) (
.
( ) (10 %

(
:

.

.
)(176
)(177
/
Standard Pressure
:
)(0 C
)) 101325 Pa (101325 N/m2 (1
.atm
:
) (1N

).(1 m2
1N
1 kg . m/s2
= 1Pa
=
= 1 kg/m.s2
2
2
1m
1m
) ) 1N = 1 kg . m / s2 where ( F = m(kg) . g(m/s2
1Pa = 1 kg / m . s2
(

.

barometer
.Torricelli
.
)(177
)(178
/
:
:
).(

.
.

.
.
(76 cm
) .Hg
.
)(178
)(179
/

.

.
:
F=ma
) (m :
m
V
m = d .V
=d
:
V = r2 h
=
:
m = d .V
)m = d ( r 2 h
:
F=m.a
F = d ( r 2 h ) a
:
A = r2
= ) (
:
)(179
)(180
/
F
A
m g
= P
A
r
= P
= P
h d
2
r
P = h . d . g
:
mg
A
=P
) (a
:
m
A
/ ) (lb/in2
/ )(kg/m2
) (d ) (g
:
Ph
) (inch Hg
)(cm Hg ) . (mm Hg

.

.
)(180
)(181
/
:

)
( .
)( ) (1 m ) (880 mm
.
.
) ( ) (carefully inverted
) ( )
(
) (

) (h )
.(

.

.

.
)
)(181
)(182
/
( .
.
.

.

.
= PHg Patm
(760
) mmHg .
)( = (1 torr
)1 mmHg

) (0 C ).(760 mm Hg
)(182
)(183
:
.
)(183
(184)
:
/
Fig. 10 : A mercury barometer is used to measure atmospheric pressure by

determining the height of a mercury column supported in a sealed glass tube.
The downward pressure of the mercury in the column is exactly balanced by
the outside atmospheric pressure that presses down on the mercury in the dish
and pushes it up the column.
Above the mercury in the tube is a vacuum. The column of mercury is
supported by the atmospheric pressure.
(184)
(185)
:
/
Fig. 11 : A Torricellian barometer

Schematic diagram of a closed-end barometer. At the level of the lower mercury
surface, the pressure both in side and outside the tube must be equal to that of the
atmosphere. There is no air inside the tube, so the pressure is exerted only by the
mercury column h mm high. Hence, the atmospheric pressure must equal the pressure
exerted by h mm Hg, or h torr.
(185)
(186)
:
/
Fig. 12 : A barometer is used to measure the pressure of the atmosphere. The pressure
of the atmosphere is balanced by the pressure exerted by the column of mercury. The
height of the column is proportional to the pressure.
Fig. 13 : Torricelli's mercury barometer
(186)
)(187
/
) (1.35951 104 kg/m3 ) (0 C
) (a = 9.80665 m/s 2

) . (760 mm = 0.76 m
) (1 atm ) (760 mm Hg ) (101325Pa :

P=h.d.g
P = ( 0.760 m ) (1.35951 104 kg/m3 ) ( 9.80665 m/s2 ) = 101325 Pa
:
1 atm = 760 mm Hg = 101325 Pa
(open-end
) manometer
.
(
(
.
) (Patm
) (
) (PHg
) (PHg = Patm
) (h
) (mmHg ).(torr

) ( .
)
)(187
)(188
/
( ) (
.

) 0
(P
)(
.

.
(
)(0 C
76 cm = 760 mm
(

) (76 cm 76 cmHg ).(760 mm Hg
) ( ) (d
.
)(0 C
) (.
)(188
(189)
:
/

) (
.
.
Fig. 14 : Some commercial pressure-measuring devices.

a) A commercial mercury barometer.
b) Portable barometers.
c) A tire gauge. This type kind of gauge registers "relative" pressure, that
is, the difference between internal pressure and the external atmospheric
pressure. For instance, when the gauge reads 30 psi (pounds per square
inch), the total gas pressure in the tire is 30 psi + 1 atm, or about 40 psi.
(189)
)(190
/
)Standard Atmosphere (atm
) - (
) (760 mm ) (0 C ).(
) (Standard Atmosphere ) .(1 atm
) (1 atm .

) (760 mm .
) (

.

) (mmHg = torr ) (SI ) (
) (N/m2
) (atm .

) (d(H2O) = 1 g/cm3 ) (d(Hg) = 13.6 g/cm3
) .(
) (
) (0 C .
. Hg ) (760 mm
.
Hg
.
)(190
)(191
/
)(

) (76 cmHg ) (h
) .(1 atm )(13.6 g/cm3
) (13.5951g/cm3 ).(1 g/cm3
) (13.6 ) (H2O
13.6
:
m H2O = mHg
( d .V )H O = ( d.V )Hg
= (13.6 g cm-3 ) VHg
(1 g cm ) V
-3
H2O
13.6 g cm-3
VH2O =
VHg
-3
1 g cm
VH2O = 13.6 VHg
) (13.6
) (Hg ) (13.6
:
1 mmHg 13.6 mmH 2O
13.6 mmH 2O
= 10336 mmH 2O = 10.336 m
1.00 mmHg
1 atm 760 mmHg
)(191
)(192
/
d Hg
d H 2O
Length of H 2O clumn = Length of Hg column
13.6 g/cm 3
= 1030 cm
Length of H 2O clumn = 76 cm
3
1.0 g/cm
Length of H 2O clumn = 10.3 m
) ( :
(
.
( ) (

.
)(10.3 m
.
.
)(192
)(193
/

" "
Measuring Pressures of Trapped Gases

).(Manometer
.
(

) (U-tube )
( ) .(
) -(

.
) (Pgas
) (h0
.
Pgas > Patm ) (Pgas

) (Patm
).(PHg
) (Pgas ) (Patm
) (Pgas = Patm ) ) ( h = 0
( .
)(193
)(194
/
Pgas = Patm + PHg
Pgas = Patm + h
Pgas = 76 cmHg + 0
Pgas = 76 cmHg

. ) ( h = h1 - h 2
.
) (Pgas ) (Patm

) ) ( Pgas > Patm () .
) (
) ( h = h1 - h 2
.
Pgas = Patm + PHg
Pgas = Patm + h
Pgas = 76 cmHg + h
) (Patm . ) (PHg
) . ( h
) (Pgas ) (Patm
)(
) ( Pgas < Patm ) : (
.
)(194
(195)
:
/
Pgas = Patm - PHg
Pgas = Patm - h
Pgas = 76 cmHg - h
Patm Pgas
.
Fig. 15 : Open-end manometers for measuring pressure in a gas-filled

bulb.
In (a), the pressure in the bulb is lower than atmospheric, so the mercury
level is higher, in the arm open to the bulb (gas pressure is less than
atmospheric pressure)
in (b), the pressure in the bulb is higher than atmospheric, so the mercury
level is higher in the arm open to the atmosphere (gas pressure is greater
than atmospheric pressure).
(195)
(196)
:
/
(196)
(197)
:
/
Fig. 17 :
b) The two-arm mercury barometer is called a manometer. In this sample,
the pressure of the gas inside the flask is greater than the external
atmospheric pressure. At the level of the lower mercury surface, the total
pressure on the mercury in the left arm must equal the total pressure on
the mercury in the right arm. The pressure exerted by the gas is equal to
the external pressure plus the pressure exerted by the mercury column of
height h mm, or Pgas (in torr) = Patm (in torr) + h torr.
c) When the gas pressure measured by the manometer is less than the
external atmospheric pressure, the pressure exerted by the atmosphere is
equal to the gas pressure plus the pressure exerted by the mercury
column, or Patm = Pgas + h. We can rearrange this to write Pgas (in torr) =
Patm (in torr) h (torr).
(197)
)(198
/

Closed- End Manometer
)
( . )(U
).(
) (Patm
.

.
Pgas
) PHg ( . Pgas = PHg

.
)(198
(199)
:
/
(199)
)(200
/

:
Experimental Method

The Behaviour of Gases Under Ordinary Conditions
) (Ideal Gas )(Real Gas

):(Ideal Gas
) (
.
.
):(Real Gas
) (

.
)(200
)(201
/

The Gas Law

.
.

.

.

) (Anglo-Irish Scientist Robert Boyle
.

) (Jacques Charles and Joseph-Louis Gay-Lussac
) .(Ballooning
.

. ) (V
) (T ) .(P
.
. ) (NO2
N2O4
.
)(201
)(202
: -
)P-V Relationship: Boyle's Law (1662

The Dependence of the Volume of a Gas on Pressure : Boyles Law
)( .
) .(1662
) Irish
) Scientist Robert Boyle( Robert
Hook
) (
.
.
) (J
) ( -
) - (
) (
)
( .
)(202
(203)
:
/
Fig. 19 : A apparatus for studying the relationship between pressure

and volume of a gas.
In (a) the pressure of the gas is equal to the atmospheric pressure. The
pressure exerted on the gas increases from (a) to (d) as mercury is added,
and the volume of the gas decrease, as predicted by Boyle's law. The
extra pressure exerted on the gas is shown by the difference in the
mercury levels (h mm Hg). The temperature of the gas is kept constant.
(203)
(204)
:
/
(204)
(205)
:
/
Fig. 21 : Boyle's law. Boyle's experiment showing the compressibility of

gases
(205)
)(206
Fig. 22 : A representation of Boyle's experiment. A sample of air is

trapped in a tube in such a way that the pressure on the air can be changed
and the volume of the air measured. Patm is the atmospheric pressure,
measured with a barometer . P 1 = h1 + Patm
) (
) (
.
.

.
)(206
)(207
/

.
P V
) (
.

.
: " "
)P(mm. Hg
)P (mmHg
724
869
951
1230
1893
2250
)V(L
)V (L
1.5
1.33
1.22
0.94
0.61
0.51
)PV (mmHg. L
) x (mm Hg )(L
1.09 103
1.16 103
1.16 103
1.2 103
1.2 103
1.1 103
) ( .

.
)(207
(208)
:
/
Fig. 23 : Boyle's law: As volume decreases, gas molecules become more

crowded, which causes the pressure to increase. Pressure and volume are
inversely related
Fig. 24 : Boyle's law.

At constant n and T, the volume of an ideal gas decreases proportionately
as its pressure increases. If the pressure is doubled, the volume is halved.
If the pressure is halved, the volume is doubled.
(208)
(209)
:
/
Fig. 25 : A demonstration of Boyle's Law. Temperature is constant.
Fig. 26 :
a) As we have seen, the pressure of a gas arises from the impacts of its
molecules on the walls of the container.
b) When the volume of a sample is decreased, there are more molecules
in a given volume, so there are more collisions with the walls. Because
the total impact on the walls is now greater, so is the pressure. In other
words, decreasing the volume occupied by a gas without changing its
temperature increases its pressure.
(209)
)(210
/

.
) (
.
Fig. 27 : Compression of gases
:
1
P
1
V = K
P
PV = K
)(210
)(211
/
) (PV ) (K
) (T ) (n
)(.
) (PV = K
) (K
) (n ) (T
.
) ( 10 atm
) (200 K PV .
"
" .Isothermal Process

:
"
"

.
.
)(211
(212)
:
/
:
.
Fig. 29 : Graphs showing variation of the volume of a gas with the

pressure exerted on the gas, at constant temperature. (a) P versus V. Note
that the volume of the gas doubles as the pressure is halved. (b) P versus
1/V
(212)
(213)
:
/
Fig. 30 : Boyle's law summarizes the effect of pressure on the volume of

a fixed amount of gas at constant temperature.
Fig. 31 : When the pressure is plotted against 1/volume, a straight line is

obtained. For real gases, Boyle's law breaks down at high pressures
beyond the scope of this graph, and a straight line is not obtained in these
regions.
(213)
(214)
:
/
( V)
1

P
1
V = K
P
K ( )
Fig. 33 : Graphical illustration of Boyle's law.

a) Volume V versus pressure P. This curve shows the inverse proportionality between
volume and pressure. As pressure, volume decreases. b) V versus 1/P. A linear plot
results.
(214)
(215)
:
/
Fig. 34 : Boyle's law.

(a) A plot of V versus P for a gas sample is a hyperbola, but (b) a plot of V versus 1/P
is a straight line. Such a straight-line graph is characteristic of equations having the
form y = m x + b (where b = o) (V = k(1/P) + 0) or PV = k
Fig. 35 : Measured values of P and V are presented in the first two columns, on an
arbitrary scale. (b, c) Graphical representations of Boyle's Law, using the data of
part (a). (b) V versus P. (c) V versus 1/P
) (
( ) P1, V1) )
( P V) ( P2, V2) (
:
P1V1 = P2 V2

( P) ( PV)
(215)
)(216
/
) .(

) (Ideal Gas
.
) ( )
( )
(
)(PV = K
) ( .
)(216
)(217
: .
) (Regnault ) (Amagat

.
) (.
)(217
)(218
) ( ) ( P, V
H2,O2, N2 :

)(

.

.

.
) (PV
:

)(218
)(219
/
)(.
P V

) ( ) (P V .
.
).(
: ) ( ) (39.95 g
PV
30.560
30.520
30.500
30.530
17.980
17.650
17.050
16.500
)P (atm
15.28
30.52
60.99
91.59
8.99
17.65
34.10
49.50
)V (L
2.000
1.000
0.500
0.333
2.000
1.000
0.500
0.333
)(C
100 C
- 50 C
) (39.95 g
) (100 C ) .(- 50 C
. ) (PV

)(219
)(220
/
.
.
) (PV
.
) (Ar
.

).(
: PV .
8.0
0.9360
4.0
0.9708
2.0
0.9891
1.0
1.0000
0.5
1.0057
P, atm
PV
) (0.5 ) (1.0 atm

) (PV
.
) (4.0 ) (8.0 atm ) (PV ) (3 %
.
.
.
)(220
)(221
/

)(
) (4 L ) (2 atm )(0 C
(2
)L
)(2
P2
2L
constant
constant
)(1
2 atm
4L
constant
constant
P
V
T
n
:
P1V1 = P2 V2
V
P2 = P1 1
V2
4L
P2 = 2 atm
2L
P2 = 4 atm

) 4 L (2 L )(P2
) (P1
) (V1 ) (V2
) (P1
): (P2
)(221
)(222
/
)P2 = P1 ( Ration of volume that increase in pressure
V1 4
= = 2
V2 2
V
P2 = P1 1
V2
4
P2 = 2 atm x = 4 atm
2
)(
5 L 15 atm
3 atm .
:
P1V1 = P2 V2
15 atm 5 L = 3 atm V2
15 atm 5L
3 atm
V2 = 25 L
= V2

.
) (V2 ) (V1
) (
) (P1 = 15 atm
= (P2
) 3 atm :
)(222
)(223
/
)V2 = V1 (pressure ratio
P
V2 = V1 1
P2
15 atm
V2 = 5 L
3 atm
V2 = 25 L
)(
2 L ) (O2 760 mmHg ) 1.42 g

( . g/L 8 atm
) (mmHg
) (atm ) (P1 ) (P2
) (atm ) (mmHg
) (atm 760 mmHg ) : (atm
:
1 atm = 760 mmHg
1atm
P1 = 760 mmHg
= 1 atm
760 mmHg

): (V2
P1V1 = P2 V2
1 atm 2 L = 8 atm V2
1 atm 2 L
8 atm
V2 = 0.25 L
= V2
)(223
)(224
/
) (Pressure ratio :
)V2 = V1 (pressure ratio
P
V2 = V1 1
P2
1 atm
V2 = 2 L
8 atm
V2 = 0.25 L
) (V2 = 0.25 L :
m
d=
V
1.42 g
=d
0.25 L
d = 5.68 g/L
)(
540 cm3
63.3 kPa 325 cm3
.
:
P1V1 = P2 V2
V
P2 = P1 1
V2
540cm3
P2 = 63.3 kPa
3
325cm
P2 = 105.17 kPa
)(224
)(225
:
Volume Temperature Relationship
) (1787 )(1802
Charles' - Gay Lusacs Law and the Absolute Temperature
)
( ) (V ) .(T

.
" " .

) (
.

.
.

. )
( ) ( .

) (
.
.
Jacques Alexander
Charles
)(225
)(226
/

) (
.
.
Charles Gay-Lussac

.

) (
1 ml
100 C .
Fig. 39 : A molecular interpretation of Charles Law the change in volume of a gas

with changes in temperature ( at constant pressure). At the lower temperature,
molecules strike the walls less often and less vigorously. Thus, the volume must be
less to maintain the same pressure.
)(226
(227)
:
/
Fig. 41 : Charles's law. At constant n and P, the volume of an ideal gas increases
proportionately as its absolute temperature increases. If the absolute temperature is
doubled, the volume is doubled. If the absolute temperature is halved, the volume is
halved.
Fig. 42 : Variation of the volume of a gas sample with temperature, at constant

pressure. The pressure exerted on the gas is the sum of the atmospheric pressure and
the pressure due to the weight of the mercury.
(227)
)(228
Fig. 43 : A demonstration of Charle's Law. Pressure is constant.

:
)(ml
100 C
0 C
1.37
1.00
1.04
1.00
1.03
1.00

%
ml
37 %
0.37
4%
0.04
3%
0.03
) (V ) (T
) (gay-Lussac
.
:
) (
273.15
) ( ".
)(228
)(229
/
:
1
V1 = Vo +
t1Vo
273.15
t1
V1 = Vo +
Vo
273.15
V t
V1 = Vo + o 1
273.15
273.15Vo Vo t1
= V1
+
273.15
273.15
273.15Vo + Vo t1
= V1
273.15
273.15 + t1
V1 = Vo
273
t1
273.15 Vo

t1
Vo
273.15
V1 = Vo +
)
(.

1
273.15
1
t1Vo
273.15
V1 = Vo +
.
) (O2) (N2
) (He) (NH3 ) (CO2 )(SO2
) (Ar
1
273.15
)(229
(230)
:
/
( 273.15) ( 273)
.(0.15)
:
273 + t1
V1 = Vo
273
( t) ( V1)
.
( )
Fig. 44 : The extrapolation of data for a number of gases suggests that the
volume of all gases should become 0 at 273 C (T = 0 on the Kelvin
scale). All gases condense to liquids well before that temperature is
reached.
(230)
(231)
:
/
Fig. 45 : Charles's law. The volumes of two different samples of gases decrease with
decreasing temperature (at constant pressure and constant molar amount). These
graphs (as would those of all gases) intersect the temperature axis at about (- 273 C).
Fig. 46 : When the temperature of a gas is increased and it is free to change its
volume at constant pressure (as depicted by the constant weight acting on the piston),
the volume increases. A graph of volume against temperature is a straight line.
(231)
(232)
:
/
(232)
)(233
)(233
)(234
/
) (linearly
.
.

. (-
) 273.15 C
) (-273.15 C (0
) K .

) (V0 = 273 cm3

273
:
1
273 = 1cm3
273
.
) (V1 :
t
V1 = V0 +
V0
273
1
V1 = 273 +
273
273
V1 = 273 + 1 = 274 cm3
273
)(234
)(235
/
2
x 273 = 2 cm 3
273
):(V1
t
V1 = V0 +
V0
273
2
V1 = 273 +
273
273
V1 = 273 + 2 = 275 cm 3
273

:
1
273 = 1cm3
273
) (V1 :
t
V1 = V0 -
V0
273
1
V1 = 273 -
273
273
V1 = 273 - 1 = 272 cm3
)(
( 150 ml .
25 C .
)(235
(236)
:
/
t
V1 = Vo + 1 Vo
273
25 C
V1 = 150 ml +
150 ml
273 C
V1 = 163.74 ml

.( )

isobar

.

.( )
Fig. 51 : Variation of the volume of a gas sample with temperature, at constant

pressure. Each line represents the variation at a certain pressure. The pressure increase
from P1 to P4. All gases ultimately condensed (become liquids) if they are cooled to
sufficiently low temperatures; the solid portions of the lines represent the temperature
region above the condensation point. When these lines are extrapolated, or extended (the
dashed portions), they all intersect at the point representing zero volume and temperature
of (- 273.15 C).
(236)
(237)
:
/
Fig. 52 : An experiment showing that the volume of an ideal gas increases as the
temperature is increased at constant pressure.
a) A mercury plug of constant weight, plus atmospheric pressure, maintains a constant
pressure on the trapped air.
b) Some representative volume-temperature data at constant pressure. The relationship
becomes clear when t (C) is converted to T (K) by adding 273.
c) A graph in which volume is plotted versus temperature on two different scales. Lines
A, B, and C represent the same mass of the same ideal gas at different pressures. Line A
represents the data tabulated in part (b). Graph D shows the behaviour of a gas that
condenses to form a liquid (in this case, at 50 C) as it is cooled. The volume does not
really drop to zero when the gas forms a liquid, but it does become much smaller than the
gaseous volume.

.(-273.15 C)
!
(V
= 0)

.(Absolute Zero)
)

(
(237)
)(238
/
) (CO2
.
) (- 273 C
) (He ).(-269 C
) V = 0
) (- 273.15 C
) (t = - 273 C
) (Celsuis Scale.
"
" . ) (1848
) zero ( . (-273.15
) .C ) (- 273.15 K
. )
( .
) . (C
.
)(Absolute Kelvin Temperature Scale
T
) (t :
T = t + 273.15
) (K
).(1848

)(238
)(239
/
) (V ) (T )(PV
. ).(
) (T = 0
:
VT
V= KT
V
=K
T

:
)
(.
The volume of a fixed amount of gas at constant pressure is directly
proportional to the absolute temperature.

.

:
V1
V
V
T
= 2 or 1 = 1
T1
T2
V2
T2
)(239
)(240
/
273 + t1
V1
V
V1 = Vo
= 2

273
T
T2
)(t1
273 + t1
V1 = Vo
273
) (t2 V2 :
273 + t 2
V2 = Vo
273
) (V1 ): (V2
273 + t1
Vo
273
=
273 + t 2
Vo
273
273 + t1
= 273
273 + t 2
273
273
273 + t1
=

273
273 + t 2
V1
V2
V1
V2
V1
V2
V1 273 + t1
=
V2 273 + t 2
V1
T
= 1
V2
T2

.
.
)(240
)(241
/
( ) (- 273 C

Vt
V1 = Vo + o 1
273
273Vo Vo (-273)
V1 =
+
273
273
273 - 273
V1 = Vo
273
V1 = 0
) (-273C
).(- 273.16 C

Vt
V1 = Vo + o 1
273

) (K ) (C :
K = C + 273
C = K 273
) (K = C + 273 :
Vt
V1 = Vo + o 1
273
Vo ( K - 273)
273
273 V Vo ( K - 273)
V1 =
+
273
273
273V + Vo K - 273Vo
V1 =
273
V1 = Vo +
)(241
)(242
/
Vo K
273
= V1
.
.
.
.
) (273.15 K
) (0 C ) .(1 atm
).(STP

.
.

)(
) (22.4 L ) (1 atm
) (0 C
).(25 C
:
)(2
25 C = 298 K
V2
constant
constant
)(1
0 C = 273 K
2.24 L
constant
constant
T
V
P
n
:
)(242
)(243
/
V1 V2
=
T1 T2
T
V2 = V1 2
T1
298 K
V2 = 2.24 L
273 K
V2 = 2.445 L

) 0 C (25 C
) (V2 ) (V1
) (T2
) (T1
T2

T1
)V2 = V1 (ratio of temperature that increase in volume

T
V2 = V1 2
T1
298 K
V2 = 2.24 L
273 K
V2 = 2.445 L
)(
) (V2 ) (V1 650 cm3

25 C ) 400 C (.
)(243
)(244
/
V1 V2
=
T1 T2
650 cm3
V2
=
)(25 + 273
)(400 + 273
V2
650 cm3
=
298 K 673 K
673 K
V2 = 650 cm3
298 K
V2 = 1467.95 cm3
:
) (V2
.
) (V1 ) (temperature ratio
.
T
V2 = V1 2
T1
400 + 273 K
V2 = 650 cm3
25 + 273 K
V2 = 1467.95 cm3
)(
2 L 25 C
) (- 30 C
.
)(244
)(245
/
V1 V2
=
T1 T2
T
V2 =V1 2
T1
(- 30 + 273)
V2 = 2 L
(25 + 273)
243 K
V2 = 2 L
298 K
V2 = 1.63 L
)(
) (T2 ) (V2 (0.6

) dm3 ) (1000 Pa ) (V1
) (0.3 dm3 ) (25 C) (T1 )(1000 Pa
...............................................................................................................
...............................................................................................................
...............................................................................................................
...............................................................................................................
...............................................................................................................
...............................................................................................................
...............................................................................................................
)(245
)(246
/

Gay-Lussac's Law of Combining Volumes

.
.
.
.

2H 2 (g) + O 2 (g)
) 2H 2 O(g

.

H2 (g) + Cl2 (g)
) 2HCl(g

.
)(

) (H2 ) (O2
) (H2O )(
)(246
)(247
:
O 2 (g)
) 2H 2O(g
)2 H 2 (g
2 Volumes + 1Volume
2 Volumes

.
) (L ) (2 L ) (1 L ) (2 L :

2H 2 (g) + O 2 (g)
) 2H 2O(g
1L
2L
2L
)(247
)(248
Fig. 54 : Law of combining volumes. When gases at the same temperature and
pressure combine with one another, their volumes are in the ratio of small whole
numbers.
)(
) (Cl2 ) (H2 HCl

.
.
.
)(1 L
) (2 L :

H 2 (g) + Cl2 (g)
) 2HCl(g
1L
2L
1L

) ( .
)(248
)(249
/

) (

) (2 L
) (2 L
.
)(

+ 3 H 2 (g)
) 2 NH3 (g
)N 2 (g
1 volume + 3 volumes
2 volumes
)(
) (

+ 2 O2 (g)
CO2 (g) + 2H2 O
)CH 4 (g
1 volume + 2 volumes
1volume + 2 volumes
)(
) (
:
S(s) + O2 (g)
) SO2 (g
1 volume
1volume
)(249
)(250
/
)(

:
4NH3 (g) + 5O2 (g)
) 4 NO(g) + 6H2 O(g
4 volumes + 6 volumes
4 volumes + 5 volumes
)(
)6H 2 O(g
) 2N 2 (g
3O 2 (g)
)4NH 3 (g
6 molecus
2 molecules
3 molecules
4 molecules
6 Volumes
2 Volumes
3 Volumes
4 Volumes
6L
2L
3L
4L
6 m3
2 m3
3 m3
4 m3
:
) (
.

100 C 7
) (4NH3 + 3O2 8
) (2N2 + 6 H2O
) (0 C 8
) (0.005 (4
) NH3 + 3 O2
2 ) (2N2
)(250
)(251
/
-
. - ) (1809
)( ) (Combining Volumes :
"
"
:

.
At constant temperature and pressure, the volumes of reacting gases can
be expressed as a ratio of simple whole numbers.
Fig. 55 : Automobile air bags are inflated with N2 gas produced by decomposition of
sodium azide
)(251
(252)
:
/
Fig. 56 : The nitrogen gas formed in the rapid reaction :

decomposition
2NaN 3 (s)
2Na(s) + 3N 2 (g)
sodium azide
fills an automobile air bag during a collision. The air bag fills within 1/20th of a
second after a front nt collision.
The rapid decomposition of sodium azide, NaN3, results in the formation of a large
volume of nitrogen gas. The reaction is triggered electrically in this air bag.

()
(C4H10) ( 4.5 dm3) ( STP)

.( ) STP
:
2C 4 H10 + 13O 2
8CO 2 + 10H 2 O
(252)
)(253
/
1mol C4 H10
22.4 dm3
n C4 H10
4.5dm3
4.5 dm3
n C4 H10 = 1mol
3
22.4 dm
n C4 H10 = 0.201mol
:
2 mol C4 H10
13 mol O 2
0.201 mol
n O2
0.201 mol C4 H10 13 mol O2
= 1.31 mol O 2
2 mol C4 H10
= n O2
O2 STP
1mol O 2
22.4 dm3
1.31 mol O 2
VO 2
1.31mol O 2 22.4 dm3 O 2
=
1mol O2
VO2
VO2 = 29.3 dm3 O2
)(
" "
) NaOH ( .
.
) (cm3 ) (STP 0.15 g Al
) : .(27 g/mol = Al
:
2Al + 2OH - + 2H 2O
3H 2 + 2AlO -2
)(253
(254)
:
/
: Al
m Al
Aw Al
0.150
n Al =
= 5.56 10-3 mol of Al
27
nA =
:
2 mol Al
3 mol H 2
5.56 10 -3mol Al
nH 2
5.56 10 -3 mol Al 3mol H 2
nH 2 =
2 mol Al
-3
nH 2 = 8.34 10 mol
22.4 dm3 = STP H2

:
22.4 dm3
1mol H2
8.34 10-3 mol H2

V H2
VH2 =
8.34 10-3 mol H 2 22.4 dm3

1mol H 2
VH2 = 0.187 dm3 H2

VH2 = 187 cm3 H 2
where 1 dm3 = 1000 cm3
(254)
)(255
: ) (V )(n
The Quantity Volume Relationship
- )(1811
Avogadros Law and the Standard Molar Volume

)
( ) ( ) (n.
)
(1811 ) (Amadeo Avogadro -
Avogadros Hypothesis

.
) (postulation ) (
): (1811
" ) (V
)) (N
( ".
Avogadro postulated that :
At the same temperature and pressure, equal volumes of all gases contain
the same number of molecules.
)(Avogadro's hypothesis
) ( 2 %
).(Avogadro's Law

)(255
)(256
/

.

) (.
.
)(
5 mol = H2 5 mol
) .(O2 H2 5 g
) (O2 5 g
:
mH2
5g
= 2.5 mol
2 1 g mol-1
5g
= 0.156 mol
2 16 g mol-1
Mw H2
m O2
Mw O2
= n H2
= n O2
n H 2 n O2
N O2 N O 2

)
(.
Avogadro's Law can also be stated as follows :
At constant temperature and pressure, the volume, V, occupied by a gas
sample is directly proportional to the number of moles, n, of gas
)(256
(257)
:
/
V n
V= K n
V
= K (constant P, T)
n

.
V1 V2
=
n1 n 2
V1 n1
=
V2 n 2
Fig. 57 : Avogadro's law. At constant T and P, the volume of an ideal

gas increases proportionately as its molar amount increases. If the molar
amount is doubled, the volume is doubled. If the molar amount is halved,
the volume is halved.
(257)
)(258
Fig. 58 : Avogadro's law : The volume of a gas is directly related to the number of
moles of the gas. If the number of moles is doubled, the volume must double at
constant temperature and pressure.
) (A, B
V = K n :
VA = K. n A
VB = K. n B
) (VA, VB ) (A, B )(nA, nB

nA = nB :
)(A, B
:
VA
K . nA
=
=1
VB
K . nB
VA = VB
:

.
)(258
)(259
/

)(

.
) (H, Cl
.

.
.

:
) (H
) (1 L ) (n ) (1 L
) (n ) (1 L )) (HCl . (n
) (HCl
.
.
)) (1 L n (2n ) (1 L
) n (2n ) (2 L ) 2n( .
).(
) (1858
.

)(259
)(260
/
.
) (STP ) (1 L ) (X ) (0.0900 g ) (1 L
) .(1.43 g
) (X
) (0.0900/1.43 ) (0.0630 .
) (32.00 amu X )(0.0630
) (32.00
).(2.016 amu
) 22.414 L : (22.414 L
0 C ) (1 atm 6.023 1023
) .(NA
) (STP 22.414 L
.
) ( ) (H ) .(O
:

.

.
)(260
)(261
/
): (Molar Volume

.
STP ) 22.414 dm3 (
) (Molar Volume ) . (STP
.

) ( Molar Volume 22.414 L 22.4 L STP
the standard molar volume of an ideal gas is taken to be 22.414 liters per
mole at STP
: .
*
Density at
)STP (g/L
1.429
1.250
0.090
0.178
Standard Molar
Volume, Vm
)(L/mol
22.414
22.394
22.404
22.428
22.426
g/mol
32.00
28.01
2.02
4.003
Formula
Gas
O2
N2
H2
He
Ideal Gas
Oxygen
Nitrogen
Hydrogen
Helium
Neon
Ne
20.18
22.425
0.900
Argon
Ar
39.95
22.393
1.784
Carbon

CO2
44.01
22.256
1.977
dioxide
Ammonia
)(
NH3
17.03
22.094
0.771
Chlorine
Cl2
70.91
22.063
3.214
Deviations in standard molar volume indicate that gases do not behave ideally.
* Experimentally determined densities of several gases at standard temperature and
pressure.
)(261
)(262
/
:
) (Vm
) (Volume Occupied ) (n
): (Formula Units
Volume Occupied
Number of Moles
= Molar Volume
V
n
= Vm

. :
)(Differences are Small Under Normal Conditions

).(Become Smaller as the Pressure of the Gas is Reduced

.
) (
)
( ) (STP
.
)(
) (27.0 L ) (1.41 g/L

. STP
( = 38.1 g/mol
1.70 g/L = STP
)(262
)(263
/
)(
) (O2
.
) ( P = 760 mmHg, T = 273 K
m O2
N
N
=
NA
Mw O2 N A
Mw O2 N
32 g mol-1 1 molecule
=
= 5.31 10- 23 g
NA
6.023 1023 molecules mol-1
=n
= m O2
)(
)(V1 = 10 L
) (V2 ) (n2 = 10 moles
:
V1
V
= 2
n1
n2
n2
n1
10 mol
V2 = 10 L
= 100 L
1 mol
V2 = V1
)(263
)(264
/
)(
) (V2 ) (O2 (T2 = 25

)) C ) (STP
) (V1 = 22.4 L :
) (P = 1 atm, T = 273 K
) (Vm ) 298 K (25 C

(0 C = 273
) K 22.4 L :
V1 Vm
=
T1 T2
Vm
22.4 L
=
273 K
298 K
298K
Vm = 22.4 L
273K
Vm = 24.45 L
)(264
)(265
: ) (
P-T Relationship
The Constant Volume Law
) (
)Amontons Law (1703
)Gay-Lussac's Law (1802
) (

(Violent
) Collisions
.
:
" ) (P
) (T ".
Fig. 59 : The pressure of a fixed amount of gas in a vessel of constant

volume is proportional to the absolute temperature. The pressure
extrapolates to 0 at T = 0 on the Kelvin scale.
)(265
(266)
:
/
Fig. 60 : Charles's law : The Kelvin temperature of a gas is directly related to the
volume of the gas when there is no change in the pressure. When the temperature
increases making the molecules move faster, the volume must increase to maintain
constant pressure.
Fig. 61 : A demonstration of Gay-Lussac's Law. Volume is constant.
(266)
)(267
/
:
P
= K
T
P T
K
:
P1
P
P1
T
= 2 or
= 1
T1
T2
P2
T2

) ( )
(50 C
.
) (P ) (T
) (isochore
.
)(
) (10 L ) (1 atm
) (25 C
75 C
)(2
P2
348 K
constant
constant
)( )(1
1 atm
298 K
constant
constant
P
T
V
n
)(267
)(268
/
P1
P
= 2
T1
T2
348
= 1
= 1.17 atm
298
T
Pf = Pi f
Ti
)(
115 kPa (35

) C
) (25 C
)( )(1
115 KPa
35 + 273 = 308 K
constant
constant
)(2
P2
298 K
constant
constant
P
T
V
n
P1 P2
=
T1 T2
)(ratio of temperatures
T
P2 = P1 2
T1
P2 = P1
298
P2 = 115
=111.3 kPa
308
) (T1 ) (P1
) ( P1 > P2 ) (P2 ) (P1

T2

T1
T
298
P2 = P1 2 = 115
= 111.3 kPa
308
T1
)(268
)(269
/
)(
) (30 C ) (3 atm
).(0 C
)(2
P2
0 + 273 = 273 K
constant
constant
)( )(1
3 atm
30 + 273 = 303 K
constant
constant
P
T
V
n
P1 P2
=
T1 T2
T
P2 = P1 2
T1
0 + 273
P2 = 3 atm
30 + 273
273 K
P2 = 3 atm
303 K
P2 = 2.7 atm

) .(Temperature Ratio
P1

: T2
T1
)(269
)(270
/
) P2 = P1 ( temperature ratio
T
P2 = P1 2
T1
273 K
P2 = 3 atm
303 K
P2 = 2.7 atm
)(
4 atm 30 C
54 C
) (.
)(2
P2
54 + 273 = 327 K
constant
constant
)( )(1
4 atm
30 + 273 = 303 K
constant
constant
P
T
V
n
P1
P
= 2
T1
T2
T
P2 = P1 2
T1
327 K
P2 = 4 atm
303 K
P2 = 4.32 atm
) (Temperature Ratio
) (P2

) (temperature ratio
T2 : T1
)(270
)(271
/
)P2 = P1 (temperature ratio
T
P2 = P1 2
T1
54 + 273
P2 = 4 atm
30 + 273
327 K
P2 = 4 atm
303 K
P2 = 4.32 atm
)(
5 C
.
P1 = P
P2 = 2P
:
P1 T1
=
P2 T2
)P (5 + 273
=
2P
T2
1 578
=
2 T2
T2 = 2 578 = 1156 K
)(271
)(272
/
P-n Relationship
) (n, P ): (T, V
" "
P n
P = K n
P
= K
n
P P
P
n
1 = 2 or 1 = 1
n1 n 2
P2
n2
)(
) (15 Kg ) (O2
) (280 atm

)(2
P2
468.75 = 234.75
constant
constant
)( )(1
280 atm
nO2 = 15 103/32 = 468.75
constant
constant
)P(atm
)n (mol
V
T
:
P1 P2
=
n1 n 2
T
P2 = P1 2
T1
)P2 = P1 (ratio of temperatures
273
P2 = 3
= 2.7 atm
303
)(272
)(273
/
n-T Relationship
) (n, T ): (P, V
"
".
1
T
K
= n
T
n T = K
n
n1T1 = n 2 T2
/
The Combined Gas Law Equation
) (n ) (V )(P
) (T
.
:
:
)(P1V1 = P2V2
:
V1 V2
=
T1 T2
)(273
)(274
/
) (
:
P1 P2
=
T1 T2
:
VT
1
V
P
1
P
KT
=V
P
VT.
PV
=K
T
)(n = constant
) (n .
:
P1V1
PV
= 2 2
T1
T2
:
P1V1
P2 V2
=
T2
T1
)(274
)(275
/
:
T) T1 = T2( (P1V1 = P2V2) :
V ) V1 = V2( :
P ) P1 = P2 (
P1 P2
=
T1 T2
V1 V2
=
T1 T2
(STP) (standard temperature :

)and pressure
:
)(0 C = 273 K, 1atm = 101.325 KPa
)(
) (10 L ) (27 C )(985 torr

)(Standard Conditions
P1 V1 P2 V2
=
T1
T2
PVT
V2 = V1 1 1 2
P2 T1
985 torr 105 L 273 K
V2 = 105
=124 L
760 torr 300K
) (V1
.
) (985 torr )) (760 torr (
)(985torr/760 torr
)(275
)(276
/
300 K ) 273 K (
)(273 K/300 K
) (factors .
985 torr 273 K
V2 = 105 L
= 124 L
760 torr 300 K
)(
) (10.0 L ) (24 C 80 KPa

20 L )(107 kPa
P1 V1 P2 V2
=
T1
T2
P2 V2 T1
107 KPa 20.0 L 513 K
=
P1 V1
80 kPa 10.0 L
= T2
)T2 = 1.37 10 3 K (1.10 10 3 C
:
P V
T2 = T1 2 2
P1 V1
107 kPa 20 L
3
3
T2 = 513 K
= 1.37 10 K= 1.1 10 C
80 kPa 10 L
)(
STP 255 cm3

25 C 85.0 KPa
)(276
)(277
)()(1
255cm3
85.0 KPa
298 K
)(2
V2
101.3 KPa
273 K
V
P
T
:
P1V1
PV
= 2 2
T1
T2
:V2
P T
V2 = V1 1 . 2
P2 T1
V P T
V2 = 1 1 2
P2 T1
255 cm 3 85.0 kPa 273 K
= V2
101.325 kPa 298 K
V2 = 195.97 196 cm 3
:
)V2 = V1 (pressure ratio) (temperature ratio
( ) (85 kPa ) (101.325 kPa )(V1

P1
85
=
P2 101.325
( ) (25 C ) (0 C )(V1

:
T2 273
=
T1 298
)(277
)(278
/
): (V2
)V2 = V1 (pressure ratio) . (temperature ratio
P T
V2 = V1 1 . 2
P2 T1
85.0 273
V2 = 255 cm 3
101.325 298
V2 = 195.97 196 cm 3
)(STP
)(
) (82.5 kPa 300 cm3

) . (25 C )(500 cm3
)(50 C
)(2
P2
500 cm3
323 K
)()(1
....... 82.5 KPa........
300 cm3
298 K
P
V
T
:
P1V1
PV
= 2 2
T1
T2
P1V1T2 = P2 V2T1
P1V1T2
V2 T1
= P2
82.5 kPa 300 cm 3 323 K

= P2
500 cm3 298 K
P2 = 49.5 kPa
)(278
)(279
): (Volume Ratio) , (Temperature Ratio

) (P1
.
(
:
V1 300
=
= volume ratio
V
500
( -
:
T2 323
=
T1 298
:
)P2 = P1 (volume ratio) . (temperature ratio
V T
P2 = P1 1 . 2
V2 T1
300 323
P2 = 82.5 kPa
= 49.5 kPa
500 298
)(
) (Ne ) (10 L ) (27 C

) (985 torr )(STP
)(Standard Conditions
)(279
)(280
P1 V1 P2 V2
=
T1
T2
PVT
V2 = V1 1 1 2
P2 T1
985 torr 105 L 273 K
V2 = 105
= 124 L
760 torr 300K
) (V1
:
) (985 torr )) (760 torr (
(985 torr/760 torr) :
300 K ) 273 K (
(273 K/300 K) :
) (factors .
) V2 = 105 ( pressure Ratio ) ( temperature ratio
985 torr 273 K
V2 = 105 L
= 124 L
760 torr 300 K
)(
) (10.0 L ) (240 C 80 kPa

20 L )(107 kPa
)(280
(281)
(1)
80 kPa
10 L
240 C = 513 K
constant
P
V
T
n
(2)
107 atm
20 L
T2
constant
P1 V1 P2 V2
=
T1
T2
T2 =
P2 V2 T1
107 kPa 20.0 L 513 K
=
P1 V1
80 kPa 10.0 L
T2 = 1.37 10 3 K (1.10 10 3 C)
:
T2 = T1 ( pressure ratio ) ( volume ratio )
P V
T2 = T1 2 2
P1 V1
107 kPa 20 L
3
3
T2 = 513 K
= 1.37 10 K= 1.1 10 C
80 kPa 10 L
()
(3 ( 4 L)
(1.5 atm) (30 C) atm)
(10 C)
P
V
T
n
(1)
3 atm
4L
30 C = 303 K
constant
(2)
1.5 atm
V2
10 C = 283 K
constant
:
(281)
(282)
/
P1V1 P2 V2
=
T1
T2
P1 T2
.
P2 T1
3 atm 283 K
V2 = 4 L
1.5 atm 303 K
V2 = V1
V2 = 7.47 L
()
(500 atm) ( 27 C)
( 60 C)
.(700 atm)
P
V
T
n
(1)
500 atm
1L
27 C = 300 K
constant
(2)
700 atm
V2
60 C = 333 K
constant
:
P1V1
PV
= 2 2
T1
T2
P T
V2 = V1 1 2
P2 T1
500 atm (60 + 273) K
V2 = 1L
700 atm (27 + 273) K

V2 = (1 L) (0.714) (1.11)
V2 = 0.79 L
( pressure ration)
(temperature ratio)
(282)
)(283
/

:
).(Pressure Ratio = P1/P2 = 500/700 = 0.4

(temperature ratio = T2/T1 = :
)333/300 = 1.11
) (V2 :
)V2 =V1 ( pressure ratio < 1) ( temperature ratio > 1
P T
V2 =V1 1 . 2
P2 T1
500 333
V2 =V1
700 300
V2 = (1 L ) (0.71) (1.11) = 0.79 L
)(
9 m3 .
.
)(2
10P = 10
V2
1/2T = 0.5
constant
)(1
P=1
9 m3
T=1
constant
P
V
T
n
)(283
(284)
( P1 = 1,
P2 = 10P1 ) ,
V2 = V1
( T1 = 1, T2 = 0.5T1 )
( pressure ratio < 1) ( temperature ratio < 1)
P T
V2 = V1 1 2
P2 T1
1 0.5
V2 =V1
10 1
V2 = 9 m3 0.1 0.5
V2 = 0.45 m 3
:
P1V1
PV
= 2 2
T1
T2
P1V1T2 = P2 V2 T1
P1V1T2 1 9 m 3 0.5
V2 =
=
= 0.45 m 3
P2 T1
10 1
()
(3 atm 4 C )
(0.9 atm, 25 C)
. (2 ml)
P1V1 P2 V2
=
T1
T2
P T
V2 = V1 1 . 2
P2 T1
3 atm 298 K
V2 = 2 ml
0.9 atm 277 K

V2 = 7.17 ml
(284)
(285)
:
/
()
273 C 570 mmHg 648 ml

.( )
(P = 1atm = 760 mmHg , T = 0C = 273 ( STP)

K
P1V1 P2 V2
=
T1
T2
P T
V2 = V1 1 . 2
P2 T1
570 mmHg 273 K
V2 = 648 ml
760
mmHg
546 K
V2 = 243 ml
(285)
)(286
/
General Ideal Gas Law

The Ideal Gas Law

) (Directly Proportional:
:
) ( V T
) ( V n
.
) (V ) (Inversely Proportional
): (P
1
V
P
:
1
P
VT
Vn
1
) V (T) ( n
P
from
Charles
from Avogadro
T
P
from Boyle
PV nT
PV = n R T
)(286
)(287
/
) (Constant of Proportionality :
PV nT
R :
PV = nRT
: R
.
.
R ) (P, V T )
) (When it Behaves Ideally :
PV
nT
=R
) (R

.
PV
( = K :
T
) (n
( n :
PV
=K
T
) (n :
PV
= K
T
K K
.
)(287
)(288
/
:
V
=K
n
P
Pn =K
n
1
T nT = K
n
Vn
) (n
PV
T
)(where constant = R
PV
n
T
PV
= constant n
T
PV
= constant
nT
PV
=R
nT
) ( :

:
.
.
)(288
)(289
/

Value of the Gas Constant
) (R
) (P ) .(V
R .
:
PV
pressure (length)3
=R
=
nT
degrees moles
force (length)-2 (length)3
degrees moles
force length
energy
=R
=
degrees moles
degrees moles
=R
R = J K -1mol-1
R = Nm K -1mol-1
: R
( ) (R atm L /mol K
)(22.414 L
) S.T.P = 273 K, 1
(atm
:
P V 1 atm 22.4136 L
=
n T 1 mol 273.15 K
=R
R = 0.082056 atm.L/mol. K 0.0821 atm. L /mol K
)(289
(290)
/
: ( R) ( ml)
R=
0.0821 L.atm
0.0821 L 103 ml L-1.atm
=
mol.K
mol . K
R = 82.1 ml.atm/mol.K
Fig. 62 :
a) Decreasing the volume of the gas at constant n and T increases the frequency of
collisions with the container walls and therefore increases the pressure (Boyle's law).
b) Increasing the temperature (kinetic energy) at constant n and P increases the
volume of the gas (Charles's law).
c) Increasing the amount of gas at constant T and P increases the volume (Avogadro's
law).
d) Changing the identity of some molecules at constant T and V has no effect on the
pressure (Dalton's law).
(290)
(291)
:
/
Fig. 63 : Schematic illustrations of Boyle's law, Charles's law, and Avogadro's law
(291)
)(292
/
( ) (R bar. L/mol K
: atm
: R
)( 1 atm = 1.01325 bar
PV
)(1.01325 bar) (22.4136 L
=
nT
) (1 mol ) ( 273.15 K
=R
R = 0.08314 L bar/mol K
R = 0.08314 L bar/mol K
( ) (R Pa . dm3/mol K
) (Pa ) (atm :
)(1 atm = 101325 Pa
) (R Pa . dm3/mol . K :
PV
nT
) (101325 Pa) (22.4136 dm 3
=R
1mol 273.15 K
=R
R= 8314 Pa . dm 3/mol . K
R = 8.314 kPa . dm 3 /mol . K
R (R = 8.314 atm :
L/mol K
:
)(292
)(293
/
1 atm = 101325 Pa
1 L = 1 dm 3
) 0.082056 atm . L 101325 Pa/atm . dm 3/L
(
0.08206 atm. L
=R
=
mol.K
mol . K
3
R = 8314.32 Pa dm / mol K
R = 8.314 kPa dm 3 / mol K
( ) (R Pa . m3/mol K
PV
nT
) (101325 Pa) (0.0224136 m 3
=R
1mol 273.15 K
R = 8.314 Pa. m3 /mol .K
=R
R = 8.314 Pa . m 3 / mol K
:
) (Pa . m3 ) (Joul :
1 Pa m3 = 1 J
R = 8.314 Pa . m 3/mol . K
R = 8.314 J/ mol K
R = 8.314 J/ mol K
( ) (R dyne. cm /mol K
dyne/cm2 )) (1 atm
1 dyne = 1 g . cm . s-2 :
)) (1 atm (76
) cm dyne/cm2 :
)(293
)(294
/
P=hdg
g
cm
) ) (980.6667 2
3
cm
s
)(d
) (a
1atm = (76.00 cm) (13.5951
1 atm = 1013251.9 g cm-1 s -2

10132252 g cm s-2
= 1013252 dyne/cm 2
2
cm
1 atm = 1.013252 106 dyne/cm2
= 1 atm
) (1 atm
: dyne. cm/mol K
) P( dyne/cm2 ) (cm3
=R
= N . m mol-1 K-1
mol K
) (1.013252 106 dyne/cm2 ) (22413.6 cm3
=R
1 mol 273.15 K
R = 83143419.47 dyne . cm/ mol K
R = 8.314 10 7 dyne . cm/ mol K
( ) (R erg/mol K
) (1 dyne
) (1 cm . :
1 erg = 1 dyne. cm
)(294
)(295
/
R :erg
) PV (1.013252 106 dyne/cm2 ) (22413.6 cm3
=R
=
RT
)(1 mol) (273.15 K
R = 83143419.47 dyne. cm/mol.K
R = 83143419.47 erg/mol.K
R = 8.31 10 7 erg/mol.K

:
1 Joul = 107 erg
R = 8.314 107 erg/mol.K
R = 8.314 Joul/K.mol
( ) (R N .m /mol K
) (N/m2 ) (m3
:R
) P(N/m 2 ) (m 3
=R
= N . m mol -1K -1
mol K
) (1 Kg ).(1 m/s2
) (N )(m . Kg . s
) (Standard Atmosphere
):(m . Kg .s
)(295
(296)
/
) (
:
P=h.d.g
P = h (m) . d (Kg/m 3 ) . g (m/s 2 ) = Kg m -1 s -2 = Kg m s -2 /m 2 = N/m 2
Newton
( h = 76 cm, d = 13.596 g/cm 3, g = 980.7 cm/s2)

: ( Kg, m)
h Hg = 76.00 cm = 0.7600 m
13.5951 g 13.5951 g 10-3 Kg g -1
=
= 13595.1 Kg m-3
cm3
1 cm3 10- 6 m3 cm-3
980.6665 cm
980.6665 cm 10-2 m cm -1
g=
=
= 9.806665 ms -2
2
2
s
s
-3
-2
P = h (m) . d (kg m ) . g (ms )
d Hg =
P = (0.7600 m) (13595.1 kg m- 3 ) (9.806665 m s- 2 )

P = 101325.1694 kg m -1 s -2 = 1.01325 105 kg m -1s -2
P = 1.01325 105 Kg m s -2 /m 2
(where N = Kg m s-2 )
P = 1.01325 10 N/m 2
5
N. ( 1 atm)
: m/mol K
P (N/m 2 ) (m3 )
= N . m mol-1 K-1
mol K
(1.01325 105 N/m 2 ) (0.0224136 m3 )
R=
1 mol 273.15 K
R=
R = 8.314 N . m/ mol K
(296)
)(297
/
( ) (R J/mol K
). (R = 8.314 N. m/mol K
):(1 m
1 Joule = N . m
:
J = N. m
R = 8.314 N. m/mol K
R = 8.314 J/mol. K
) (8.314 J/mol K
) (Pa ).(m3
( ) (R Cal/mol K

) (calorie :
1 Cal. = 4.184 J
R :
8.314 J / mol K
4.184 J / Cal
=R
R = 1.987 C al/K m ol 2 C al/m ol K

1 dyne = 10-5 N
)(297
(298)
/
:(1 m)
1 Joule = N . m
N/m2 dyne/cm2
1dyne 1 10-5 N
P=
=
= 0.1 N/m 2
2
-4
2
cm
1 10 m
P = 1dyne/cm 2 = 0.1 N/m 2
:
1atm = 1.013 106 dyne/cm2
1dyne/cm 2 = 0.1N/m2
1dyne/cm2 = 0.1 N/m2
1.013 106 dyne/cm2 = P
P=
0.1N/m 2 1.013 106 dyne/cm2

= 1.013 105 N/m 2
2
1dyne/cm
(1 J = 1 ( J/K.mol ) N.m/K.mol R
N. m)
R=
R=
PV
nT
(1.013 105 Newton m-2 ) ( 0.0224136 m3 )
(1 mol) (273.15 K)
R = 8.314 J/K.mol
: k
( Boltzmann constant) (k)

(Gas Constant per Molecule)
(298)
(299)
/
k=
R
8.314 107 erg K -1 mol-1
=
= 1.380 10-16 erg / K. molecule
23
-1
NA
6.023 10 molecules . mol
R
8.314 J K -1 mol-1
k=
=
= 1.380 10-23 J / K . molecule
23
-1
NA
6.023 10 molecules . mol
R :

R
0.082056
82.056
0.08314
8.314
8.314
8.314
8.314
8.314 x 107
8.314 x 107
1.987
R
atm L / mol K
atm ml / mol K
bar L / mol K
KPa. dm3/mol K
Pa. m3 / mol K
N. m / mol K
J / mol K
dyne. cm/mol K
erg / mol K
cal / mol K
atm
atm
bar
kPa
Pa
N/m2
Pa
dyne/cm2
dyne/cm2
L
ml
L
dm3
m3
m3
m3
cm3
cm3
()
4.20 g F2(g)
.(F = 19) : ) 720 torr 42 C
PV = nRT
4.20 g
-1 -1
38 g mol-1 ( 0.08206 L atm mol K ) ( 42 + 273 )
nRT
V=
=
= 3.00 L
P
720 torr
-1
760 torr atm
(299)
)(300
/
)(
740 cm3 ) (He 145 Lb/in2

22 C ) . (He
=4
.(1 atm = 14.7 Lb/in2) :
PV = nRT
m
RT
Mw
PV
m = Mw
RT
= PV
145Lb in -2
740 cm3
-2
-1
1000 cm3 L-1
-1 14.7Lb in atm
m = 4 g mol
= 1.20 g He
( 0.08206 L atm mol-1 K-1 ) ( 295 K)
)(
1.20 L ) (N2
. )(90 C
)(300
(301)
:
/
P1V= nRT1
P2 V= nRT2
P1V nRT1
=
P2 V nRT2
T
P2 =P1 2
T1
P2 = 1atm
363 K
= 1.22 atm
298 K
()
2.5g
.(H = 1 = ( ) R = 0.0821 L.atm /mol K)
PV = n R T
RT
V = n
P
m H2
V=
Mw H
2
RT

0.0821 L. atm mol-1 K -1 273 K

2.5 g
V=
-1
1atm
(2 1)g mol
0.0821L. atm mol-1 K-1 273 K

V = (1.25 mol)
1atm
V = 28 L
()
( 6.02 1022 molecules)

(R = 0.0821 L. atm mol -1 K-1)
(301)
)(302
:
N
NA
=n
6.02 1022 molecules

=n
6.023 1023 molecules/mole
n = 0.1 mole
: N : NA
:
PV = nRT
nRT
P
) ( 0.1mol) ( 0.0821 L. atm mol-1K-1 ) ( 273 K
) (1 atm
=V
=V
V = 2.24 L
)(
0.32 mol CO2 8 dm3 100 C

)(R = 0.0821 L. atm. mol-1. K-1
) (1 dm3 = 1 L (8 dm3 = 8
)L
:
)(302
)(303
/
PV = nRT
nRT
=P
V
) ( 0.32 mol ) ( 0.0821 L. atm mol-1K -1 ) ( 373 K
=P
)(8 L
P = 1.225 atm L
)(
200 ml 45 C

800 mmHg (R = 0.0821 L. atm. mol-1 K- :
).1
1000
atm ) (760 :
PV = nRT
PV
=n
RT
800 mmHg 200 ml
760 mmHg/atm 1000 ml/L

n=
-1 -1
) ( 0.0821 L. atm mol K ) ( 318 K
n = 8.06 10-3 mol
)(
) (560 cm3 1.55 g

.(R = 0.0821 L. atm. mol -1. K-1) :
)(303
(304)
PV = nRT
m
PV =
RT
Mw
m
Mw =
RT
PV
1.55
-1
-1
Mw =
(0.0821 L. atm. mol K ) (273 K)
3
3
(1atm)
(560
cm
/1000
cm
/L)
Mw = 62 g/mol
()
0.75 L 5g
(35 cm Hg) ( 40 C)
35 cm Hg
= 0.46 atm
76cmHg/1atm
T= 40 + 273 = 313 K
P=
PV=nRT
m
RT
Mw
mRT
Mw =
PV
5g
PV =
(0.0821 atm.Lmol -1K -1 ) (313 K)
Mw
(5 g ) (0.0821 atm.Lmol-1K -1 ) (313 K)
Mw =
( 0.46 atm ) ( 0.75 L )
PV =
Mw = 372.42 g/mol
(304)
)(305
/
)(
CH4 20 L 190 cmHg

) (-5 C :
(
.(R = 0.0821 L. atm. mol -1 K-1) (H = 1, C = 12) :
) (atm ) (K :
190 cmHg
= 2.5atm
76cmHg/atm
=P
T = ( - 5 C + 273) = 268 K
( : n
)( 2.5 atm
PV = nRT
PV
=n
RT
) ( 20 L
)(0.0821 L. atm. mol- K-1 ) (268 K
n = 2.27 mol
=n
( : m
)Mw CH4 = (12 + 4 1 = 16
m CH4 = n Mw
m CH4 = 2.27 16
m CH4 = 36.32 g
)(305
)(306
/
( : N
N
NA
=n
N = n NA
N = 2.27 mol 6.023 10 23molecules mol-1
N = 1.37 10 24 molecules
)(
) (g mol-1 1.12 g
240 ml 755 torr 100 C
755 torr
= 0.993 atm
760 torr/atm
240 ml
=V
= 0.24 L
1000 ml/L
T = 100 C + 273 = 373 K
=P
PV = nRT
m
RT
Mw
m
= Mw
RT
PV
)(1.12 g ) (0.0821 L.atm mol -1K -1) (373 K
= Mw
) ( 0.993 atm) (0.24 L
= PV
Mw = 144 g/mol
)(
)(H = 7%, C = 55.8 %, O = 37.2%

1.45 g ) (530 cm3
100 C ) (740 mmHg .
)(306
)(307
/
) .(H = 1, C = 12, O = 16 :
:
740 mmHg
= 0.974 atm
760 mmHg/atm
=P
530 cm3
=V
= 0.53 L
1000 cm3 /L
T = 100 + 273 = 373 K
P V= n R T
m
=PV
RT
Mw
mRT
= Mw
PV
)(1.45 g ) (0.0821 L atm mol-1 K-1 ) (373 K
= Mw
)(0.974 atm) (0.53 L
Mw = 86 g/mol
) (100 g
= 7.7 g ) (55.8 g
) (16 g :
m O + m H + mC
37.2 + 7 + 55.8 = 100 g
:
mO 37.2
= 2.325 mol
Aw O 16
= nO
mH
7
= = 7 mol
Aw H 1
= nH
mC
55.8
=
= 4.65 mol
Aw C
12
= nC
)(307
)(308
/

)(2.325
:
:
O
2.325
:
2.325
: 1
H
7
2.325
: 3
:
:
C
4.65
2.325
2
C2H3O :
(2 12 + 3 1 + 1 16 = 43) :
:

=

86
=2
=
43
2(C2H3O) = C4H6O2 :
)(
) (N2 ) (0.29 L )(25 C

) (0.1 g O2
) (0.997 atm .
= .(14
)(308
)(309
:
m O2
Mw O2
0.1 g
= 3.125 10 -3 mol
(2 16) g/mol
= n O2
= n O2
) + (
:
Pt V = n t RT
) ( 0.997 atm ) ( 0.29 L
Pt V
RT
= nt
= nt
)(0.0821 L.atm/K.mo) (25 + 273

n t = 0.0118 mol
:
n t = n O2 + n N 2
n N 2 = n t - n O2
n N 2 = 0.0118 - 3.125 10-3
n N 2 = 8.675 10-3 mol
:
m N 2 = n N 2 Mw
)m N 2 = ( 8.675 10 -3 ) (2 14
m N 2 = 0.2429 g
)(309
)(310
/
)(
) (O2 ) (HBr
) .
(H =1, O = 16, Br = 80 :
) (O2 ): (HBr
RT
m O2
Mw O2
m HBr
RT
Mw HBr
= PO2 . V
= PHBr .V
m O2 = m HBr
:
m O2
RT
Mw O2
PO
1
Mw HBr
= 2
m HBr
PHBr Mw O2
1
RT
Mw HBr
Mw HBr 81
=
Mw O2 32
PO2 . V
PHBr .V
=
PO2
PHBr
HBr
)(
) (10 L
).(R = 0.0821 at. L/mol K) (STP
)(310
)(311
= 0.446 mol
) (10 L
) (1 atm
PV = nRT
PV
=n
RT
)(0.0821 L.atm mol-1K -1 ) (273 K
=n
:
N H2 = n H2 . N A
N H 2 = 0.446 mol 6.02 10 23 molecules/mol = 2.68 10 23 molecules
:
N H = 2.68 1023 2 = 5.36 1023 atoms
)(
) (10 g ) (4.62 L ) (35 C ) (762 torr

) (12.3 g ) (51 C
.
) (10 g :
)(311
)(312
/
m
RT
Mw
m
= Mw
RT
PV
)(10 g ) (0.0821 L.atm mol-1K-1 ) (308 K
= Mw
)(762 torr/760 torr atm-1 ) (4.62 L
Mw = 54.59 g/mol
= PV
): (10 + 12.3 = 22.3 g

m
m
= RT P
RT
Mw
MwV
)22.3 g ) (0.0821 L.atm mol-1K -1 ) (324 K
(
=P
)(54.59 g/mol) (4.62 L
P = 2.35 atm
= PV
760 torr
P = 2.35 atm
=1786 torr
atm
)(
NH3
H2
CO2
HCl
)P (atm
1
0.9
0.23
1.5
)V (L
2
26.7
10
8.2
)n (mol
0.082
1
0.1
0.5
)m (g
1.4
2
4.4
18.25
)N (molecule
4.9 1022
6.02 1023
6.02 1022
3.01 1023
)T (C
25
20
5
27
)T (K
298
293
278
300
)(
CO
C4H8 .
) (H = 1, C = 12, O = 16 :
)(312
)(313
/
m CO
RT ............1
Mw CO
RT.........2
m C4 H 8
Mw C4 H8
= PCO .VCO
= PC4 H8 .VC4 H8
) (1 ): (2
mCO
RT
Mw
PCO .VCO
CO
=
PC4H8 .VC4H8 mC4H8
RT
Mw
C
H
4 8
Mw C4 H8
PCO
=
PC4H8
Mw CO
PCO
56 2
=
=
PC4H8 28 1
PCO . PC H
8
)(
) (R ) (Pa. m3. mol-1. K-1

)(STP
P = 1 atm = 101325 Pa
V = 1 L = 1 10-3 m3
T = 0 C = 273 K
:
) (V = 22.4 L = 22.4 10-3 m3
: R
)(313
)(314
/
PV
nT
101325 Pa 22.4 10-3 m3
=R
1 mol 273 K
R = 8.314 Pa. m3 . mol-1 K -1
=R
)(
CO2 ) (100 C
)(1.5 atm ) .(C = 12, O = 16
:
MwCO 2 = 1 12 + 2 16 = 44 g/mol
:
P Mw = d R T
P Mw
RT
) (1.5 atm ) ( 44 g/mol
) ( 0.0821 L.atm/K.mol ) (373 K
=d
=d
d = 2.16 g/L
: g/cm3
2.16 g
L
2.16 g
=d
1000 cm 3
d = 2.16 10 -3 g/cm 3
=d
)(314
)(315
/
)(
).(0.00187 g/cm3
: g/L
0.00187 g
cm 3
0.00187 g
=d
10-3 L
d = 0.00187 1000 = 1.87 g/L
=d
:
P Mw = d R T
d
= Mw
RT
P
1.87 g/L
Mw=
) ( 0.0821 L.atm/K.mol ) ( 273 K
1atm
Mw = 42 g/mol
)(
10531 g 1.531 ml
10 C 2 atm
0.28 g 15.0 ml 25 C
)(315
)(316
g1
RT1
Mw
g
P2 V2 = 2 RT2
Mw
= P1V1
or
or
P1V1 = n1RT
P2 V2 = n 2 RT2
g1
RT1
P1 V1
Mw
=
P2 V2
g2
RT2
Mw
) ( 2 atm ) (1.531 10-3 L ) ( 0.28 g ) ( 298 K

P1V1g 2 T2
=
= P2
V2 g1T1
) (150 10-3 L ) (1.531 g ) ( 283 K
P2 = 0.00306 atm
)(
) 21%
(79% 10.0 cm
) (0 C, 100 C ) (1 atm )
.(0 C
/ :
4
4
22
= r3
(10) 3 = 4190 cm 3 = 4.19 L

3
3
7
Pt = 1 atm :
PO2 = 0.21 atm
PN2 = 0.79 atm,
:
=
N = n . NA
)(316
)(317
/
:
PV
RT
=n
0.79 atm 4.19 L

= 0.14786 mol
0.082 L atm/K mol 273 K
0.21 atm 4.19 L
= n O2
= 0.0393 mol
0.082 L atm/Kmol 273 K
= n N2
: N
N N2 = N A n N2
N N2 = 6.023 1023 0.14786 = 8.9 1022 molecules
N O2 = N A n O2
N O2 = 6.023 1023 0.0393 = 2.366 10 22 molecules
/ : 100 C

:
P1 P2
=
T1 T2
) (P ) = (P
N2 2
N2 1
T2
T1
( P ) = ( P ) TT = 0.79 373
= 1.079 atm
273
N2 1
N2 2
:
P1 P2
=
T1 T2
) (P ) = (P
O2
O2 1
T2
T1
( P ) = ( P ) TT = 0.21 373
= 0.28692 atm
273
O2 1
O2
)(317
)(318
/
:
PV
RT
=n
1.079 atm 4.19 L

= 0.14786 mol
0.082 L atm/K mol 373 K
0.28692 atm 4.19 L
= n O2
= 0.0393 mol
0.082 L atm/Kmol 373 K
= n N2

.
)(
) (A ) (500 ml ) (B 1000 ml
) (STP B 100 C
(
( B A
) : = 1.29 g/L .(STP
)(318
(319)
:
/
P V
PV
=
T
T
V
P (VA + VB )
VB
= P A +
T1
T + 100
T
P (VA + VB )
P (VA + VB )
T ( T + 100 )
T
T
P (V + VB )
P=
=
= A
VA ( T + 100 ) +T VB
T
VA ( T + 100 ) +T VB
VA
VB
+
T ( T + 100 )
T + 100
T
P=
P=
P (VA + VB ) ( T + 100 )
VA ( T + 100 ) + T VB
76 cmHg ( 500 cm3 +1000 cm3 ) ( 273 + 100 )
500 cm3 (273 + 100 K) + 273 K 1000cm3

P = 92.6cm Hg
76 cmHg 1500 cm3 x 373 K

500 cm3 373 K + 273 K 1000 cm3
: B
Po V = n o RTo , P V= n R T
Po V n o RTo
P
n T
=
o = o o
PV nRT
P
nT
Po n T = P n o To
PTo 92.6 273
n
=
=
= 0.89
n o Po T
76 373
89% B
11% A
: A
0.11 1.29 = 0.1419 g
()
16.5 C 27.34 ml 0.0825 g

. 704 mmHg
(319)
)(320
m
RT
Mw
m
= Mw
RT
PV
=PV
0.0825 g
0.082 atm.L/mol.K 289.5 K = 77.3 g/mol
704 mmHg
27.34 ml
760 mmHg/atm 1000 ml/L
= Mw
)(
8 L 1000 atm
1.5 Kg
.
:
m
RT
Mw
P V Mw
1000 atm 8 L 18 g/mol
=T
=
)= 1170 K (897 C
mR
1500 g 0.082 atm. L/K.mol
= PV
)(
) ( 1.56 g/cm3
) . CO2 .(44.01 g/mol
44.01 g/mol = CO2

:
)(320
(321)
/
m
V
m
44.01 g
V=
=
= 28.2 cm 3 /mol
3
d
1.56 g/cm
d=
1mol of CO 2contains N A molecules = 6.022 10 23molecules

V(one molecule) =
28.2 cm 3/mol
= 4.68 10 -23cm 3/molecule
23
6.022 10 molecules/mol
()
(0.5 atm) ( 0.25 mol)

.(R = 0.08206 L.atm/K.mol) : ( 50 C)
PV=nRT
0.5 atm V = ( 0.25 mol
V=
( 0.25 mol )
( 0.08206 atm L/K mol ) (298 K)
( 0.08206 atm L/K mol ) (298 K)

= 12.23 L
0.5
()
(27 C) NH3 ( 3.4 g)

(2 atm)
( Mw
NH3
= 17, m NH3 = 3.4 g. R = 0.0821 L atm/K. mol
: PV = nRT
(321)
(322)
/
m
PV =
RT
Mw
m RT
V=
Mw P
3.4 g
0.0821 L . atm mol -1K -1 300 K
V=
17 g mol -1
2 atm
V = 2.463 L
()
( 2.8 L) ( 10 g)
.(R = 0.0821 atm L/mol K) : ( 2 atm) ( 27 C)
m
RT
Mw
m
Mw =
RT
PV
10 g
Mw =
(0.0821 atm L/Kmol) (300 K)
2 atm 2.8L
Mw = 44 g/mol
PV=
()
1.2 atm 27 C g/L ( C2H6)
.(V = 1 L, R = 0.0821 atm. L/K. mol)
(322)
)(323
PV = nRT
m
= PV
RT
Mw
m
PMw = RT
V
PMw = dRT
PMw
=d
RT
1.2 atm 30 g/mol
=d
= 2.46 g/L
( 0.0821 atm.L/mol K ) 300 K
)(
) (560 cm3 ) (1 g
) (1.5 g ) (880 cm3
. .

PV = nRT
m
RT
Mw
m
= Mw
RT
PV
= PV
)(323
(324)
:
/
m
RT
PV
m CO2 RT
Mw =
Mw CO2
Mw X
44
Mw X
m CO2
PVCO2
Mw CO2 VCO2
=
m X RT
mX
Mw X
PVX
VX
1
= 560 Mw X = 42 g/mol
1
880
(324)
)(325
/
) (d )(Mw
Gas Density and Molar Mass

Using the Gas Laws to Determine Molecular Weight
:
m
d=
V

.

) .(Mw

. (22.4
) L ) . (1 atm, 25 C
22.4 L
.
PV = n R T
m
=PV
RT
Mw
m
) P Mw = ( RT
V
P Mw = d R T
)(325
)(326
/
:
: m g
: Mw )(g/mol
: d g/L .
g/ml g/cm3 :
) (1 ml = 1 cm3 / .
: R ).(0.0821 L. atm/mol K

Molecular Weight of A gas by Limiting Density Method
) (n ) (V :
PV = nRT
) (m ) (Mw
:
m
Mw
=n
:
m
RT
Mw
=PV
:
m
RT
V
P Mw = d R T
= P Mw
d
Mw = R T
P
.
)(326
)(327
/
) (Mw ) (R
d

P
) (P ) .(

d

P
)) (P .(
d

P
) (P
d

P
limiting Value :
d
RT
P
= Mw
:
d
Mw = R T
P
)(327
)(328
/
.
limiting Density Method
.

.
) (17.034
) (1.0080 :
17.034 = Atomic weight of N 2 + 3 1.0080
Atomic weight (N 2 ) = 17.034 - 3.024 = 14.010

: Regnualts method

)(328
)(329
Fig. 65 : Determining the density of an unknown gas. A bulb of known volume is

evacuated, weighed when empty, filled with gas at a known pressure and temperature,
and weighed again. Dividing the mass by the volume gives the density.
Volatile Substances
.Victor Mayer Method

:

.

.
)(329
)(330
/
)(
CO2 ).(STP
Mw CO2 = (1 12 + 2 16) = 44 g/mol

PMw = d RT
) (1atm
P Mw
RT
=d
) ( 44 g/mol
)(0.0821 atm.L.mol-1 K -1 ) (273 K
d = 1.96 g/L
=d
) (1 mol
= 22.4 L
44 g = CO2 :
m
V
44 g
=d
22.4 L
d = 1.96 g/L
=d
)(
O2 )(STP
) = .(16
)(330
(331)
:
/
Mw O2 = 2 16 = 32 g/mol
PMw = d R T
d=
P Mw
RT
1atm 32 g/mol
(0.082 L.atm/mol K) (273 K)
d = 1.43 g/L
d=
22.4 L ( 0 C)
32 g/mol
:
m
32 g
=
V
22.4 L
d = 1.43 g/L
d=
()
( ) 74 cm Hg) ( - 5 C) ( N2)
.(14 =
74 cm Hg
= 0.974 atm
76 cm Hg/ atm
T = (- 5 + 273) = 268 K
Mw N 2 = 2 14 = 28 g/mol
P=
P Mw = d R T
P Mw
(0.974 atm) (28 g/mol)
d=
=
= 1.24 g/L
RT
(0.0821 L. atm K -1 mol-1 ) (268 K)
(331)
)(332
/
)(
) (1.23 g/L )(STP

).(R = 0.0821 L. atm/mol. K
PMw = dRT
dRT
P
)(1.23 g/L) (0.0821 L atm mol-1K -1 ) (273 K
= Mw
)(1 atm
Mw = 27.57 g/mol
= Mw
)(
) (2.3 g/L ) (- 25 C
) (2.35 atm )(R = 0.0821 L. atm. mol-1 K-1
PMw = dRT
dRT
P
)(2.3 g/L) (0.0821 L. atm. mol-1K -1 ) (- 25 + 273
= Mw
)(2.35 atm
Mw = 19.93 g/mol
= Mw
)(
) (Ar ) (- 5 C ) (1 g/L
) (atm ) = .(40
)(332
)(333
PMw = d R T
dRT
=P
Mw
)(1 g/L) (0.0821 L. atm. mol-1 K-1 ) (- 5 + 273
=P
40
P = 0.55 atm
)(
)(2 g/mol
) (1.4 g/cm3 ) (1.4 109 atm
)(R = 0.0821 L. atm. mol -1 K-1
): (g/L
0.0014 g
cm3
0.0014 g
=d
1cm3
1000 cm3 /L
=d
)(0.0014 g
= 1.4 g/L
0.001 L
=d
:
P Mw = d R T
P Mw
=T
dR
)(1.4 109 atm) (2 g/mol
=T
= 2.44 1010 K
) (1.4 g/L) (0.0821 L.atm mol-1 K -1
)(333
)(334
/
)(
) (C2H6 ) (1.2 atm ) (27 C

) (g/ml ) : .(H = 1, C = 12) :
PMw = d R T
PMw
RT
)(1.2 atm) (2 12 + 6 1
=d
)(0.0821 L. atm. mol-1 K -1 ) (300 K
d =1.46 g/L
=d
g/ml :
1.46 g 1.46 g
=
= 1.46 10 -3 g/ml
L
1000 ml
=d
)(334
)(335
/

)(
) (Cl2 ) (9.125 g
) (HCl ) (20 C ) (836 mmHg
KMnO4 :
2KMnO 4 + 16HCl
8H 2O + 2KCl + 2MnCl 2 + 5 Cl 2

.
HCl :
mHCl
Mw HCl
= n HCl
9.125g
= 0.25 mol
)(1 + 35.5
= n HCl
:
16 mol HCl
5 mol Cl2
0.25 mol HCl
nCl2
5 0.25
= 0.0781 mol
16
= n Cl2
)(335
)(336
/
:
PV = nRT
nRT
=V
P
0.0781 mol 0.0821 L.atm mol -1K -1 (20 + 273) K
=V
= 1.71 L
836 mmHg
760 mmHg atm -1
)(
CaH2 ) (0.6 L
) (H2 ) (20 C ) (1.0 atm :
CaH 2 + 2H 2 O
) Ca(OH)2 + 2H 2 (g

:
PH 2 V = n H 2 RT
PH 2 V
RT
=n
1.0 atm 0.6 L

0.0821 L.atm mol-1 K -1 (20 + 273) K
n H 2 = 0.025 mol
= n H2
:
1 mol CaH 2
2 mol H 2
n CaH 2
0.025 mol H 2
1 0.025
2
n Ca(OH)2 = 0.0125 mol
= n CaH 2
)(336
)(337
/
:
mCaH2
Mw CaH2
= n CaH2
m CaH2 = n CaH2 Mw CaH2

m CaH2 = 0.0125 mol (40 + 2 1) g mol-1
m CaH2 = 0.525 g
)(
15 g
:
Ca + 2H 2 O
Ca(OH)2 + H 2
) = .(40
:
m Ca
Mw Ca
= n Ca
15 g
40 g mol -1
n Ca = 0.375 mol
= n Ca
:
1 mol Ca
1mol H 2
n H2
0.375 mol Ca
1 0.375
= 0.375 mol
1
= n H2
)(337
)(338
/
:
PV = nRT
nRT
P
0.375 mol 0.0821 L. atm mol -1K -1 273 K
=V
1 atm
V = 8.40 L
=V
)(
) ( CO2
) (0.05 mol CaCO3
:
CaCO 3 (S) + 2HCl
) CaCl 2 + H 2O + CO 2 (g
1.12 L :
)(
4.6 g Na (40
) C ) (0.8 atm :
2Na + 2H 2O
2NaOH + H 2
3.2 L :
)(338
)(339
/
)(
) (100 L
:
2KClO3
2KCl + 3O2
)(K = 39.1, Cl = 35.5, O = 16
364.49 g :
)(
C2H5OH ) (146 L )(O2

) (27 C ) (91.2 cmHg :
C 2 H 5OH + 3O 2
2CO 2 + 3H 2 O
)(H = 1, C = 12, O = 16
109.066 g :
)(
)(STP ) (112 g
).(KClO3
MnO 2
) 2KCl(s) + 3O 2 (s
2KClO 3 (s)
heat
VO2 = 30.7 L
)(339
)(340
/
)(
) (1.80 g ) (KClO3
) (KCl ) . (KClO3
) (405 ml ) (25 C ).(745 torr
(
( KClO3
( )(0.0162 mol
( %KClO3 = 73.3 %
)(340
)(341
/

)Daltons Law of Partial Pressures (1807
.
" "

.
.

.
. ) (25 C
24 mm Hg
24 mmHg
.25 C 760 mmHg
:
Pt = Pair + PH2O
Pt = 760 + 24 = 784 mmHg
=
). (24 mmHg
.
) (N2 500 mmHg
524 mmHg .25 C
) (1801 :
"
".
)(341
)(342
/

.
.

.

.
Fig. 66 : Dalton's Law of partial pressures. Partial pressure of oxygen gas (small
dots) is 250 torr, and partial pressure of nitrogen gas (large dots) is 300 torr
Fig. 67 : Schematic illustration of Dalton's law of partial pressures.
)(342
(343)
:
/
Fig. 69 : Dalton's law of partial pressures
(343)
(344)
:
/
Fig. 70 : An illustration of Dalton's Law. When the two gases A and B are mixed in
the same container at the same temperature, they exert a total pressure equal to the
sum of their partial pressure.
Fig. 71 : A molecular interpretation of Dalton's Law. The molecules act

independently in the mixture, so each gas exerts its own partial pressure due to its
molecular collisions with the walls. The total gas pressure is the sum of the partial
pressures of the component gases.
1 L
:
0.5 atm ( N2)
0.75 atm ( O2)
0.1 atm ( H2)
(Pt)
:
(344)
)(345
/
Pt = PN2 + PO2 + PH2
Pt = 0.5 + 0.75 + 0.1
Pt = 1.35

).(
) (4 mmHg
) .(6 mmHg
).(10 mmHg
:
"
"
) (n .
Pt = P1 + P2 + .+ Pn
) (

.
). (Partial Pressure
) (A, B, C ) (nA, nB, nC
:
)(345
)(346
/
nAR T
V
n RT
PB V= n B RT PB = B
V
nCR T
= PC V= n C RT PC
V
Pt = PA + PB + PC
= PA V= n A RT PA
n RT
n A RT
n RT
+ B
+ C
V
V
V
(n + n B + n C ) R T
Pt = A
V
nt R T
= Pt
V
Pt V = n t RT
= Pt
:
PV = nRT
:
Pt V = nt RT

) (Pressure Fraction
PA
Pt
pressure fraction =
)(346
)(347
/
PA V = n A RT
Pt V = n t RT
PA V n A R T
=
Pt V n t R T
PA
n
= A = XA
Pt
nt
PB
n
= B = XB
Pt
nt
PC
n
= C = XC
Pt
nt
) (XA, XB, XC ) (Mole Fraction (A, B,

) .C :
X = 1
:
PA = XA Pt
PB = XB Pt
PC = XC Pt

.
.
.

.

(effective
)(347
)(348
/
) volume

.

Collecting Gases Over Water

.
. ) (
)
)
(
. ) (Vapor Pressure
.

.
)(348
(349)
:
/
Fig. 74 : Pressure of a wet and dry gas
Fig. 75 : Collection of a gas over water. The water vapor is shown in the collection
bottle as (dark dots), and the gas as (green dots).
(349)
(350)
:
/
Fig. 77 : Apparatus for preparing hydrogen from zinc and sulfuric acid.
Zn 2+ (aq) + H2 (g) . The hydrogen is collected by displacement
Zn(s) + 2H + (aq)
of water.
(350)
(351)
Fig. 78 : Collection gas over water
:
vapor Pressure of Water at Different Temperatures
T
C
0
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
23
P
kPa
0.61
0.65
0.71
0.76
0.81
0.87
0.93
1.00
1.07
1.15
1.23
1.31
1.40
1.49
1.60
1.71
1.81
2.81
P
mmHg
4.6
4.9
5.3
5.7
6.1
6.5
7.0
7.5
8.0
8.6
9.2
9.8
10.5
11.2
12.0
12.8
13.6
21.1
T
C
24
25
26
17
18
19
20
21
22
27
28
29
30
31
32
33
34
35
P
kPa
2.97
3.17
3.36
1.93
2.07
2.20
2.33
2.49
2.64
3.56
3.77
4.00
4.24
4.49
4.76
5.03
5.32
5.63
P
mmHg
22.4
23.8
25.2
14.5
15.5
16.5
17.5
18.7
19.8
26.7
28.3
30.0
31.8
33.7
35.7
37.7
39.9
42.2
T
C
40
45
98
99
100
101
50
55
60
65
70
75
80
85
90
95
96
97
P
kPa
7.37
9.59
94.30
97.75
101.325
105.00
12.33
15.73
19.92
25.00
31.16
38.54
47.34
57.81
70.10
84.54
87.67
90.94
P
mmHg
55.3
71.9
707.3
733.2
760.0
787.6
92.5
118.0
149.4
187.5
233.7
289.1
355.1
433.6
522.8
634.1
657.6
682.1
()
(351)
)(352
: . )(100 C
) (760 mm Hg ).(1 atm
.
:
= + .
Pt = Pgas + PH 2O
= .
Pgas = Pt - PH2 O
= .
PH2 O = Pt - Pgas

.

) (.
.
)(352
)(353
/
) (
:
Pgas = Pt - PH 2O
:KClO3
2KClO3 (s)
) 2KCl(s) + 3O 2 (g
MnO 2
).(
)(353
(354)
:
/
Fig. 81 : An apparatus for collecting gas over water. The oxygen

generated by heating potassium chlorate (KClO 3) in the presence of a
small amount of manganese dioxide (MnO 2), which speeds up the
reaction., is bubbled through water and collected in a bottle as shown.
Water originally present in the bottle is pushed into the trough by the
oxygen gas.

.
P
: P
Pt = PO2 + PH2O
PO2 = Pt - PH2O
(354)
)(355
/
Partial Volume

Partial Volume
.

P ) (n1 )(V1
:
n1RT
P
= V1
:
n 2 RT
P
= V2
:
n 3RT
P
= V3
) (i :
n i RT
P
= Vi
): (Vt
Vt = V1 + V2 + V3 + ...+ Vi
( n1 + n 2 + n3 +...+ ni ) RT
P
) ( V1 + V2 + V3 + ...+ Vi
n t = n1 + n 2 + n 3 +...+ ni
nt R T
P
= Vt
)(355
(356)
:
/
:
V1 =
n1RT
P
:
Vt =
nt R T
P
:
n1RT
V1
P
=
n
Vt
t R T
P
V
n
1 = 1 = X1
Vt
nt
V1
= X1
Vt
:
V1 = X1Vt
V2 = X 2 Vt
V3 = X 3 Vt
:
V
Volume Fraction = 1
Vt
Volume Fraction
.
n
n + n 2 + n 3 +...+ n i
n
n1
n
n
+ 2 + 3 +..........+ i = 1
= t =1
nt
nt
nt
nt
nt
nt
(356)
)(357
/
)(
7.50 g) (N2 6.00g

) (He 2.50 L ).(15 C
) (N = 14, He = 4) :
/ :
m
7.5 g
=
= 0.27 mol
Mw 28 g/mol
m
6
= n He
= = 1.5 mol
Mw
4
n t = n N 2 + n He = 0.27 + 1.5 = 1.77
= n N2
:
Pt V = n t RT
n t RT
V
)1.77 0.0821 (15 + 273
= Pt
2.50
Pt = 16.74 atm
= Pt
)(

23C 23.50 mmHg 754 mm
Hg
)(357
)(358
/ :
Pt = PH2O + PH2
PH2 = Pt - PH2O
PH2 = 754 - 23.50
PH2 = 730.5 mmHg
:
PH2 = X H2 Pt
PH2 730.5
=
= 0.97
P
754
X H2 =
)(
) (A
) 0.495 g (B) (66.0
) 0.182 g (45.5 (76.2

) cmHg .
mA
0.495 g
=
= 0.0075mol
Mw A 66 g mol-1
m
0.182
= nB = B
= 0.004 mol
Mw B 45.5
nt = n A + n B = 0.0075 + 0.004 = 0.0115 mol
n
0.0075
= XA = A
= 0.6522
nt
0.0115
n
0.004
= XB = B
= 0.34783
nt
0.0115
PA = X A Pt = 0.6522 76.2 cmHg = 49.7 cmHg
PB = X B Pt = 0.34783 76.2 cmHg = 26.5 cmHg
= nA
)(358
)(359
/
)(
) (C6H14 6
250 C .
.
m
1
=
= 0.0556 mol
Mw 18
m
1
= n Hexane
=
= 0.0116 mol
Mw
86
n t = n H2O + n Hexane = 0.0556 + 0.0116 = 0.0672 mol
= n H2O
Pt V = n t RT
n t RT
V
0.0672 mol 0.082 L atmK-1 mol-1 523 K
= Pt
6L
Pt = 0.492 atm
= Pt
Pt = 374 mmHg
)(
) (10 L ) (100 atm

) (0.4 L ).(20 atm
( )(10 L
( .
.
:
)(359
)(360
/
P1V1 = P2 V2
100 10 = 20 V2
V2 = 50 L
VO2 = 50 - 10 = 40 L
) = (40 L
:
40
100 = 80 %
50
( :
40
= 100 cylinder
0.4
)(
) (42 C
)(- 38 C

) (2000 m3
) (780 mmHg .
:
PV = n R T
780
) 2000 103 = n1 0.0821 (42 + 273
760
n1 = 0.795 105 moles
)(360
)(361
/
:
PV = n R T
780
) 2000 103 = n 2 0.0821 (- 38 + 273
760
n1 = 1.065 105 moles
:
n 2 - n1 = 1.095 105 - 0.795 105 = 0.270 105 moles
) :
).(2 g/mol
Mw . n
2 0 .2 70 10 5
=
= 54 K g
1 0 00
1 00 0
= m Kg
)(
) (0.15 g ) (0.700 g
) (0.340 g ) (1 atm (27
)C
(
(
( .
( :
0.15
= 0.075mole
2
0.700
= n N2
= 0.025mole
28
0.340
= n NH3
= 0.02mole
17
n T = n H2 + n N2 + n NH3
= n H2
n T = 0.075 + 0.025 + 0.02 = 0.12 moles
)(361
)(362
/
:
0.075
= 0.625
0.12
0.025
= 0.208
0.12
0.02
= 0.167
0.12
n H2
nT
n N2
nT
n NH3
nT
= X H2
= X N2
= X NH3
( :
PH 2 = PH 2 =X H 2 PT = 0.625 1= 0.625atm
PN 2 = X N 2 PT = 0.208 1 = 0.208 atm
PN H 3 = X N H 3 PT = 0.167 1 = 0.167 atm
( :
PV = n R T
)1 V = 0.12 0.082 (27 + 273
V = 2.952 L
)(
) ( .

.753 mmHg
34 C 425 cm3
760 mmHg 0
C 34 C 40 mmHg
)(362
)(363

753 mmHg .
:
Pt = PH 2 + PH 2O
PH 2 = Pt - PH 2O
PH 2 = 753 - 40 = 713 mmHg
0 C 760
mmHg ) : (n = K
P1V1
PV
= 2 2
T1
T2
)(363
)(364
/
:
P
713 mmHg
760 mmHg
T
307 K
273 K
V
425 cm3
V2
n
K
K
:
P1V1
PV
= 2 2
T1
T2
P
T
V2 = V1 1 2
P2
T1
713 mmHg
273 K
3
V2 = 453 cm3

= 355 cm
307 K
760 mmHg
)(
) (0.250 L ) (CO
) (10 C ) .(765 mmHg

)(9.2 mmHg
CO :
PT = PCO + PH 2O
PCO = PT - PH 2 O
PCO = 765mmHg - 9.2 mmHg = 755.8mmHg
)(364
)(365
/
PCO2 V = n CO2 R T
PCO2 V
= n CO2
RT
755.8
0.250
760
=
= 0.0107 mole
)0.0821 (10 + 273
n CO2
)(
) (500 cm3 ) (A
) (76 mmHg ) (800 cm3 )(B
) (152 mmHg
.
nt ) (Vt
Pt Vt = nt R T :
/ A
PA VA = n A RT
PA VA
RT
75
0.500
760
= nA
= 0.00223 mol
)0.0821 (0 + 273
= nA
)(365
)(366
/
/ : B
PB VB = n B RT
PB VB
RT
152
0.800
760
= nB
= 0.00714 mol
)0.0821 (0 + 273
= nB
/ :
n t = n A + n B = 0.00223 + 0.00714 = 0.00937 mol
)(Vt = VA + VB
) (nt = nA + nB ): (Pt
Pt Vt = n t RT
n t RT
Vt
= Pt
0.00937 0.0821 273

)(0.500 + 0.800
Pt = 0.1615 atm
= Pt
:
/ A
)A ( V2 )T
= ( P2
))A (1300
( P1 )A ( V1 )A
76 500 = ( P2
76 500
= 29.2 mmHg
1300
= ( P2 )A
)(366
)(367
/
/ B
)B ( V2 )T
= ( P2
))B .(1300
( P1 )B ( V1 )B
152 800 = ( P2
152 800
= 93.5 mmHg
1300
= ( P2 )B
/ :
Pt = PA + PB = 29.2 + 93.5 = 122.7 mmHg
): (atm
122.7
= 0.1615 atm
760
= Pt
)(
750 mmHg 35
mmHg
PT = PH2O + Pgas
750 = 35 + Pgas
Pgas = 750 - 35 = 715 mmHg
)(
) (32 g ) (O2 ) (112 g )(N2

) (1 atm .
)(367
)(368
/
32
= 1mol
32
112
= 4mol
28
m O2
= n O2
Mw O2
m N2
= n N2
Mw N2
n T = n O2 + n N2 = 1+ 4 = 5 mol
1
= 0.2
5
4
= 0.8
5
n O2
nT
n N2
nT
= X O2
= X N2
PO2 = X O2 PT = 0.2 1 = 0.2 atm

PN2 = X O2 PT = 0.8 1= 0.8 atm
)(
) (N2 ) (O2 )(CO2

:
Pt = PN2 + PO2 + PCO2
25 KPa 35 KPa
45 KPa :
Pt = 25 kPa + 35 kPa + 45 kPa = 105 kPa

.
)(
) (200 cm3 N2 ) (25 C ) (35 KPa

) (350 cm3 O2 ) (25 C ) (45 KPa
300 cm3
25 C
)(368
)(369

O2, N2
) (300 cm3

:
For O2
P2
300 cm3
45 kPa
350 cm3
P2
300 cm3
For N2
35 kPa
200 cm3
P
V
P2 :
P1V1 = P2 V2
V
P2 = P1 1
V2
200
P2 = 35
300
P2 = 23.3 kPa
) (200 cm3 ) (300 cm3

) (P1 ) (P2
P1 > P2
P1 :
V1 200
=
= 0.667
V
300
:
)P2 = P1 (0.67
) P2 = 35(0.67
P2 = 23.3 = PN2
)(369
)(370
/
/ O2 :
P1V2 = P2 V2
O2 350 cm3 300 cm3 P1

:
V
350
P2 = P1 1 = 45 kPa
300
V2
P2 = 52.5 kPa = PO2
:
PT = PN2 + PO2 = 23.3 + 52.5
PT = 75.8 kPa
)(
) (10.0 L ) (0.200 mol )(0.300 mol

(0.400 mol) ).(25 C
(
(
( : nt
n t = 0.200 mol CH 4 + 0.300 mol H 2 + 0.400 mol N 2 = 0.900 mol of gas
V = 10.0 L, T = 25 + 273 = 298 K
PV = nRT
n t RT
V
)(0.900 mol) (0.0821 L atm/Kmol) (298 K
= Pt
10.0 L
Pt = 2.20 atm
= Ptotal
)(370
)(371
/
(
PV = nRT :
)(0.200 mol) (0.0821 L atm/K mol) (298 K
= 0.489 atm
V
10.0 L
n H RT
)(0.300 mol) (0.0821 L atm/K mol) (298 K
= 2
=
= 0.734 atm
V
10.0 L
n N 2 RT
)(0.400 mol) (0.0821 L atm/K mol) (298 K
=
=
= 0.979 atm
V
10.0 L
=
n CH4 RT
= PCH4
PH 2
PN 2
Pt
Ptotal = PCH4 + PH2 + PN2
Ptotal = 0.489 atm + 0.734 atm + 0.97 atm = 2.20 atm
)(

) (25 C
245 cm3 98.5 KPa
( O2 25 C
25 C 3.17 KPa
( )(STP
:
Pt = Pgas + PH 2O
:
Pt = PO2 + PH2O
PO2 = Pt + PH2O
PO2 = 98.5 - 3.17 = 95.33 kPa
)(371
)(372
/
.
( ) V(O2 (P = 101.325 kPa, T = 273 K) STP
) (i
245 cm3
95.33 KPa
298 K
) (f
V2
101.325 kPa
273 K
V
P
T
) VO2 = V1 (pressure ratio) .( temperature ratio

95.33 273
3
VO2 = 245
= 211.17cm
101.325 298
)(
)(HCl
:
Mg(S) + 2 HCl(aq)
) H 2 (g) + Mg 2+ (aq) + 2Cl- (aq
) (10 L
) (0.5 g
) (488.61 torr .
( ) .(Aw = 1
(
).(22.76 torr
( .
).(nt
( .(
.
( :
)(372
)(373
/
0.5 g
= 0.25 mol
2 g/mol
m H2
Mw H 2
= n H2
( :
PT = PH 2 O + PH 2
P H 2 = PT - P H 2 O
PH 2 = 4 88 .61 to rr - 2 3 .7 6 to rr
PH 2 = 4 64 .91 to rr
( ) ( X H ): (XH2O
2
PH 2
PT
= X H2
464.85
488.61
X H2 = 0.95
= X H2
X H 2O = 1 - X H 2
X H 2O = 1 - 0.95
X H2O = 0.05
( : nt
) (nH2
)(nH2O
n H2
nt
= X H2
n H2
X H2
=nt
0.2 5
0.9 5
n t = 0.263 m ol
= nt
)(373
)(374
/
( )n(H2O

:
n t = n H 2 + n H 2O
n H 2O = n t - n H 2
n H 2 O = 0.263 - 0.25
n H 2 O = 0.013 mol
( : T

:
PH2 V = n H2 RT
PH2 V
n H2 R
=T
464.91 torr
) (10 L
760 torr/atm
=T
= 298 K = 25 C
) ( 0.25mol ) ( 0.082 Latm/K.mol
or
PT V = n T RT
PT V
nTR
=T
488.61 torr
) (10 L
760 torr/atm
= 298K = 25 C
=T
) ( 0.263 mol ) ( 0.082 Latm/K.mol
)(374
)(375
/
)(
) (0.5 atm ) (O2 ) (0.2 atm )(N2

) (0.15 atm NO2
Pt = PO2 + PN 2 + PNO2
Pt = 0.5 + 0.2 + 0.15 = 0.85 atm
)(
) (60 ml 755 torr

25 C
24 torr .
/ :
Pt = PO2 + PH2O
PO2 = Pt - PH2O
PO2 = 755 torr - 24 torr = 731 torr
:
732 torr
= 0.963 atm
760 torr/atm
60 ml
=V
= 0.06 L
1000 ml/L
T = 25 + 273 = 298 K
= PO2
)(375
)(376
/
PO2 V = n O2 RT
PO2 V
= n O2
RT
) (0.963 atm) ( 0.060 L
=n
)(0.0821 L. atm. mol-1 . K -1 ) (298 K
n = 2.36 10-3 mol
)(
H2 20 L 74.7 cmHg
27 C
2.7 cm.Hg
:
Pt = PH 2 + PH 2O
PH 2 = Pt - PH 2 O
PO2 = 74.7 cm.Hg - 2.7 cmHg = 72 cm. Hg
:
72 cm Hg
= 0.95 atm
76 cmHg/atm
V = 20 L
T = 27 + 273 = 300 K
= PH2
PH2 V = n H 2 RT
PH2 V
RT
= n H2
) (0.95 atm) ( 20 L
)(0.0821 L. atm. mol-1. K -1 ) (300 K
n = 0.77 mol
=n
)(376
)(377
/
:
m = n . Mw
m = 0.77 mol (2 1) g/mol
m = 1.54 g
:
N H2 = n . N A
N H 2 = 0.77 6.02 10 23 = 4.6354 10 23 molecules
)(

26 C 80 cmHg 225 ml
. 26 C 10 cm Hg
.
Pt = PN2 + PBenzene
PN2 = Pt - PBenzene
PN2 = 80 cm.Hg - 10 cmHg = 70 cm. Hg
)(377
)(378
/
:
70 cm Hg
= 0.921 atm
76 cm Hg
225 ml
=V
= 0.225 L
1000 ml/L
T = 26 + 273 = 299 K
= PN2
PV = nRT
PV
=n
RT
)(0.921 atm) (0.225 L
= 8.44 10-3 mol
-1
-1
)(0.0821 L. atm. mol . K ) (299 K
=n
:
m = n Mw
m = 8.44 x 10-3 mol (2 14) = 0.23632 g
)(
H2 750 ml
) (25 C ) . (755 torr
24 torr
0.06 g :
)(
500 ml ) (N2 (25

) C 75.5 cm Hg
) (25 C 2.4 cm Hg
)(378
)(379
:
Pt = PH2 + PH2O
PH2 = Pt - PH2O
PH2 = 75.5 - 2.4 = 73.1 cmHg
73.1 cmHg
= 0.962 atm
76 cm . Hg/atm
= pH2
:
PV = nRT
PV
=n
RT
)(0.962 atm) (0.500 L
=n
)(0.0821 L. atm. mol-1K -1 ) (298K
n = 0.02 mol
:
N H2 = n N A
N H 2 = 0.02 6.023 1023 = 1.204 1022 molecule
)(
) (24.8 g ) (30 C
) (736 mmHg
) (25 C )) (3.1 cmHg = (16
)(379
)(380
/
1 cmHg
10 mmHg
P
736 mmHg
1cmHg 736 mmHg
10 mmHg
P = 73.6 cmHg
Pt = PH 2O + PO2
=P
PO2 = Pt - PH 2O
PO2 = 73.6 cmHg - 3.1 cmHg = 70.5 cmHg
70.5 cmHg
= 0.93 atm
76 cmHg/atm
= PO2
:
m
Mw
=n
24.8 g
(2 16) g/mol
24.8 g
=n
= 0.775mol
32 g/mol
=n
:
PV = nRT
nRT
P
)(0.775 mol) (0.0821 L. atm. mol-1K -1 ) (298 K
=V
)(0.928 atm
V = 20.43L
=V
)(
) (0.1 mol
) (2.5 L ) (745 torr
) (23.8 torr .
)(380
)(381
:
Pt = Pg + PH2O
P(g) = Pt - PH2 O
P(g) = 745 torr - 23.8 torr = 721.2 torr
721.2 torr
= 0.95 atm
760 torr/atm
= )P(g
:
PV = nRT
PV
=T
nR
)(0.95 atm) (2.5 L
) (0.1 mol) (0.0821 L. atm. mol-1K -1
T = 289.28 K
=T
)(
) (8 g
:
2A g 2 O (s)
) 4A g(S ) + O 2 (g
) (35 C
) (1 atm
)) (0.0555 atm (O = 16, Ag = 107.9) :
)(381
(382)
/
Pt = PH 2 O + PO2
PO2 = Pt - PH 2 O
PO2 = 1 atm - 0.0555 atm = 0.9445 atm
: Ag2O
n Ag 2O =
m
Mw
8
8g
=
(2 107.9 + 16)
231.8 g/mol
n Ag 2O = 0.0345 mol
n Ag 2O =
2Ag 2O(s)
4Ag(s) + O2 (g)
2 mol Ag 2 O
1mol O2
0.0345 mol Ag 2 O
n O2
n O2 =
(1mol O2 ) ( 0.0345 mol Ag2 O) = 0.01725 mol

( 2 mol Ag 2O )
:
PV = nRT
nRT
V=
P
0.01725 mol ) (0.0821 L. atm. mol-1K -1 ) (35 + 273)K
(
V=
(0.9445 atm)
V = 0.4618 L
(382)
)(383
/
)(
) (800 cm3 ) (Ar

) (0.583 g ) (Ne
) (1.17 atm ) (22 C = (Ne
)20, Ar = 40

:
Pt V= n t RT
Pt V
RT
= nt
)(1.17atm) (800/1000
(0.0821 L.atm. K-1mol-1 ) (22 + 273) K
n t = 0.0386 mol
= nt
)(
)(HCl
:
Mg(S) + 2 HCl(aq)
) H 2 (g) + Mg 2+ (aq) + 2Cl- (aq
) (10 L
) (0.5 g
) (488.61 torr .
( ) .(H = 1
(
).(22.76 torr
)(383
)(384
/
( .
).(nt
( .(
.
( :
m H2
0.5 g
=
= 0.25 mol
Mw H2 2 g/mol
= n H2
( :
PT = PH 2 O + PH 2
PH 2 = PT - PH 2 O
PH 2 = 488.61 torr - 23.76 torr
PH 2 = 464.91 torr
( ) ( X H ): (XH2O
2
PH2
PT
464.85
X H2 = 0.95
= X H2
488.61
X H 2O = 1 - X H 2
= X H2
X H2O = 1 - 0.95 X H2O = 0.05
( : nt
) (nH2
)(nH2O
)(384
)(385
/
n H2
= X H2
nt
n H2
X H2
=nt
0 .2 5
0 .9 5
n t = 0 .2 6 3 m o l
= nt
( )n(H2O

:
n t = n H 2 + n H 2O
n H 2O = n t - n H 2
n H 2 O = 0.263 - 0.25
n H 2 O = 0.013 mol
( : T

:
PH 2 V
n H2 R
= PH 2 V = n H2 RT T
464.91torr
) (10 L
760 torr/atm
=T
= 298K = 25 C
) ( 0.25mol) ( 0.082 Latm/K.mol
PT V
nTR
= PT V = n T RT T
488.61 torr
) (10 L
760 torr/atm
=T
= 298 K = 25 C
) ( 0.263 mol ) ( 0.082 Latm/K.mol
)(385
)(386
/
)(
) (100 ml ) (20 C
750 mmHg ) (105 ml
25 C 750 mmHg
25 C
(V1 = 100 ml, V2 = 105 ml, T1 = 20 C = 293 K, T2 = :

25 C = 298 K,
)? = )P(H2O
Pt = 750 mmHg, P1 = 750 mmHg , P2 = ?,
) (P2
) (Pt .
) (P2 :
P1V1 P2 V2
=
T1
T2
750 mmHg 100 ml
P 105 ml
= 2
293 K
298 K
750 mmHg 100 ml 298 K
= P2
293 K 105 ml
P2 = 726.47 mmHg
Pt = PH2O + Pgas
PH2O = Pt - Pgas
PH2O = 750 - 726.47
PH2O = 23.53 torr
)(386
)(387
/
)(
( 1.25 g O2
25 C 749 mmHg
25 C (R = 0.0821 L. atm/K. mol) 23.8 mmHg
) .(H = 1, O =16 :
( .
:
Pt = PO2 + PH2O
PO2 = Pt - PH2O
PO2 = 749 - 23.8
PO2 = 725.2 mm. Hg
725.2 mm.Hg
760mmHg/atm
PO2 = 0.954atm
= PO2
:
P V=nRT
1.25
0.954 V =
) (0.0821 L . atm/K.mol) (298 K
2 16
0.039 0.0821 298
=V
0.954
V= 1 L
( :
:
)(387
)(388
/
PV = nRT
23.8
)atm 1 L= n H 2O (0.0821 L atm/K. mol) (298 K
760
n H2O =1.28 10-3 mol
)(
127 cm3 ) (STP

(745
) mmHg (21
) mmHg 23 C

:
Pt = PH 2O + Pgas
Pgas = Pt - PH2O
Pgas = 745 mmHg - 21 mm.Hg
Pgas = 724 mmHg
P2 = 724 mmHg
:
P1V1 P2 V2
=
T1
T2
760 127
724 V2
=
273
296
3
V2 = 144.5 cm
)(
20 L CO

20 C ) 750 mm.Hg
)(388
)(389
20 C )) .(17.5 mmHg (R = 0.0821 :
.(L.atm/K. mol
/ :
Pt = PH2O + PCO2
PCO2 = Pt - PH2O
PCO2 = 750 mmHg - 17.5 mmHg = 732.5 mmHg
732.5 mmHg
= 0.964 atm
760 mmHg /atm
= PCO2
CO2
:
PV = nRT
0.964 atm 20 L = n CO2 0.0821 L. atm/K. mol 293 K
0.964 atm 20 L
(0.0821 L.atm/K.mol) 293 K
n CO2 = 0.80 mol
= n CO2
0.8 mol
.
1 mol C
n C = 0.8 mol CO 2
1 mol CO 2
n C = 0.8 mol
m C = n C . Aw
m C = 0.8 12
m C = 9.6 g
)(389
)(390
/
)(
50.0 g O2 50.5 g
CH4 600 mmHg

) . (C = 12, O = 16, H = 1 :

:
m O2
50.0 g
=
= 1.56 mol
Mw O2 32 g/mol
= n O2
mCH4
50.5g
=
= 3.16mol
Mw CH4 16g/mol
= n CH4
n t = 1.56 + 3.16 = 4.72 mol

nO
1.56 mol
= X O2 = 2
= 0.33
nt
4.72 mol
n CH4 3.16 mol
= XCH4
=
= 0.67
nt
4.72 mol
:
PO2 = XO2 Pt
PO2 = 0.33 600 mmHg = 198 mmHg
PCH 4 = XCH4 Pt
PCH 4 = 0.67 600 = 402 mmHg
)(390
)(391
/
)(
2 1023 N2 8.0 1023

CH4 740 mmHg
) . .(C = 12, H = 1, N =14

:
N N2
2 1023
= n N2
=
= 0.332 mol
N A 6.023 1023
NCH4
8.0 1023
= n CH4
=
=1.33 mol
N A 6.023 1023
n t = n N2 + n CH4 = 0.332 + 1.33 = 1.662 mol
n N2
0.332
=
= 0.2
nt
1.662
n CH4 1.33
= X CH4
=
= 0.8
nt 1.662
PN2 =X N2 Pt = 0.2 740 mmHg = 148 mmHg
= X N2
PCH4 = XCH4 Pt = 0.8 740 mmHg = 592 mmHg

)(
152 cm3 25 C
758 mmHg .
23.76 mmHg
) : (H = 1, O = 16 :
)(391
)(392
/
:
( ) (H2(

( H2 H2O .
( :
Pt = PH2 + PH2O
PH2 = Pt - PH2O
PH2 = 758 - 23.76
PH2 = 734.24 mmHg
( :
PV = nRT
) (152 10-3 ) = n H2 (0.0821 L. atm/mol.K) (298 K
) ( 734.42
734.42
-3
) (152 10
760
= n H2
)(0.0821 L. atm/mol.K) (298 K
n H2 = 0.006 mol
( :
:
)(392
)(393
/
PH2 = X H2 Pt
PH2
Pt
= X H2
734.24 mmHg
758 mmHg
X H2 = 0.969
= X H2
X H2O = 1- X H2
X H2O = 1 - 0.969 X H2O = 0.031
)(
370 ml 23 C
0.992 atm
)) (STP 23 C (0.1088 atm
:
Pt = P1 + PH2 O
P1 = Pt - PH2O
P1 = 0.992 - 0.1088
P1 = 0.8832 atm
V2 :
P1V1 P2 V2
=
T1
T2
0.8832 370 1 V2
=
296
298
V2 296 = 0.8832 370 298
0.8832 370 298
= 329 ml
296
= V2
)(393
)(394
/
)(
1.5 g 25 C 730
mm.Hg
( .
( .
( : V2
:
P1V1 P2 V2
=
T1
T2
730 1000
760 V2
=
298
273
V2 = 880 ml
V2 = 0.880 L
( :
PV= nRT
m
PV=
RT
Mw
1.5
1 0.880 =
0.082 273
Mw
Mw = 38.16 g/mol
)(
0.560 g O2 0.560 g N2
0.600 atm
( N = 14, O = 16 :
)(394
)(395

:
0.560 g
= 0.0175 mol
32 g/mol
0.560 g
= 0.02 mol
28 g/mol
m O2
= n O2
Mw O2
m N2
= n N2
Mw N2
0.0175
= 0.47
0.0375
0.02
= 0.53
0.0375
n O2
nt
n N2
nt
= X O2
= X N2
PO2 = X O2 . Pt = 0.47 0.600 = 0.282 atm

PN 2 = X N 2 . Pt = 0.53 0.600 = 0.318 atm
)(
50 C 1.00
L 1.00 atm
) (1.00 L 1.00 atm 95 C
50 C
) ( :
P1V1 P2 V2
=
T1
T2
P2 V2 T1
V1T2
= P1
)(1 atm)(1.00 L) (323 K

)(1.00 L) (368 K
P1 = 0.878 atm
= P1
)(395
)(396
/

:
Pt = (P1 )g + PH2O
PH2O = Pt - (P1 )g
PH2O = 1 - 0.878
PH2O = 0.122 atm
)(
500 ml 30 C
1.01 atm
100 C 1.00 atm ) 0.042 = 30 C
.(atm
) ( :
Pt = (P1 )g + PH 2O
(P1 ) g = Pt - PH 2O
(P1 ) g 1 = 1.01 - 0.042
(P1 ) g = 0.968 atm
) (V2
:
P1V1 P2 V2
=
T1
T2
P1V1T2 0.968 atm 500 ml 373 K
=
= 595.8 ml
P2 T1
1 atm 303 K
= V2
)(396
)(397
/
)(
0.225 atm CH4 C2H6

) (0.165 atm .
(
( 9.73 L 35 C
.
(
( :
Pt = PC H 4 + PC 2H 6
P t = 0 .2 2 5 + 0 .1 6 5
P t = 0 .3 9 0 a tm
PCH 4 = X CH 4 P t
PCH 4
CH 4
Pt
0 .2 2 5
= X CH4
0 .3 9 0
X C H 4 = 0 .5 7 7
=
PC 2H 6
C 2H 6
Pt
0 .1 6 5
= X C 2H 6
0 .3 9 0
X C 2H 6 = 0 .4 2 3
=
)(397
(398)
/
: (
Pt V= n t R T
nt=
Pt V
RT
0.39 atm 9.73L

0.0821 L.atm/mol.K 308 K
n t = 0.150 mol
nt=
: (

:
(n
= 0.150 mol, XCH4 = 0.577, XC2H6 = 0.423
n CH4
nt
n CH4 = XCH4 n t
XCH4 =
n CH4 = 0.577 0.150

n CH4 = 0.09 mol
n C2 H 6
nt
n C2 H 6 = X C 2 H 6 . n t
X C2 H 6 =
n C2H6 = 0.423 0.150

n C2H6 = 0.063 mol
(398)
)(399
/
:
m CH4
Mw CH4
= n CH4
)mCH4 = n CH 4 . Mw CH 4 mCH 4 = 0.09 (12 + 4 1

mCH4 = 1.44 g
m C2 H 6
Mw C2H6
= n C2 H 6
)mC2 H6 = n C2 H6 . Mw C H m C2 H6 = 0.06 (2 12 + 6 1
2 6
mC2 H6 = 1.80 g
)(
40 g O2 40 g He
0.900 atm ) (He = 4, O = :
.16
:
40
= 1.25mol
32
m O2
Mw O2
= n O2
m He 40
= = 10 mol
Aw 4
n O2
1.25
=
=
= 0.11
nt
11.25
= n He
n He
10
=
= 0.89
nt
11.25
X O2
= X He
)(399
)(400
/
:
PO2 = X O2 . Pt
PO2 = 0.11 0.900
PO2 = 0.099 atm
PHe = X He . Pt
PHe = 0.89 0.900 PHe = 0.801 atm
)(
100 C ) (0.800 atm ) (50% )(He

50% ) (Xe . .
) (100 g :
m He
50.0 g
=
= 12.5 mol He
Aw He 4.00 g mol-1
m Xe
50.0 g
= n Xe
=
= 0.381 mol Xe
Aw Xe 131.3 g mol-1
= n He
) (X :
n He
12.5
=
= 0.970
n He + n Xe 12.5 + 0.381
n Xe
0.381
=
=
= 0.030
n He + n Xe 12.5 + 0.381
= X He
X Xe
:
Pi = Xi Ptotal
PHe = 0.970 0.800 = 0.776 atm
PXe = 0.030 0.800 = 0.024 atm
)(400
)(401
/
)(
(A) : ) 0.495 (66.0 ) (B

) 0.182 g (45.5 ).(76.2 cmHg
.
) 49.7 cm Hg = (A )26.5 cm Hg = (B
)(
) (C6H14 )(6 L
) (250 C .
.
P = 374 mmHg :
)(401
)(402
/
) (Grahams Law of Diffusion 1829

Graham's Law : Diffusion and Effusion of Gases

) (mix
(when they come in
) contact .
) (Diffusion )(
).(Effusion
) (Diffusion ) (Effusion

.

Gas Diffusion

) (.

) (

.
.
Mixing of different gases by random molecular motion with
frequent collisions is called diffusion
)(402
(403)
:
/
Fig. 83 : Diffusion is the mixing of gas molecules by random motion under conditions
where molecular collisions occur.
Fig. 84 : A representation of diffusion of gases. The space between the

molecules allows for ease of mixing one gas with another. Collisions of
molecules with the walls of the container are responsible for the pressure
of the gas.

.
.
) ( .
.
:
(403)
)(404
/
( )(
.
( ) (a bottle of perfume )(odor
.
(random molecular
) motion ) (frequent collisions
).(diffusion
(
H 2S
) (the smell of rotten eggs ) (released

) (can be detected .

.
) (concentrated ammonia) (NH3
) (at one end of a lab bench
.

) .(
Fig. 85 : The path traveled by a single gas molecule. Each change in direction
represents a collision with another molecule.
)(404
(405)
:
/
(instantly)( gradually)
.
) (

.( )
Fig. 86 : NH3 gas (left) and HCl gas (right) escape from concentrated aqueous
solutions. The white smoke (solid NH4Cl) shows where the gases mix and react
NH 3 (g) + HCl (g)
NH 4Cl
Fig. 87 : A demonstration of gas diffusion. NH3 gas (from a bottle containing

aqueous ammonia) combines with HCl gas (from a bottle containing hydrochloric
acid) to form solid NH4Cl. Because NH3 is lighter and therefore diffuses faster, solid
NH4Cl first appears neared the HCl bottle (on the right).
(405)
)(406
/

.
) (
.
)(
Gas Effusion
) (
) (

.
) (Effusion
.

.
Effusion is a process in which gas molecules escape without
collisions through a tiny hole into a vacuum is called effusion
)
(

.
) ( - .
)(406
(407)
:
/
Fig. 89 : Effusion is the escape of a gas through a pinhole without molecular

collisions.
Fig. 90 : Gas effusion. Gas molecules move from a high-pressure region (left) to a
low-pressure one through a pinhole
(407)
(408)
:
/
.( )
.

.
Fig. 91 : Effusion of gases.

a) A molecular interpretation of effusion. Molecules are in constant motion;
occasionally they strike the opening and escape.
b) Latex balloons were filled with the same volume of He (yellow), N2 (blue) and O2
(red). Lighter molecules, such as He, effuse through the tiny pores of the latex
balloons more rapidly than does N2 or O2. The silver party balloon is made of a metalcoated polymer with pores that are too small to allow rapid He effusion.
c) If a bell jar full of hydrogen is brought down over a porous cup full of air, rapidly
moving hydrogen effuses into the cup faster than the oxygen and nitrogen in the air
can effuse out of the cup. This causes an increase in pressure in the cup sufficient to
produce bubbles in the water in the beaker.
)
He (
.
.
. ( )
(408)
)(409
/

)(
.

.
) (rate of effusion
.
The rate of effusion is the number of molecules passing through
a porous hole in a given time.
r1 t 2
Mw 2
= =
r2 t1
Mw1
The longer the time it takes, the slower is the rate of effusion.
) (Thomas Graham

) (

d2
d1
= Rate1 .
Rate2

:
"
"
)(409
)(410
/
:
1
d
: r . .
r1, r2 d1, d2 :
1 d2
d1 1
1
1
r1 = K
d1
d1
r1
1
1
r1 = K
d2
d2
r2
1
d1
=
1
d2
r1
=
r2
r1
u2
d2
= = 2
r2
u
d1
1
d1
1
d2
K
K
r1
=
r2
:
m
RT
V
P Mw = d R T
= P Mw
:
d Mw
)(410
)(411
/
1
1
r1 = K
Mw1
Mw1
r1
1
1
r1 = K
Mw 2
Mw 2
r2
1
Mw1
1
Mw 2
r1
=
r2
1
Mw1
1
Mw 2
K
K
1
Mw 2
Mw1
1
r1
=
r2
r1
=
r2
r1
u2
Mw 2
= = 2
r2
u
Mw1

Rate1
Mw 2
=
Mw1
Rate2
) (t
:
Mw 2
Mw1
d2
u2
=
=
2
u
d1
t
rate of effusion 1 r1
= = = 2
rate of effusion 2 r2
t1

. .
:

.
)(411
)(412
/

.

.

.
) (

.

:
) (A, B

:
Mw B A
=
Mw A B

.
:
)(412
)(413
/
Mw A
t
= A
Mw B
tB
) (tA, tB A, B .

.
:
)
(
) ( ) (
.
) (Pitchblende
238
92
) (99.28 % U
) .(0.71 %
238
92
235
92
.
) (F2 .UF6

) UF6
UF6
235
92
238
92
352
(349
.
UF6
352
=
= 1.0043
UF6
349
UF6
235
92
235
92
238
92
rate of diffusion of
rate of diffusion of
UF6
238
92
1.0043.
)(413
)(414
/
) (1.0043
) (
235 UF6
235
.
Isotopes
.
Isobars
115
50
Sn & 115
49 Sn :

.
.

)(
1.414 SO2
.
) (R = 0.0821 atm L/mol. K ) : (S = 32, O = :
16
(
)(414
)(415
/
(
( : MwX
:
Mw SO2
rX
=
rSO2
Mw X
)(32 + 2 16
Mw X
= 1.414
64
(1.414 ) =
Mw X
64
64
=2
Mw x = = 32 g/mol
Mw X
2
2
( :
P Mw X = d X R T
P Mw X
RT
)(1atm) (32 g/mol
= dX
)(0.0821 L atm/Kmol) (273K
d X = 1.43 g/L
= dX
)(
A 1.44 min
1.8 min
) (A .
)(415
)(416
) (A
A .
r1 c1 t 2
d
Mw 2
== = = 2
r2 c 2 t1
d1
Mw1
2
Mw A
=
Mw O2
2
tA
t O2
Mw A
1.44
=
16
1.8
2.0736 Mw A
=
3.24
16
16 2.0736
=10.24g/mol
= Mw A
3.24
)(
) (H2 ) (O2
(MwO2 = 32 g/mol, MwH2 = 2 g/mol) :
32
= 16 = 4
2
Mw O2
M H2
rH2
rO2
rH2 = 4 rO2
)(416
)(417
/
)(
)( 1.14
) . = .(16
Mw O2
rX
=
rO2
Mw X
32
Mw X
= 1.14
32
32
(1.14 ) =
= 1.2996
Mw X
Mw X
32
= Mw X
= 24.62 g/mol
1.2996
2
)(

) .((N = 14, O = 16 :
Mw NO2
rNO
=
rNO2
Mw NO
46
= 1.24
30
rNO
)(14 + 2 16
=
=
rNO2
)(14 + 16
1.24.
)(
) HBr (Mw = 81 ) CH4 (Mw = 16 HBr

4 ml/S CH4
)(417
)(418
Mw HBr
Mw CH4
81
= 2.25
16
rCH4
rHBr
rCH4
4
rCH4
= 2.25 rCH4 = 2.25 4 = 9 ml/s
)(
4.69
) CO2 .(C = 12, O = 16) :
Mw CO2
rX
=
rCO2
Mw X
44
Mw X
= 4.69
44
( 4.69 ) =
Mw X
44
44
= 21.9961
= Mw X
= 2 g/mol
Mw X
21.9961
2
) (2 .
)(
) (A ) (B
A B
)(418
)(419
rA
Mw B
1
=
=
rB
Mw A
2
rA
= 0.707
rB
)(
X 112.25S
O2 84.7S
.
) = .(16
Mw O2
rX
t
Mw X
=
= X
rO2
Mw X
rO2
Mw O2
:
tX
Mw X
=
rO2
Mw O2
Mw x
112.5
=
84.7
32
2
2
112.5 Mw x
=
84.7 32
12656.25
Mw X
12656.25 32
= Mw X
=
= 56.45 g/mol
7174.09
32
7174.09
)(419
)(420
/
)(
1.44 g
) (0.09 g
.
:
m
0.09
=
= 0.09 g/L
V
1
m 1.44
= d O2
=
=1.44 g/L
V
1
= d H2
d O2
d H2
1.44
=4
0.09
=
=
rH2
rO2
rH2
rO2
) (H2 ) (O2 .
)(
) (0.1 mol 2.5 L

745 torr ) (93.5 %
) (N2 ) = (N
.14
) (g rg ) (N2 rN2
:
)(420
)(421
/
r(g) = 0.935 rN2
Mw N 2
)Mw (g
)r(g
rN2
Mw N 2
)Mw (g
)(2 14
)Mw (g
2
= 0.935
= 0.935
= 0.935
(2 14)
2
( 0.935) =
Mw
)(g
28
= 0.874225
)Mw (g
28
= 32 g/mol
0.874225
= )Mw (g
)(

112.2 s 84.7 s
.
)(421
)(422
/
Mw O2
Mw X
t O2
tX
84.7 S
32
=
112.2 S
Mw X
2
2
84.7 S 32
=
112.2 S Mw X
32
= 0.57
Mw X
32
= 56.14 g/mol
0.57
= Mw X
)(
) (STP
5.00 min
) 6.30 min
)(O = 16
Mw O2
Mw X
t O2
tX
6.30
32
=
5
Mw X
2
2
6.30 32
=
5 Mw X
32
32
= 1.5876
= 20.16 g/mol
= Mw X
Mw X
1.5876
)(422
)(423
/
PMw = d X RT
P Mw
RT
1atm 20.16 g/mol
= dX
)(0.0821 L.atm/ K. mol) (273 K
d X = 0.899 g/L
= dX
)(
0.572 g/L 25 C 0.500

atm N2 ) 9.50 ml/S
= .(14
( 6.28 ml/S
( dX :
d N2
dX
t N2
tX
2
9.50 0.572
=
6.28 d X
0.572
0.527
= 2.29
= dx
= 0.250 g/L
dx
2.29
)(423
)(424
/
( :
P Mw X = d R T
dX R T
P
)( 0.25 g/L ) (0.0821 L atm/Kmol) (298K
= Mw X
) ( 0.500 atm
= Mw X
Mw X = 12.2 g/mol
)(
3.1 ) F2
= .(9
( 4 g/mol
)(
0.323
) . = .(4
( 38.13 g/mol
)(424
)(425
/

Brownian Motion

.
) (1827

.
) (focusing .

.
.
.

.

.
.
)(425
)(426
/

Molecular Kinetic Theory of Gases

hypothesis and Ideal Gas Model

.
) (Boltzmann ) (Maxwell
.
.

.

.

.

.
.
)(426
)(427
/
.
.
) (1857 (1822 Rudolf Clausius
) 1888
(experimental
) observations : .

:
( )(
) ) (a gas consists of small particles (atoms or molecules
.
(
)
) (V = 0
.

)
( .

.
The actual volume occupied by gas molecules is extremely small compared
to the volume that the gas occupies. The volume of the container is
considered equal to the volume of the gas. Most of the volume of a gas is
empty space, which allows gases to be easily compressed.
A gas is composed of molecules whose size is much smaller than the
distances between them. This concept accounts for the ease with which
gases can be compressed and for the fact that gases at ordinary temperature
and pressure mix completely with each other. These facts imply that there
must be much unoccupied space in gases that provides substantial room for
additional molecules in a sample of gas.
)(427
)(428
/
(
.
The attractive forces between the particles of a gas can be
neglected

) (

. .
Except when gas molecules collide, forces of attraction and repulsion
between them are negligible. This concept is consistent with the fact that
all gases behave in the same way, regardless of the types of noncovalent
interactions among their molecules.
) (rapid velocities (in all

) directions .
)(428
(429)
:
/

Gas particles are in constant motion, moving rapidly in straight paths.
When gas particles collide, they rebound and travel in new directions.
When they collide with the walls of the container, they exert gas pressure.
An increase in the number or force of collisions against the walls of the
container cause an increase in the pressure of the gas.
Gas molecules move randomly at various speeds and in every possible
direction. This concept is consistent with the fact that gases quickly and
completely fill any container in which they are placed.
(
(Perfectly Elastic)
.

.
When collisions between molecules occur, they are elastic. The speeds of
colliding molecules may change, but the total kinetic energy of two
colliding molecules is the same after a collision as before the collision.
That is the collision is elastic. This concept is consistent with the fact that
a gas sample at constant temperature never " runs down" , with all
molecules falling to the bottom of the container.
(429)
)(430
/

.
.

) (Mean Free Path
.
(
.
(

.
)(430
(431)
:
/
The average kinetic energy of gas molecules is proportional to the

Kelvin temperature. Gas particles move faster as the temperature
increases. At higher temperatures, gas particles hit the walls of the
container with more force, which produces higher pressures.
The average kinetic energy of gas molecules is proportional to the
absolute temperature. Though not part of the kinetic molecular theory,
this useful concept is consistent with the fact that gas molecules escape
through a tiny hole faster as the temperature increases, and with the fact
that rates of chemical reactions are faster at higher temperatures.
The kinetic theory helps explain some of the characteristics of gases. For
example, we can quickly smell perfume from a bottle that is opened on
the other side of a room, because its particles move rapidly in all
directions. They move faster at higher temperatures, and more slowly at
lower temperatures.
Sometimes tires and gas-filled containers explode when temperatures are
too high. From the kinetic theory, we know that gas particles move faster
when heated, hit the walls of a container with more force, and cause a
buildup of pressure inside a container.
( )
Ideal Gas )(
( )
)
273 K 1 atm)
(
.
(431)
(432)
/

( )(

.
A gas is composed of molecules (discrete molecules) that are separated
from each other by distances far greater than their own dimensions. The
molecules can be considered to be "points"; that is, they posses mass but
have negligible volume.
The individual molecules are very small and are very far apart relative to
their own sizes.
( ) (
.
Between collisions, the molecules exert no attractive or repulsive forces
on one another; instead, each molecule travels in a straight line with a
constant velocity.
(
.
( elastic)
(there is no energy gain or loss) .
The gas molecules are in continuous , random, straight-line motion with
varying velocities.
Gas molecules are in constant (continuous) motion in random directions,
and they frequently collide with one another. Collisions among molecules
are perfectly elastic. In other words, energy can be transferred from one
molecule to another as a result of collision. Nevertheless, the total energy
of all the molecules in a system remains the same.
. (
The average kinetic energy of the molecules is proportional to the
(absolute) temperature of the gas in Kelvins. Any two gases at the same
temperature will have the same average kinetic energy (The average
kinetic energies of molecules of different gases are equal at a given
temperature).
For instance, in samples of H2, He, CO2 and SO2 at the same temperature,
all the molecules have the same average kinetic energies. But the lighter
molecules, H2 and He, have much higher average velocities than do the
heavier molecules, CO2 and SO2, at the same temperature.
The average kinetic energy of a molecule is given by :
average molecular KE = KE T
(432)
(433)
:
/
or
average molecular speed = u
T
molecular weight
1
KE = m u 2
2
m : mass of the molecule and u is its speed.

u 2 : mean square speed; it is the average of the square of the speeds of all
the molecules :
u2 =
u12 + u 22 +..................+ u 2N
,
N
N : the number of molecules

Assumption 4 enables us to write :
KE T
1
m u 2 T
2
1
m u 2 = KT
2
According to the last equation the absolute temperature of a gas is a

measure of the average kinetic energy of the molecules, the higher the
temperature the more energetic the molecules. (Molecular kinetic
energies of gases increase with increasing temperature and decrease with
decreasing temperature).
We have referred only to the average kinetic energy, in a given sample,
some molecules may be moving quite rapidly while others are moving
more slowly.
.(
.
According to the kinetic molecular theory, gas pressure is the result of
collisions between molecules and the walls of their container. It depends
on the frequency of collision per unit area and on how 'hard' the
molecules strike the wall.
(433)
)(434
/
( : .
(
.
( : .
( .
( : .
( .
( : .
( .
( : .
( .
( :
(
.
( : .
(
.

) .(T, P, V

.

. .
)(434
)(435
/
) (1 cm2 .
.

:
( )(

.
.
) (STP ) (99.96 %
. (2.7 1019
) molecules/ml ) (STP
) (3.7 10-7 cm ) (12 .

.
:
) (
.
.

.
.
:

.
.
)(435
)(436
/

.

) (1/2mu2 ) (m : u .
.
.

) 0 C 1000
(mph .

) ( .
.
:

:
( .
( .

.

.

)(436
)(437
/
) (.

.

. ).(
.
.
.

.
)(
)(437
)(438
.
.
.

:
1
m N u2
3
1
PV = m ( nN A ) u 2
3
= PV
:
: P : V Pa : N m3 : m
: u 2 . )(m2/s2
)(438
)(439
/
)(
kPa ) (2 1021 molecule N2

) (1 L
)) .(244036 m2/s2 (14 = N
: Kg
Mw N2 = 2 14 = 28 g mol -1
Mw N2 = 0.028 kg mol -1
0.028 kg mol-1
=
6.023 1023molecules mol-1
Mw N2
NA
= m
m = 4.65 10-26 kg molecule
:
1
m N u2
1
2
3
= PV = m N u P
3
V
1
) ( 4.65 10-26 kg molecule-1 ) ( 2 1021 molecule) ( 244036 m 2s -2
P= 3
1L
-3
1000 L m
P = 7565.116 Kg / m s2
P = 7565.116 Pa
P = 7.565 kP
(where 1 Pa = 1 Nm-2 = (kg m s-2 ) (m-2 ) = kg /m s2
)(439
)(440
/

Fundamental Equation of the Kinetic Theory

Kinetic Equation of Gases
) (
) (P ) (m ).(u
) (L
) (L3 )(L2
: )(X, Y, Z
) (N )(m
) (u .
)(440
)(441
/

) (
) (u
) (x, y, z )(
) (1/3 ) (1/3)N X
Y .Z
.(X, Y, Z) :

.
) (ux, uy, uz
) ( Root Mean Square Velocity u

2
u 2 = u x2 + u 2y + u z2
) (A
)( ) (x ) .(u m/s
2 L cm
) (L
) (L 2 L
.
u m/s
u cm
)(441
)(442
/

:

2L
=
ux

) (
) (
u
collisions/second/
2L

) ( ) (- u
) ( ) (A
x :

mu
= - mu
)) (A
( :
= mu - ( - mu) = 2 mu Kg m s-1

) (:
=

)(442
)(443
/
=

2L
)(2mu
2
u mu
-1
Force = ( 2 mu ) =
kg m s
2L L
) (B
:
mu 2

) (A. B X :
mu 2 mu 2 2mu 2x
+
=
L
L
L
) (y, z :
2mu 2y 2mu 2z
,
L
L
.
:
2
2mu 2x 2mu y 2mu 2z 2m 2

2mu 2
2
2
+
+
=
( u x + u y + uz ) = L Newtons
L
L
L
L
)(443
)(444
/
Newtons
2m u 2
L
N :
2 m N u2
L
:
F 2 m N u2
= =P
A
AL
P A
:
A = 6 L2
:
2 m N u2
1
m N u2
=
6 L2 L
3
L3
L3 = V
=P
1
m N u2
=P
3
V
1
m N u2
3
= PV
.
) (mN
(V) ) (d )(mN/V
:
)(444
)(445
/
1
d u2
3
=P

:
1
m u2
2
= ke
:
: ke ) (J
: m )(kg
: u 2 )(m2/s2
) (N :
1
m N u2
2
= KE

Derivation of the Ideal Gas Laws from the Kinetic Equation

.

.
.
.
.
.
)(445
)(446
/
(pressure depends on two factors) :
(
The number of molecules striking the walls per unit time
(
how vigorously the molecules strike the walls
) (average speed
) (force of the collisions ).(remain the same
)(molecular collisions

) (with the walls per second
.
) (number of molecules per unit
.volume
.
)(as volume decreases, pressure increases and vice versa
.
)
( .

)
( .
) (
).(
)(446
)(447

.
.

.
)(447
)(448
/

.
.
1
)m u 2 T (Kelvin
2
1
m N u 2 NT
2
1
)m N u 2 = KT N..................( 2/3
2
21
2
2
m
N
u
=
KTN
32
3
21
2
2
m N u = KT N
32
3
2
PV = K T N
3
at constant T, N
PV= constant
= PV
)(448
)(449
/
:
1
T(Kelvin) mc 2
2
1
PV = Nmc2
3
2N 1 2
= PV
mc
3 2
1
T mc2
2
PV NT
)PV = const (for fixed N and T
PV = nRT
- :
.

)
(
the average kinetic energy is directly proportional to the absolute
temperature.

)
(.
)(449
)(450
/
Doubling the absolute temperature of a sample of gas doubles the average
kinetic energy of the gaseous molecules, and the increasing force of the
collisions of molecules with the walls doubles the volume at constant
pressure.

.
.

)

The volume of gas will expand until the gas pressure is balanced by the
constant external pressure.
) (

.
)(450
)(451
/
.

.
.
Halving the absolute temperature decreases kinetic energy to half its
original value, at constant pressure, the volume decreases by half because
of the reduced vigor of the collision of gaseous molecules with the
container walls.

"" .

" " .
" ".
)(451
)(452
:
2
KTN
3
2
KTN
=V
P
3
V
2
KN
=
T
3
P
at constant P, N
V
= constant
T
= PV
P
- ) ( = constant :
T
) (

. .

)

( .
.
.
.
.
- ::
)(452
)(453
/
:
.

.

.
) (1, 2
:
1
P1V1 = m1 N1u12
3
1
P2 V2 = m 2 N 2 u 22
3
:
P1V1 = P2V2
:
1
1
)m1 N1u12 = m 2 N 2 u 22 .............( 3
3
3
2
m1 N1u1 = m 2 N 2 u 22

:
1
1
m1u12 = m 2 u 22
2
2
i.e.
)(453
)(454
/
m1 N1u12 = m 2 N 2 u 22
:
1
1
m1u12 = m 2 u 22
2
2
m1 N1 u12 m 2 N 2 u 22
=
1
1
2
m1 u1
m 2 u 22
2
2
2 N1 = 2 N 2
)(divided by 2
N1 = N 2
" :
"N
.
:
V
=K
n
:
2
) ( KTN
3
V
2 KT
=
N
3 P
= PV
V
= constant
N
atconstant P,T
) (N ) (n :
V
= constant
n
.
).(n/V
)(454
)(455
/
n
T
V
For two gases 1 and 2 :
P
n1
nT
T1 = K 1 1
V1
V1
n2
n T
T2 = K 2 2
V2
V2
P1
P2
(V1 = V2, P1 = P2,

) T1 = T2 :
n1 = n2

)(mathematical expression of Avogadro's law
( :

.
:
1
m u2
2
= ke
) (A, B :
1
m A u A2
2
1
ke B = m B u B2
2
= ke A
)(455
)(456
/
keA = keB
1
1
mA u A2 = mB u B2
2
2
:
1
1
)m A u A2 = m B u B2 ....................(x 2
2
2
1
m A u A2 = m B u B2 ............................ x 2
u B . mA
u A2 m B
=
....................................
u B2 m A
) (
u A2
mB
=
2
uB
mA

:
u A2
mB
=
u B2
mA
rA
Mw B
=
rB
Mw A
u A2
mB
=
2
uB
mA
)(456
)(457
/
u A2
mB
=
2
uB
mA
m
m = d V
V
VB d B
VA d A
= d
u A2
=
u B2
VA = VB
dB
dA
u A2
=
u B2
rA
dB
=
rB
dA
) (A :
1
m NA u 2
3
=PV
:
Mw = m NA
:
1
Mw u 2
3
3PV
= u2
Mw
3P
= u2
d
= PV
) (Mw/V ) (d ) (V/Mw ).(1/d

) (r ) (u
:
)(457
)(458
/
3P
d
1
d
.
( :
) (
.
(collide with the
) walls
.
.
As a result, each gas exerts a partial pressure that is independent of the
presence of other gas, and the total pressure is due to the sum of all the
molecule-wall collisions.

)
( .

:
E = E1 + E2 + E3 + E4 +
)(458
)(459
/
V
:
:
1
N1m1 u12
3
21
P1V = N1m1 u12

32
2
P1V = E1
3
= P1V
: E1 .
:
1
N 2 m2 u 22
3
21
P2 V = N 2 m2 u 22
32
2
P2 V = E 2
3
= P2 V

:
2 E2
3V
= P2
2 E1
,
3V
= P1
(Partial
) . Pressure
. (E = E1 + E2 + E3 +
) E4 +
2
V
3
)(459
)(460
/
Ptotal = P1 + P2 + ...
) (Ptotal

.
( ) (Brownian Motion
.
) (bombarding
.

).(
)(460
)(461
/
) (chunk
.

.
.

Kinetic Energy and Temperature
:
1
m N u2
3
=PV
:
: N : (m) : u 2
.
:
PV = n R T
:
1
m N u2
3
PV = n R T
=PV
)(461
(462)
/
1
m N u2
3
PV= nRT
1
m N u 2 = nRT ..... 3
3
m N u 2 = 3 nRT........... n
PV=
N
m u 2 = 3RT............... 2
n
1
3
m N A u 2 = RT
2
2
(N A : Avogadro's Number = 6.023 1023 )
1
3
mu 2 N A = RT
2
2
3
ke N A = RT = KE
2
(KE : Kinetic Energy for One Mole, ke : Kinetic Energy for One Molecule)
ke =
3 R
2 NA
ke =
3
kT
2
(k : Boltzman's Constant =
8.314 J/K. mol

= 1.381 10-23 J/K)
23
6.022 10 molecules/mol
: n
3
nRT
2
3
KE =
(8.314) n T
2
KE = 12.47 n T
KE =
(462)
)(463
/
) (8.314 JK-1mol-1 R
25C
:
3
3
R T = (8.314 J K-1 mol-1 ) (298 K) = 3720 J mol-1
2
2
:
KE
3 R
=
T
NA
2 NA
= ke

Boltzmans Constant
) ( k :
R
8.314 J mol-1 K -1
=
= 1.3804 10-23 J/ K . molecule
NA 6.023 1023 molecules mol-1
=k

:
3
kT
2
= ke
) (25 C :
3
(1.3806 10-23 J K -1 ) (298 K) = 6.17 10-21 J
2
= ke
)(463
(464)
:
/

1
Nmu 2 = nRT
3
1
n N A mu 2 = nRT
3
1
N A ( mu 2 ) = RT
3
1
1
N A 2 mu 2 = RT
3
2
2
1
N A mu 2 = RT
3
2
2
N ( avg KE per molecule ) = RT
3 A
2
N A ( avg KE per molecule) = RT
3
This equation shows that the absolute temperature is directly proportional

to the average molecular kinetic energy, as postulated by the kinetic
molecular theory. Because there are N AV molecules in a mole, so the lefthand side of this equation is equal to the total kinetic energy for a mol of
molecules.
2
N A ( avg. KE per molecule ) = RT
3
2
N A (Ke) = RT
3
2
KE = RT
3
KE : total kinetic energy per mole of gas
: n
KE =
2
nRT
3
(464)
)(465
2
RT
3
2 R
Ke =
T
3 N AV
= )N A (Ke
2
(k ) T
3
= Ke
)(
:
( 0.1 mol
( 1 mol .
3
nRT
2
3
= )KE(0.1mol
0.1 8.314 273 = 340.46 J
2
3
= )KE(1mol
1 8.314 273 = 3404.58 J
2
= KE
)(
) (27 C kJ
3
nRT
2
3
= KE
) 1 x 8.314 (27 + 273
2
KE = 3741.3 J
= KE
KE = 3.741 kJ
)(465
)(466
/
)(
) (0.2 mol ) (27 C kJ
3
nRT
2
3
= KE
) 0.2 8.314 (27 + 273
2
KE = 748.26 J
= KE
KE = 0.75 kJ
)(
) (14 g ) (CO ) (25 C

)) (J (C = 12, O = 16 :
:
m
14 g
=
= 0.5
)Mw (12 + 16
= n CO
:
3
nRT
2
3
= KE
) 0.5 8.314 (25 + 273
2
KE = 1858.18 J
KE = 1.86 kJ
= KE
)(466
)(467
/
)(
) (K
.
T 298 K
) (.
3
)n R T.............(1
2
1
3
)KE = n R (273)........(2
2
2
= KE
) ( ) ( :
3
1
KE
(273) n R
2
2
=
3
KE
nRT
2
1
273
=
2
T
T = 2 273
T = 546 K
)(
) (4 g ) (N2 (250
) ml ) (KE 12471 J/mol
: :
)(467
)(468
/
3
nRT
2
3
= 12471
1 (8.314) T
2
T = 1000 K
= KE
:
PV=nRT
nRT
V
4
0.0821 1000
28
P=
0.250 L
P = 46.91 atm
=P

Molecular Speed

.
:
PV = nRT
:
)(468
(469)
/
1
m N u2
3
1
PV = m (nN A ) u 2
3
1
PV = n (mN A ) u 2
3
1
PV = n Mw u 2
3
PV = n R T
PV =
1
n Mw u 2 = n R T ................
3
Mw u 2 = 3 R T
3RT
u2 =
Mw
3
)
n
3RT
Mw
rms : root - mean - square
u 2 = u rms =
u 2 =
3RT

Mw
1
m N u2
3
1
n R T = m N u2
3
for 1 mol N = N A
PV=
1
m NA u 2
3
m N A = Mw
RT =
1
Mw u 2
3
3RT
u2 =
Mw
3RT
u2 =
Mw
RT=
(469)
(470)
:
/

1
m N u2
3
1
n R T = m nN A u 2
3
1
RT = m N A u 2
3
PV=
u2 =
3RT
mN A
u 2 = u rms =
3RT
Mw
u 2
:
u 2
1
1
KE = m N A u 2 = Mw u 2
2
2

:
KE =
KE =
3
RT
2
1
3
Mw u 2 = RT.................( 2)
2
2
2
Mw u = 3RT
3RT
u2 =
Mw
3RT
u 2 = u rms =
Mw
(470)
3
RT
2
)(471
u2
)Root Mean Square Velocity (rms

The equation :
3RT
Mw
shows that the (rms) speed of a gas increases with the square root of its
temperature (in Kelvins). Because Mw appears in the denominator, it
follows that the heavier the gas, the more slowly its molecules move.
= u 2 = u rms
:
u12 + u 22 + u 32 +...........+ u 2n
n
= u2
:
( :
3RT
Mw
= u2
) (T
).(Mw
( u 2
) (m/s R
Mw Kg/mol g/mol
) (R = 8.314 J/K.mol ) ( 1 J = 1 N.m :
kg . m
m = kg m2 S-2
2
S
= J = N. m
)(471
)(472
/
3RT
Mw
= u2
)3 R(J mol-1 K -1 ) T(K

= u
) Mw (kg mol-1
2
)3 R(kg m 2 s -2 mol-1 K -1 ) T(K

= m . s-1
-1
) Mw (kg mol
= u2
m/s km/h :
km km 1000 m/km
=
h
h 3600 s/h
km
3.6 = m s-1
(
. ) (Mw
2
u )(R = 8.314 J/K.mol , Mw = Kg/mol
:
3RT
Mw
= u2
:
PMw = d RT
P Mw
dRT
=
d Mw
d Mw
P RT
=
d Mw
3RT
= u2
Mw
3P
d
= u2
)(472
)(473
/
)(
) (N2 ) (25 C
) (Mw ) (SI 0.02802 Kg
) (1 J = 1 Kg m2 s-2 :
3RT
Mw
)3(8.3143) (298
0.02802
= u2
= u2
u 2 = 515 m s-1
u 2 = 1854 km h -1
u 2 =1150 mi h -1
) (
.

.
: ) )
u2
(0.921
) 25 C (298 K )1000 C (1273 K

1000 C
mi h-1
8180
5830
2730
2190
2050
1740
1380
1010
830
25 C
-1
ms
3660
2600
1220
970
910
780
620
450
370
-1
mi h
3960
2820
1320
1060
990
840
670
490
400
-1
ms
1770
1260
590
470
440
380
300
220
180
Gas
H2
He
H2O
N2
O2
CO2
Cl2
HI
Hg
)(473
)(474
/
)(
) (H2
).(H = 1
Mw = 2 10-3 kg/mol
R = 8.314 J/K.mol, T = 273 K
3RT
Mw
3 (8.314 J mol -1 K -1 ) 273 K
2 10-3 kg mol-1
3 (8.314 kg m 2 S-2 mol -1 K -1 ) 273 K
2 10-3 kg mol -1
= u2
2
= u
= u
u 2 =1.84 103 m/S

)(
) (N2
) (He )(27 C
.(N = 14, He = 4) :
)(474
(475)
Mw He = 4 10 -3 kg/mol
Mw N 2 = 28 10 -3 kg/mol
u 2 (He) =
u
(He)
(He)
3RT
Mw
3
(8.314 J mol
-1
K -1 ) 300 K
4 10 -3 kg mol -1
3
(8.314 kg m
s -2 mol -1 K -1 ) 300 K
4 10 -3 kg mol -1
u 2 (He) = 1367.4 m/s

u2
(N 2 )
at T K
u 2 (N 2 ) =
3RT
= 1367.4 m/s
Mw
2
3 8.314 T
2
= (1367.4 m/s )
-3
28 10
3 8.314 T
= 1869782.76
28 10 -3
1869782.76 28 10 -3
T=
3 8.314
T = 2099 K
()

(H = 2.016 ( ) R = 8.314 J/K.mol)
(475)
)(476
3RT
Mw
) 3 (8.314 J mol-1K -1 ) ( 273 K
) kg mol-1
( 2.016 10
-3
) 3 (8.314 kg.m2 s-2 mol-1 K-1 ) ( 273 K

) kg mol-1
-3
( 2.016 10
= u2
2
= u
= u
u 2 = 1.84 103 m/s
m/s : km/s
1.84 103 m
= u
s
) (1.84 103m / 1000 m km -1
2
= u
1s / 3600 s h -1
2
u 2 = 6624 km h -1
m/s Km/h :
m/s 3.6
1.84 10 3.6 = 6624 km h -1
3
(6624 Km/h) H2

.
)(476
)(477
/
)(

) (0.1 mol
( :
3RT
Mw O2
) 3 (8.314 J K -1 mol-1 ) ( 273 K
) kg mol-1
-3
( 32 10
) 3 (8.314 kg. m 2 s-2 K -1 mol-1 ) ( 273 K

) Kg mol-1
-3
( 32 10
= u2
= u
= u
u 2 = 461.3 m/s
m/s : km/s
461.3 m
s
) (461.3 m / 1000 m km-1
2
= u
1s / 3600 s h -1
= u2
u 2 = 1660.68 km h -1
:
461.3 m s-1 3.6 = 1660.68 km h -1
)(477
)(478
/
)(
) (N2
) (273 K Km/h
3RT
Mw
= u2
)3 (8.314 J K -1mol-1 ) (273 K

= u
)(28 10-3 kg mol
2
)3 (8.314 N. m K -1 mol-1 ) (273 K

)(28 10-3 kg mol
= u2
)3 (8.314 kg m2 s-2 K-1 mol-1 ) (273 K

= u
)(28 10-3 kg mol
2
u 2 = 493.14 m S-1
m/S : km/h
10-3

1
3600
u 2 = 493.14 m s -1
u 2 = 493.14 m s -1 3.6 = 1775.3 km h -1
)(
:
) (HBr, O2, N2, H2, He
)(H = 1, Br = 80, O = 16, N = 16, H = 1, He = 4
)(478
)(479
)3R (J K -1mol-1 )T(K

)Mw (kg mol
= u2
) (where J = N. m = kg. m S-2 . m = kg m2 s-2

)3R (kg m2 s-2 K-1 mol-1 )T(K
= u
= m/s
) Mw (kg mol-1
2
3 8.314 273
= 290.1 m/s = 1044.36 km/h
80.91 10-3
= )u 2 (HBr
3 8.314 273
= 461 m/s = 1659.6 km/h
32.00 10-3
= ) u 2 (O2
3 8.314 273
= 493 m/s = 1774.8 km/h
28.01 10-3
= ) u 2 (N 2
3 8.314 273
= 1835.99 m/s = 6609.56 km/h
2.02 10-3
=) u 2 (H 2
3 8.314 273
= 1304.72 m/s = 4696.99 km/h
4.0 10-3
=)u 2 (He

.
) (STP ) (493 ms-1
.
) (
.493 ms-1
.
.

.
)(479
)(480
/
) (
. ) (Jupiter
) (appreciable ) (H2 ) (He
.
.

) (11000 m/s (escape
) velocity

.
) (320

).(Jupiter retains both heavy and light gases in its atmosphere
) (small planets
(solar
) system
) (Mercury and Venus .
) () (revealed
) (measurable amounts of helium
) (in the atmosphere of Mercury .
)) (Massive bodies such as stars
( (are mainly composed of H .
).and He

(Mean Free
)(480
)(481
/
) Path
).(Collision Frequency
O2, N2 ) (1000 A
STP
)(
NH3 )(25 C
)) (m/s )(R = 8.314 J/K. (N = 14, H = 1
).mol
661.23 m/s :
)(481
)(482
)(u

The Average Velocity
u :
u1 + u 2 +.......u n
n
=u
u1, u2, ..un (n)

.
u :
8RT
Mw
) ( Mw = m N A
=u
8RT
m NA
=u
= k k :

NA
8kT
m
=u
:
3RT
Mw
= u2
:
u2 u
:
)(482
)(483
/
u12 + u 22 + u 32 +...........+ u2n
n
= u
:
u1 + u 2 + u 3 +....... + un
n
=u
).(10 %
u , u2
u, u 2 :
8RT
Mw
3RT
Mw
u
u2
8RT Mw
=
Mw 3RT
u2
8
3
= 0.92
u
u2
u
u2
: = 0.921 .
u2
u = 0.921
)(483
)(484
/
: )
(
: 273 K

( u ) m s-1
1845
1305
493
461
393
652
1698
1202
454
424
362
600
-1
H2
He
N2
O2
CO2
CH4
( u )m s
2
)(484
)(485
/

Distribution of Molecular Speeds

Maxwell and Boltzman Distribution
.
.
.

. .

.1860

.

.
Average Kinetic Energy
)
(

.

.

)(485
)(486
/
.
""
.
.
.
( :

(
.
( :
(
.
:
1
m N u2
3
=PV
2
u

.
:
1
m u2
2
= ke
ke .
)(486
)(487
/
) (Maxwell ) (Boltzman

) (T
).(Mw

.
)(487
(488)
:
/
Fig. 106 : The effect of molar mass on the distribution of molecular

speeds at a given temperature. On average, heavier molecules move
slower than lighter ones.
(488)
(489)
:
/
Fig. 107 :
a) The range of molecular speeds for several gases, as given by the Maxwell
distribution. All the curves correspond to the same temperature. The greater the molar
mass, the narrower the spread of speeds.
b) The Maxwell distribution again, but now the curves correspond to the speeds of a
single substance at different temperatures. The higher the temperature, the broader the
spread of speeds.
Fig. 108 :
a) The distribution of speeds for nitrogen gas at three different temperatures. At the
higher temperatures, more molecules are moving at faster speeds.
(b) The distribution of speeds for three gases at 300 K. At a given temperature, the
lighter molecules are moving faster, on the average.
(489)
(490)
:
/
Fig. 109 : The distribution of speeds for helium atoms at different temperatures.
Fig. 110 : The distribution of speeds for nitrogen atoms at different temperatures.
(490)
(491)
:
/
Fig. 111 : Graphs of molecular speeds (or energies) versus numbers of molecules are
called Boltzmann distribution curves. They are named after Ludwig Boltzmann
(1844-1906), an Australian physicist who helped develop the kinetic molecular theory
of gases.
Fig. 112 : The Maxwellian distribution function for molecular speeds. This graph
shows the relative numbers of O2 molecules having a given speed at 25 C and at
1000 C. At 25 C, most O2 molecules have speeds between 200 and 600 m/s (450
1350 miles per hour). Some of the molecules have very high speeds, so the
distribution curve never reaches the horizontal axis. The average molecular speed is
higher at 1000 C than at 25 C.
(491)
)(492
:
.
) ( ) (
.
)

(

.
) (
) (

) ) (Most Probable KE .
)(492
)(493
/
)
(

)
(
.
.

.

) (

)
( .

.
" " .
) ( :
( .
( -

).(T1
)(493
)(494
/
(
.
:
) (
.
.
: a b T1
.T2 .
V1
.

.
.
) (a ) (b ) (

.
)(494
)(495
)* (u ) ( u
) ( u
2
) (u*) (The Most Probable Speed

) ) (Maximum .(
: speeds 273
K
) (Mean Speed
:
u1 + u 2 + u 3 + u 4 +.......................+ u N
= u
: N .
:
)(495
)(496
u12 + u 22 + u 32 + u 24 +.......................+ u 2N
N
2
= u
)* (u
) ( u
) *. ( u > u

) ( u
) . ( u
:
u* : u : u 2 : 1 : 1.128 : 1.225
:
u2
u* 0.8
u 0.9 u 2

. ) (
) . (273, 1273, 2273 K

.

.

)(496
)(497
) ( u*, u, u 2
)(
: ) (N2

( u*) m s-1
394.4
870
1162
-1
( u )m s
( u ) m s-1
493
1066
1424
454
981
1311
273
1273
2273
)(497
)(498
/

Attractive Forces

.
.
.
.
) (Xe, Kr, Ar, Ne, He
) (Cl2, O2, N2, H2

.
.

) (
.
)
( .
.

.
)(498
)(499
/

) (
: .

.
.

) (71
) (28 .

. -
) (C5H12 ) (36 C
) (9.5 C
)(499
)(500
/

) ( .

.
) ( .
)(500
)(501
: ) (.
)(
)(501
)(502
/
) (
.
.
. )(distorted
) ( ) . (
) (
.
. ) (
) ( .

.
.

.

.
.

.
.
.
.
.
)(502
)(503
/
.

.
.

.
.
.

:
P V = constant
:
P V = nRT
:
PV
=1
nRT
PV
nRT
P ) (
)(
)(
)(503
(504)
:
/
(504)
(505)
:
/
Fig. 131 : Plot of PV/RT versus P of 1 mole of a gas at 0 C. For 1 mole of an ideal
gas. PV/RT is equal to 1, no matter what the pressure of the gas is. For real gases, we
observe various deviations from ideality at high pressures. At very low pressures, all
gases exhibit ideal behaviour; that is, their PV/RT values all converge to 1 as P
approaches zero.
Fig. 132 : A plot of the compression factor Z = PV/nRT as a function of pressure for a
variety of gases. For an ideal gas, this ratio is equal to 1 for all pressures. For a few
real gases with very weak intermolecular attractions, PV/nRT is always greater than 1.
For most gases, at low pressures the attractive forces are dominant and PV/nRT< 1.
At high pressures, repulsive forces become dominant and PV/nRT >1.
(505)
(506)
:
/
Fig. 133 : The nonideal behaviour of real gases compared with that of an ideal gas
Fig. 134 : The nonideal behaviour of real gases compared with ideal behaviour. For a
gas that behaves ideally, PV = nRT at all pressures, so PV/nRT = 1 at all pressures
(horizontal line). We can test a gas for ideal behaviour by measuring P, V, n, and T
for a sample of the gas at various pressures and then calculating PV/nRT. This plot
shows that different gases deviate differently from ideal behaviour, and that the
deviations from ideality become more pronounced at higher pressures.
(506)
)(507
: ) (PV/RT P ) (0 C
) (PV/RT = 1 .
.
PV/RT
P .
) CO2 (1 mol )(320 K

nRT :
nRT = (1 mole ) x ( 0.0821 L atm mol -1 K -1 ) x ( 320 K ) = 26.3 atm . L
) (nRT = 26.3 PV

PV
=1
nRT
)( PV
:
)) (nRT
(
PV nRT
:
)(507
)(508
/
)PV (atm . L
26.2
25.2
21.6
9.8
)V (L
26.2
2.52
0.54
0.098
)P (atm
1
10
40
100
)
( ) (PV ) (nRT
.
:
.
:
) (

.
) (:

.
)( .
)(508
(509)
:
/
Fig. 136 : A molecular interpretation of deviations from ideal behaviour.

a) A sample of gas at a low temperature. Each sphere represents a molecule. Because
of their low kinetic energies, attractive forces between molecules can now cause a few
molecules to 'stick together'.
b) A sample of gas under high pressure. The molecules are quite close together. The
free volume is now a much smaller fraction of the total volume.
(509)
)(510
/

:
(
Deviation Resulting from Neglecting Intermolecular Forces

) ( .
.
)
(
.
Fig. 137 : A gas molecule strikes the walls of a container with diminished force. The
attractive forces between a molecule and its neighbors are significant.
)(510
)(511
:
.
. .

.
) (

.

:
( :
:
:

) (
.
)(511
)(512
/
:

.
( :

.

:
2 m N u2
L
=F

2
u .

) ( .
)(512
)(513
/

).( -
)(513
(514)
:
/
Fig. 143 : Effect of intermolecular forces on the pressure exerted by a

gas. The speed of a molecule that is moving toward the container wall
(red sphere) is reduced by the attractive forces exerted by its neighbors
(gray spheres). Consequently, the impact this molecule makes with the
wall is not as great as it would be if no intermolecular forces were
present. In general, the measured gas pressure is lower than the pressure
the gas would exert if it behaved ideally.
(514)
)(515
/

.
) ( :
Pideal = Pmeas + P
= Pideal + Pmeas

P :
(
n

V
n

V
) (Pideal
" " ) (Pmeas
n2
2 :
V
n2
P 2
V
n2
P = a 2
V
) (a

)(515
)(516
/

n2
. a 2
V
a n2
+
V2
correction term

real
observed pressure

= Pideal
) (Pmeas :
a n2
V2
Pmeas = Pideal
(
Deviation Resulting from Neglecting Molecules Volumes

)(- 273 C

.

:
.
)(516
)(517
/

:
( :
)
(

.
( :

) (b
).(V
:
) (van der Waals

) Videal gas
% 100 (
:
nb
V = V
)real (measured
ideal
)(517
)(518
/
: b b
.
: n .
) : (nb n .
) : (V nb
.
:
)) (Videal ) (100 %
( : ) ( )(Videal
)(nb
) (b .
b ) (n
) (nb ) (nb ) (V
) (b
) .(
:
) ( 4/3 3 ) N( ) b = 4 N ( 4/3 3
)(518
(519)
:
/

( N )
4 3

3
4 3
b = 4 N 3
Larger molecules have greater values of b, and the greater the number of
molecules in a sample (higher n), the larger is the volume correction. Te
correction term becomes negligibly small, however, when the volume is
large (or the pressure is low).
(519)
)(520
/

(van der Wallss Equation of State
:
PV = n R T
)
( )
(

)( .
a n2
= Pideal
Preal
+
observed pressure
correction term

V = V
-
nb
)real (measured
ideal
:
PV=nRT
)(520
)(521
= nR T
n
Pm easured + a 2
Vm easured - nb = nR T

V
m easures corrected volume
corrected pressure
2
n
a
Pm easured +
Vm easurednb

2

V m easured
correction for volume

of m olecules (adjusts measured V dow n
correction for
m olecular attraction
(adjusts measured P up)
a n2
P
+
meas.
( V - nb ) = n R T
V 2 meas
:
)van der Waals Equation of State for A real Gas
) : (a, b
.

) (PV = nRT
).(PV = nRT
)(521
(522)
/
The quantities a and b are experimentally derived constants that differ for
different gases. When a and b are both zero, the van der Waals equation
reduces to the ideal gas equation.
(Pmeasured)
: (Vmeasured)
a n2
P
+
measured
( Vmeasured - n b ) = n R T
V2
nRT
an 2
Pmeasured =
V - nb
V2
nRT
Vmeasured =
+ nb
a n2
P + 2
V
a, b
.
(522)
)(523
/
:
b, L mol-1
0.0237
0.0171
0.0266
0.0279
0.0322
0.0318
0.0391
0.0399
0.0428
0.0398
0.0427
0.0408
0.0371
0.0266
0.0443
0.0571
0.0305
0.0638
0.0562
0.0564
0.138
0.06702
0.08407
a, atm. L2 . mol- 2
0.034
0.211
0.244
1.34
1.35
1.36
1.39
1.49
2.25
2.32
3.59
3.67
4.17
4.19
4.45
4.47
5.46
5.49
6.49
6.71
20.4
9.523
12.02
Gas

)(
He
Ne
H2
NO
Ar
O2
N2
CO
CH4, methane
Kr
CO2
HCl
Ammonia, NH3
Xe
HBr
C2H4, ethelene
H 2O
C2H6
Cl2
SO2
CCl4
CH3OH
C2H5OH
) ( :
) (a
. ) (a
.
C2H5OH
b .
.
) (b NH3 H2 NH3
H2 .
)(523
)(524
/
a .
C2H5OH, CH3OH, H2O, :
NH3 .

: .
.
a .
O2, CH4. C2H6
He .
) (CO2, O2, N2 )(a
.
) (He ) (a
. ) (a
)(524
)(525
/

)( ) (a :
Ar > Ne > e
a, b
.

. a, b
.
( :
.
(

:
(
.
(
.

:
(

.
(
.
(
(
( ) (.
( .
(

.
( : ) (He, H2 .
( NH3
.
)(525
)(526

:
): (n = 1
a
P + 2 ( V- b ) = R T
v
:
a
ab
+ 2
V
V
PV = RT + Pb -
( :
ab
P V Pb, 2
V
a

V
) b V

a
ab
+ 2
V
V
PV = RT + Pb -
:
a
V
PV = RT -
:
PV RT
)(526
)(527
/
a
P V
V
PV
. Z P
).(NH3, N2, CH4
: ) (PV/RT = Z
.
Z ) (1.0
) (Z = 1.0
.
)(527
)(528
/
( :
P :
a
ab
+ 2
V
V
PV = RT + Pba
ab
V 2 ,
V V

:
PV = RT + Pb
) (PV
) (RT ) (Pb .
PV
).(
( :
P V . :
a
ab
a
b, 2 + 2 :
V
V
V
PV = RT + Pb -
V, P
:
PV = RT
.
V
) ( P
:
)(528
)(529
/
PV = RT

.
:
) (H2
a ab
,

V V2
a
ab
+ 2 :
V
V
PV = RT + Pb -

) (a
a
V2
. )(b

:
a
ab
+ 2
V
V
PV = RT + Pb
PV = RT + Pb -
PV H2, He
RT P b
PV
.
)(529
)(530
: PV/RT .
Z 1.0 1.0
.
( P b ) , a :
V

V
) (P b .

).(
)(530
)(531
: .
:
) (-172.8 C Z P ) 200 K
( .
) ) (-164 C ( ) 500 K(
) ( .
) (Spheres
) (74% .
) (Mw (NA) (d)
) (Molecular Volume Vm :
3
Mw
d = 0.74
6
NAd
= Vm
) (b ) (excluded volume :
b = 4NVm
)(531
)(532
/

)(
1.0 mol 20.0 L

27.0 C:
(
( :
:
) (a = 5.464 L2 atm mol-2, b = 0.03049 L mol-1
( :
)RT ( 0.08205 L atm / K mol ) (300 K
=
= 1.23 atm
V
20.00 L mol-1
=P
(
RT
a
- 2
V-b V
( 0.08205 L atm/K mol ) (300 K) - 5.464 = 1.218 atm
=P
400 L2 mol-2
) ( 20 - 0.0304
=P
)(
6 mol ) (CO
) (3 L ) (25 C .
(R = 0.0821 L. atm K-1 mol-1) : :
)(a = 1.49 atm.L2 mol-2, b = 0.0399 L/mol2
)(532
)(533
/
: :
PV = nRT
nRT
V
6 mol 0.0821 L.atm mol -1K -1 298 K
=P
3L
P = 48.932 atm
=P
/ :
a n2
P +
(V- nb) = nRT
V2
1.49 (6) 2
P
+
) ( 3 - (6 0.0399) ) = 6 0.0821 (25 + 273

(3) 2
( P + 5.96 ) (2.7606) = 146.795

146.795
P =
- 5.96 = 47.22 atm
2.7606
) (48.932 atm
) (47.22 atm
.
)(
3 g H2 225cm3
0 C
(
( .
(R = 0.0821 L . atm/mol . K) : :
)( a = 0.072 L2. atm/mol2. b = 0.244L/atm
) = .(1
)(533
)(534
( :
PV = nRT
nRT
V
3g
) (0.0821 Latm/K.mol) (273 K

2 1
=P
)(225 10-3 L
P = 149.42 atm
=P
n2
P
+
a
( V- nb ) = nRT
V2
1.5)
(
P + 0.244
) (0.225 - 1.5 0.0271) = (1.5 mol ) ( 0.0821 L.atm/molK) ( 273 K
2
)(0.225
(P + 10.84) (0.184) = 33.62
33.62
0.184
P = 182.72 - 10.84
= P + 10.84
P = 171.88 atm
)(
) (b )
(.
( CH4
( He
( C2H2
( C3H8
) (b
.
)(534
)(535
/
) (b
) (C3H8 .
)(
) (2 mol ) (N2
) (1 L ) (0 C :(
( ) (.
= R
b = 0.0391L mol-2,
(a = 1.39 atm.L 2 mol-2,
)0.0821
( )(PV = n R T
)(P (ideal gas) = 44.827 atm
( ) :
a n2
P
+
(V- nb) = nRT

V2
)( P(real gas) = 43.07 atm

.
)(
) (10 L
) (800 mmHg ) (30 C ) (8 g )(CO2
) (6 g ) (O2 N2
N2
.
(C = 12, N = 14, O = 16) :
)(535
)(536
/
)(R = 0.0821 L. atm K-1 mol-1
) ( a = 2.5 atm L2 mol-2, b = 0.032 L mol-2
/ ) (CO2, O2 :
m
8
=
= 0.1818 mol
)Mw 12 + (2 16
m
6
= n O2
=
= 0.1875 mol
Mw
2 16
= n CO2
/ ): (nt
Pt V = n t RT
Pt V
RT
= nt
800
atm 10 L
760
= nt
)(0.0821 L atm mol-1 K -1 ) (303 K
n t = 0.4231 mol
/ :
) n t = n N2 + (n CO2 + n O2
) n N2 = n t - (n CO2 + n O2
)n N2 = 0.4231 - (0.1818 + 0.1875
n N2 = 0.0538 mol
/ :
PN 2 V = n N 2 R T
n N2 R T
= PN 2
V
)(0.0538 mol) (0.0821 L.atm K -1 mol -1 ) (303 K
= PN 2
10 L
PN 2 = 0.1338 atm
)(536
)(537
/
/ :
n2
P
+
a
( V - nb ) = nRT
V2
(0.0538) 2 2.5
P
+
) (10-(0.0538 0.032) ) = 0.0538 0.0821 (30 + 273

(10) 2
( P + 7.2361 10 ) (9.9983) = 1.3383

-5
1.3383
- 7.2361 10-5
9.9983
P = 0.13378 atm
=P
)(
(R = 0.0821, a = 3.6 atm.L 2 mol-2, b = 0.0427 L. ):

mol-2

) (3.5 mol ) (CO2
) (0.75 L ) (22 C :
( ) : (113.024 atm :
( ) : (62.88 atm :
)(
:
) (R = 0.0821 L . atm K-1 mol-1, a = 4.17 atm.L2 mol-2, b = 0.037 L. mol-2
6.8 g ) (- 4 C
) (4 L :(
( .
( :
)(537
)(538
/
) (2.20849 atm :
( ) ( :
(2.175 atm ) :
)(
) (1 mol ) (O2
) (1 L ) (0 C (R = 0.0821 L. atm K-1 mol-1) :
(a = 1.136 atm. L2 mol-2, b = 0.03183 L. mol -2) :
(22.01417 atm) :
)(
) (2 mol ) (NH3 ) (5 L (27

) C . :
(a = 4.17 atm L2 mol-2, b = 0.037 L mol-2, R = 0.0821 L. atm K-1
)mol-1
(9.33 atm) :
)(
) (C2H5OH ) (85 C
35 L :
)(538
)(539
/
(R = 0.0821 L. atm mol-1 K-1) : :
)(a = 12.02 atm L2 mol-2), (b = 0.84 L. mol-2
( ) (0.851 atm) :
( ) (0.840 atm :
)(539
)(540
/

-

Liquefaction of Gases

.

Critical Temperature

.
).(Tc

.

.
.
: Critical Pressure
) (
.
.
) (647 K ) (374 C ) (H2O .

) (647K .
) (CO2
)(540
)(541
/
) (304 K ) .(31 C
)(5.2 K
) (- 267.9 C

. ) (

.
)(541
(542)
/
Critical Conditions of Gases :
Methane
Ethane
Propane
n-Butane
Iso-butane
191
306
370
425
408
Pc,
atm
45.8
48.2
42.0
37.5
36.0
Pentane
470
33.3
0.268
Iso-pentane
Neo-pentane
Hexane
Heptane
Octane
Ethylene
Propylene
1- Butene
-1-Pentene
461
434
508
540
569
282
365
420
474
32.9
31.6
29.9
27.0
24.6
50.0
45.6
39.7
40.0
0.268
0.260
0.264
0.260
0.258
0.268
0.276
0.276
-
Acetic Acid
Acetone
Acetylene
595
57.1
0.200
509
309
46.6
61.6
0.237
0.274
Benzene
562
48.6
0.274
1,3-Butadiene
Cyclohexane
Dichloro-difluoro
methane
Ethylene
425
553
42.7
40.0
0.270
0.271
Methyl Alcohol
Methyl Chloride
Methyl Ethyl Ketone
Toluene
Tri-Chloro
Fluoro
Methane
()11
Tri-Chloro Trifluoro Ethane(13
)
Bromine (Br2)
Chlorine, Cl2
Helium (He)
Hydrogen (H2)
Neon (Ne)
Nitrogen (N2)
Oxygen (O2)
( )Ammonia (NH3)
Carbon Dioxide (CO2)
Carbon Monoxide (CO)
Hydrazine
Hydrogen Chloride (HCl)
Hydrogen Sulfide (H2S)
Nitric Oxide (NO)

Nitrous Oxide (N2O)
385
39.6
0.273
Sulfur (S)
282
50.0
0.268
Diethyle Ether

Ethyl Alcohol
Ethylene
Oxide
467
35.6
0.261
516
63.0
0.249
468
71.0
0.25
Compounds Tc , K
513
416
533
594
471
Pc,
atm
78.5
65.9
39.5
41.6
43.2
0.220
0.276
0.26
0.270
0.277
487
33.7
0.274
584
417
5.3
33.3
44.5
126.0
155
406
304
102
76.1
2.26
12.8
26.9
33.5
50.1
111
72.9
0.307
0.276
0.300
0.304
0.307
0.291
0.29
0.242
0.276
133
34.5
0.294
653
325
145
81.5
0.266
374
88.9
0.284
180.0
310
64
71.7
0.25
0.271
1313
116
431
77.8
0.268
491
83.8
0.262
647
218
0.320
Zc
Compounds
Tc , K
0.290
0.284
0.276
0.274
0.282
Sulfur Dioxide
(SO2)
Sulfur Trioxide (SO3)
Water (H2O)
(542)
Zc
)(543
/

Critical Volume

. ) (
isopentane
.
: .

isothermals (553K = 280
) C
) (473 K = 200 C .
) (39 105 N/m2

)(543
)(544
/

).(
= (460.8 K = 187.8 C

) (458 K = 185C
.
.
.
.
)(two phase region

) (critical point
. ).(
.

) ( .
) (

)(Z
) (compressibility factor ) (Z:
PV=ZnRT
) (Z :
)(544
)(545
/
(
( .
:
( )reduced pressure (Pr
( )reduced temperature (Tr
:
P
Pc
= Pr
T
Tc
= Tr
) (Z :
)Z = f (Pr, Tr
) (Z Tr, Pr
) ( ) (Z )(Tr
).(Pr
)(545
(546)
:
/
(546)
)(547
/

.
) (b ) .(V b

:
1
V2
:
a
V2
=P
) (a :
a
V2
P+
:
a
P + 2 ( V- b ) = RT
V
for n moles :
a n2
P + 2 ( V- nb ) = nRT
V
van der Walls equation )(a, b

.
) ( ) (a, b
PV = nRT :
)(547
)(548
/

.
)(a, b
) (a), (b :
:
a
P + 2 ( V- b ) = RT
V
V2
:
+ a ) (V - b) = V 2 RT
( PV
PV 3 - PV 2 b + aV- ab = V 2 RT
P(V 3 - V 2 b) = V 2 RT + ab - aV
)P(V 3 - V 2 b) = V 2 RT + a (b - V
)a (b - V
V 2 RT
+
) ( V3 - V 2 b ) ( V3 -V 2 b
)a (b - V
V 2 RT
+ 2
2
)V (V - b
)V (V - b
)a (b - V
RT
+ 2
)( V - b ) V (V- b
)a ( V - b
RT
- 2
)( V - b ) V (V- b
RT
a
- 2
V- b V
=P
=P
= P
= P
= P
)(548
)(549
RT
a
- 2
V- b V
= P
:
RT
a
- 2
V- b V
- RT
2a
P
+ 3
=
2
V
) V T ( V - b
=P
2P
2RT
6a
- 4
= 2
3
V
) V T ( V - b

.
- RT
2a
P
+ 3
=
2
V
) V T ( V - b
- RTC
2a
P
=0
+
=
2
VC3
) V TC ( VC - b
2a
VC3
RTC
)- b
( VC
:
2P
2 RTC
6a
=0
= 2
3
4
V
V
V
b
(
)
TC
C
C
6a
VC4
2RTC
) ( VC - b
6a
RTC
2a
= 3 :
4 :
2
VC
( Vc - b ) VC
2RTC
) ( VC - b
)(549
(550)
/
RTC
( Vc
- b)
2RTC
VC - b
RTC
( Vc
2a
VC3
=
6a
VC4
(V - b)
- b)
2RTC
2a VC4
= 3
VC 6a
Vc - b
V
= c
2
3
3Vc - 3b = 2Vc
3Vc - 2Vc = 3b
Vc = 3b
RTC
( Vc - b )
2a
:
VC3
Vc = 3b : ( Vc)
:
RTC
( Vc
- b)
RTC
( 3b - b )
2a
..................where Vc = 3b
VC3
2a
( 3b )
RTC
2a
=
2
4b
27b3
27 b3 RTC = 8 a b2
Tc =
8 a b2
27 b3 R
Tc =
8a
27Rb
P + 2 ( V- b ) = RT
V
(550)
(551)
:
/
Pc +
RTC
a
=
2
Vc ( Vc - b )
Pc =
RTc
a
- 2
( Vc - b ) Vc
: ( Tc, Vc) Pc
RTc
a
- 2
Vc - b Vc
8a
, Vc = 3b
Tc =
27Rb
:
Pc =
RTc
a
- 2
Vc - b Vc
8a
R
a
27Rb
Pc =
2
3b - b
( 3b )
8a
R
a
27Rb
Pc =
- 2
2b
9b
4
8a 1 a
Pc = R
- 2
27Rb
2b
9b
4a
a
Pc =
- 2
2
27b
9b
4a
3a
a
Pc =
Pc =
2
2
27b 27b
27b 2
(551)
)(552
/
8a
Tc
= 27bR
a
Pc
27b 2
Tc
8a
27 b 2
=
Pc
27 b R
a
Tc
8b
=
Pc
R
8 b Pc = R Tc
RTc
8 Pc
a
) (b
27b 2
=b
= Pc
:
27 TC2 R 2
64 Pc
=a
) (a
.
:
a
P + 2 ( V- b ) = RT
V
) (a ) (b
.
) (n :
a n2
P
+
V- nb ) = nRT
(2
V
)(552
)(553
/
) (P ) (a, b :
RTc
8 Pc
=b
27 TC2 R 2
=a
64 Pc
)(
) (NH3 ) (2 moles
) (5 L )(27 C
a n2
P + 2 ( V- nb ) = nRT
V
a n2
P +
( V- nb ) = nRT
V2
a n2
nRT
P+
=
2
V
V - nb
nRT
a n2
=P
- 2
V - nb
V
) (
Pc = 111 atm , Tc = 406 K :
N/m2 :
N/m 2
= 1.125 107 N/m 2
atm
Pc = 111atm 101325
:
V = 5 Liter = 5 10-3 m3
) (a, b :
)(553
)(554
RTc
8 Pc
=b
27 R 2 TC2
=a
64 Pc
RTc
8 Pc
=b
406 K 8.314 J/Kmol

= 3.7515 10-5 J.m 2 /N.mol
7
2
8 1.1247 10 N/m
but J = N.m
=b
b = 3.7515 10-5 m3 /mol

27 TC2 R 2
=a
64 Pc
2
27 ( 406 K ) 8.314
J 2 m2
K. mole
74
=a
=
0.42
N. mol2
) 64 1.1247 107 (N/m 2
2
N.m4
mol2
nRT
a n2
=P
- 2
V - nb
V
2 8.314 300
4 0.4274
=P
= 9.445 N/m 2
-6
-3
-5
( 5 10 ) - ( 2 3.7515 10 ) 25 10
a = 0.4274
:
PV = nRT
P 5 10-3 = 2 8.314 300
P = 9.977 N/m 2

.
)(
) (250 Kg ) (N2
) (8.68 atm ).(25 C
)(554
)(555
/
(
( ). (Z
Z
0.7
0.99
0.99
0.4
Pr
0.262
0.259
3.86
3.86
Tr
0.214
2.365
4.67
0.422
) (126 K
)) (Pc = 33.5 atm (N = 14 :
( ) (28 g/mol :
PV = nRT
) (n :
m
250 103g
=n
=
= 8.9286 103 mol
-1
Mw
28 g mol

) (R ) ((8.314 J/K. mol
/:(N/m2)
1 atm = 1.01325 105 N m -2
P = 8.68 1.01325 105 = 8.7950 105 N/m 2
P = 33.5 1.01325 105
P = 3.3944 106 N/m2
PV = nRT
8.765 105 V = 8.9286 103 8.314 298
V = 25.152 m 3
)(555
)(556
/
.
( :
PV = Z nRT
) Z = f(Pr Tr
P 8.7950 105
= Pr
=
= 0.2591
Pc 3.3944 105
T
298
=
= 2.3651
Tc
126
= Tr
) (Z ) (0.99
) (Pr, Tr
:
8.795 105 V = 8.9286 103 0.99 8.314 298
V = 24.9005 cm3
.

:
V = 25.1520 - 24.9005 = 0.2515 m3
)(
( ) (100 g
) (CO ) (5 L
).(40 C
( )( .
).(C = 12, O = 16
)(556
)(557
( :
an 2
P
+
V - nb ) = nRT
(2
V
100
= n CO
= 2.273 moles
44
) (a, b :
27 Tc2 R 2
=a
64 Pc
:
Pc = 92.7 atm = 9.393 106 N/m2
Tc = 304 K
27 (304)2 (8.314)2
=a
= 0.287 N.m4 /mol2
6
) 64 (9.393 10
n2
P
+
a
( V - nb) = n R T
V2
P + 0.287 ( 2.273) ( 5 10-3 ) - ( 2.273 3.363 10-5 ) = 2.273 8.314 313

-3 2
5
10
(
)
)
2
)0.287 ( 2.273
) ( 5 10
-3 2
2.273 8.314 313
) ) (( 5 10 ) - ( 2.273 3.363 10
-5
-3
=P
P = 1.201 106 - 5.932 104

P = 1.1416 106 N/m 2
( :
)(557
)(558
/
PV=nRT
P 5 10-3 = 2.273 8.314 313
P = 1.183 106 N/m 2
)(0.0414 106 N/m2

.

.
)(
) .(100 atm ) (O2

) (100 L )Compressibility (Z
Factor
) (Z
.
)Z = f (TrPr
) (Pr, Tr
. ) ( :
)(558
)(559
/
Pc = 50.1 atm
Tc = 155 K
P 100
=
= 1.996
Pc 50.1
= Pr
T
273
=
= 1.761
Tc
155
= Tr
) (
) (1.996 ) (1.761 (1.80
) & 1.70 ) (Z
).(Z
Z = 0.927
) (Z :
P V= Z n R T
m
0.082 273
32
100 100 = 0.927

m = 15420.33 g
m = 15.420 Kg
)(559
)(560
/

Measurement of Critical Constants

.isothermal process ) (

) (dL ) (dV )(
) (.

:
( ) (
)) (A (
) (B ). (
) (
)(560
)(561
( ) (A )
(.
( )(
) (
critical
) temperature (
(
.critical pressure
.
) . (Cailletet and Mathias

) (
) (dL ) (dV
)(561
)(562
/
) (Orthobaric Densities
:
(d + dV )
T=a+b L
) : (a, b : T
(dL = dV = dC) :
: dC : .
:
TC = a + b d C
Tc dc Vc
( Critical Volume

) ( .Iso-pentane
( ) (dL ) (dv
orthobaric densities
)(562
)(563
/
( (1886) L. Calletet and V. E Mathias
:
1
( d L + d V ) = a + bT
2
) (a, b ) (T .
) (
) (AC )(BC
.
) (C
critical density
critical volume .

. :
W = dV . Vv + dL . VL
) (W .
)(563
)(564
/
) (dL, dV

) (dL, dV
.

Liquefaction Methods of Gases

.

) (

.
.

.

.
)
(
)(
)
)(564
)(565
/
(

.

.

) (O2 ) (H2 ) (He )(N2

.

critical temperature
critical pressure
.
) ( .
)(565
)(566
/
: ) (P, V, and T .
Tc, K
33.3
5.3
190.2
405.6
647.2
134.4
44.8
126.0
179
154.4
513.1
324.6
150.7
304.2
430.4
470.3
417
561.6
209.4
289.8
Vc Liters/mol
0.070
0.062
0.099
0.072
0.056
0.090
0.044
0.090
0.058
0.074
0.118
0.087
0.076
0.094
0.123
0.310
0.124
0.256
0.107
0.120
Pc, atm
12.8
2.26
45.6
112.2
217.7
35.0
26.9
33.5
65
49.7
78.5
81.6
48.0
72.8
77.7
33.0
76.1
47.9
54.3
57.9
H2
He
CH4
NH3
H2 O
CO
Ne
N2
NO
O2
CH3OH
HCl
Ar
CO2
SO2
n-C2H12
Cl2
C 6 H6
Kr
Xe
:

) (647.2 K .

) (HCl, CO2, NH3
.

) (H2, N2 ) (33.3 K, 126.1 K
.
)(566
)(567
/

) (5.3 K
.
) (
.
Joule Thomson effect
"

".

-
.
) (Thomas Andrews :
) (Thomas Andrews
) (1869

.
.

) (
:
)(567
)(568
:
.
( ) (48.1 C
.
(
:
( ) : (ab
) (CO2.
( ) : (cd
) (CO2.
( ) : (bc
) (CO2 ) (b
) (c ) (CO2
.
)(568
)(569
/
(
.
( ) ( )
( .
( ) ( P = 0 :
P
=0
V T
:
( )(
.

.
(

(gas critical
) temperature
.

.

)(569
)(570
/
.

:
3
RT
2
= ke

.

.
.
)(570
)(571
/
) (Thomas Andrews )(1869

. .
( ) (A-B .
( ) (B-C )
( .
( ) (C .
( ) (B-C )(31 C
D
.
( ) (31 C .
CO2 ) (31 C .
CO2 ) (31 C .
)(571
)(572
/

Liquefaction Methods
(
Faradays Method
) (1823 )
(
CO2 SO2
NO Cl2
.
).(
) (V

.

) (.
HCl, Cl2,
...H2S, CO2, SO2, NH3 He, H2,
N2, O2 ) (3000 atm
permanent gases

)
) (a (.
)(572
(573)
:
/
. :
(573)
)(574
/
) (Andrews 1869

) (

.
.

.

)Pictet Method (1877
) (1877 ) (O2) (H2

)
) ( . )
( )
(
) (-56 C
) (CO2 ) (CO2
) (-130 C
) (O2 . ) (

) (- 218 C ).(- 228.71 C
)(574
)(575
/
(TC = - 228.71 C) Ne
) (TC = - 239.9 C ).(TC = - 267.84 C
)
( :
( )) (Lind and Hampsons Method(
) (Joule Thomson Effect
) (.
( ) (Cloud's and Haylans Method
).(Adiabatic Expansion
: Lind-Hampsons Method
-

.

. ) (
.
)(575
)(576
: .
)(576
)(577
/

.

.
:
- CO2
- ) ) (compressor
)) (200 atm ) (2.00 107 N/m2
) ( .
.
-

) heat exchanger (
. ) (c
) (D (1
) atm )) (V ( .
) ( ( - 78
) .C
)(577
)(578
/

.
- )(c
.
- ) ) (compressor
...
(
) .(V
.
) (N2, O2
) (He, H2

)
(
- ).(Joule Thomson Effect

(- 80 C) H2
.(- 240 C) He
)(578
)(579
/
:
Cloud Haylans Method

) ( .
) (200 atm .
) ( .

)
( ) (
- ) (.

.

) (
) (1908 Kammerlingh
Onnes ).(He
).(
) (P )(A

.

.
)(579
)(580
/

.

) (1927
) (Debye and Giaque
) (1.0 K
)(580
)(581
/
)(adiabatic demagnitization .

) .(not ferromagnetic
) (paramagnetic ............. .
- ).(ferromagnetic

.
.
.
)(Kr, Ne, Ar, O2
.
) (NH3, SO2 -
)( ) (Cl2CF2 .
.
) (O2 ) (He
.
) (Cl2 .
)(581
)(582
/
)(
) (18 L
) (70 cm. Hg ).(27 C
(R = 0.0821 L. atm/K . mol) :
:
PV = n R T
PV
=n
RT
70 cm Hg
76 cm Hg atm -1 18 L
=n
-1 -1
( 0.0821 L atm mol K ) (27 + 273) K
n = 0.673 mol
)(
) (10 L ) (27 C
)) (74 cm Hg ).(R = 0.0821 L. atm mol-1 K-1
:
PV = n R T
m N2
PV =
RT
Mw N
2
P V Mw N 2
= m N2
RT
74 cm Hg
-1
76 cm Hg -1 10 L (2 14) g mol
m N2 =
0.0821 L . atm mol -1 K -1 (27 + 273) K
m N2 = 11.07 g
)(582
)(583
/
)(
) (0.5 g (1.0 g)
) (15 L ) .(25 C :
(
( .
( .
( :
0.50 g
= 0.01786 mol
( 2 14 ) g mol-1
1.0 g
= 0.03125 mol
( 2 16 ) g mol-1
m N2
Mw N 2
m O2
Mw O2
= n N2
= n O2
n t = n N 2 + n O2 = 0.01786 + 0.03125 = 0.04911 mol
( :
n N 2 = 0.01786 mol, n O2 = 0.03125 mol, n t = 0.04911 mol
)a
PN2 V = n N 2 R T
0.01786 mol 0.0821 L. atm mol-1 K -1 (25 + 273) K
V
15 L
= 0.029131 atm
=
n N2 R T
= PN2
PN2
)b
PN2 V = n N 2 R T
0.03125 mol 0.0821 L. atm mol-1 K -1 (25 + 273) K
15 L
n O2 R T
= PO2
V
= 0.0510 atm
PO2
( :
)(583
)(584
/
PN2 = 0.029131 atm, PO2 = 0.0510 atm
Pt = PN2 + PO2
Pt = 0.029131 + 0.0510
Pt = 0.080 atm
)(
) (O2
) .(27 C ) (R = 8.314 107 erg/mol K )(1erg = 1g . cm2/s2
)(AwO = 16
:
3RT
Mw
= u 2 = u rms
Mw ).(R
) (R = 8.314 J/mol K = 8.314 kg m 2/s2 mol K
) (Mw kg/mol R .kg
R :
) (8.314 107 erg/mol K = 8.314 107 g . cm2/s2 mol K

3RT
= u rms

Mw
) .(g/mol : cm/s
)(584
(585)
/
u rms =
u rms =
3RT
Mw
3 ( 8.314 107 g cm2 s-2 mol-1 K -1 ) ( 27 + 273) K
( 2 16 ) g mol-1
u rms = 2338312500 cm2 s-2

u rms = 48356.1 cm s-1
u rms = 483.56 m s-1
()
.
.(AwH = 1) ( R = 8.314 J/mol K)
dHg = 13.59 g/cm3 :
3RT
u rms =
Mw
( kg/mol) Mw
: ( R)
(R = 8.314 J/mol K = 8.314 kg m2/s2 mol K)
u rms =
u rms =
u rms =
3RT
Mw
3 ( 8.314 kg m2 s-2 mol-1 K -1 ) ( 0 + 273) K
2 1
-1
kg mol
1000
3404583 m2 s-2
u rms = 1845.15 m s-1
(585)
)(586
3RT
= u rms ) (PV
) (RT
Mw
:
3PV
Mw
= u rms
P V
cm/s .m/s
) ( :
Vm = 22.4 L = 22400 cm3
:
P = 1 atm
P = 76 cm Hg
P=h.d.g
) P = ( 76 cm 13.59 g cm-3 981 cm s -2
P = 1013216.04 g/cm s 2
P = 1013216.04 dyne/cm
): (g/mol
P = 1013216.04 g cm-1 s-2
3PV
Mw
) 3 (1013216.04 g cm -1 s-2 ) ( 224000 cm 32 mol-1
2 g mol-1
= u rms
= u rms
u rms = 184510.3 cm /s
u rms = 184.510 m /s
)(586
)(587
/
)(
) (N2 )(27 C
) .(70 cm Hg :
)(R = 8.314 J/mol K = 8.314 kg m 2/s2
)(8.314 107 erg/ mol K = 8.314 107 g cm2/s2
)(AwN = 14
) (
:
3RT
Mw
3PV
= u rms
Mw
= u rms
:
3RT
Mw
= u rms
3 (8.314 107 g cm 2 s -2 mol -1 K -1 (27 + 273) K

(2 14) g mol-1
= u rms
u rms = 51694.85 cm/s

u rms = 516.95 m/s
) (R = 8.314 kg m2 s-2 mol-1 K-1

): (kg mol-1
)(587
(588)
/
3RT
Mw
u rms =
3 (8.314 kg m2 s-2 mol-1 K -1 (27 + 273) K
u rms =
2 14
-1
kg mol
1000
u rms = 516.95 m/s
:
P = 70 13.59 980.5 = 932749.65 g cm2 s-2
nRT
V=
P
1 mol ( 0.0821 L.atm mol-1 K-1 ) (27 + 273) K
V =
70
atm
76
V = 26.7411 L = 26741.1 cm3
u rms =
u rms =
3PV
Mw
3 ( 932749.65 g cm2 s-2 ) 26741.1 cm 3
(2
14 )
u rms = 51695.6 cm/s 2

u rms = 516.956 m/s 2
()
:
(O2) (
(CO2) (
.(O = 16, C = 12) :
(NA = 6.023 1023)
(588)
)(589
Mw O2 = 2 16 = 32 g/mol
Mw CO2 = (12 ) + ( 2 16 ) = 44 g/mol
32 g mol-1
= 5.320 10-23 g molecule-1
6.023 1023 molecules mol-1
44 g mol-1
=
= 7.305 10-23 g molecule-1
23
-1
6.023 10 molecules mol
Mw O2
NA
Mw CO2
NA
= m O2
= m CO2
)(
) (O2 ) (4.25 104 cm/s

) (CO2 .
) (O = 16, C = 12 :
:
Mw CO2
Mw O 2
44
32
u O2
u CO 2
4.25 104
=
u CO2
4.25 10 4
44
32
= 3.62 104 c ms-1
= u CO2
u CO2
)(

) (3.62 104 cm/s
).(25 C
)(589
)(590
) (KE
:
( KE )273 K T273
( KE )298 K T298
1
m O u12
2 2
1
( KE )298 K = mO2 u 22
2
( KE )273 K 1/2 mO2 u12 T1
=
=
( KE )298 K 1/2 mO2 u 22 T2
= ( KE )273 K
u12 T1
=
u 22 T2
u1
T
= 1
u2
T2
4.25 104 cm s -1
273
=
u2
298
4.25 104 cm s -1
= u2
273
298
u 2 = 4.440 104 cm/s
)(
) (Ne ) (25 C
) (Ar .
)(590
)(591
u Ne
=
u Ar
Aw Ar
Aw Ne
2
Aw Ar
u Ne
=
u
Ar
Aw Ne
u 2 Ne
Aw Ar
=
2
u Ar
Aw Ne
2
u 2 Ne
39.95
=
u 2 Ar
20.18
u 2 Ne
= 1.980
u 2 Ar
)(
( ) (1 mol ).(25 C
( .
( :
3
nRT
2
3
= KE
) 1 mol (8.314 J mol -1 K -1 ) ( 298 K
2
KE = 3716.360 J/mol
= KE
KE = 3.720 kJ/mol
( ) (3716.360 J .
)(N = 6.023 1023
:
)(591
)(592
/
KE mole
NA
= Ke molecule
3716.360
6.023 1023
= 6.17 10-21 Joule/molecule
= Ke molecule
Ke molecule
)(
) (kg/m3 ) (105 N/m2

).(3 102 m/s
:
1
m N u2
3
= PV
.
) (mN
(V) ) (d )(mN/V
:
1
m N u2
3
1 mN 2
=P
u
3 V
1
=P
(d ) u 2
3
3P
d= 2
u
= PV
)(592
)(593
/
P = 1 105 N m-2
P = 1 105 (kg m s-2 ) m -2
P = 1 105 kg m-1 s-2
3P
d = 2
u
): (kg m-1 s-2

) 3 (1 105 kg m-1 s-2
=d
) ( 3 10 m s
) 3 (1 10 kg m s
=d
) ( 9 10 m s
-1 2
-2
-1
-2
d = 3.33 kg/m 3
)(
) (100 g ) (31.014 %
) (0.99456
) .(150 C .
:
31.014%
m N2 =
100 g = 31.014 g
100%
100 - 31.014
= mCH 4
100 g = 68.986 g
100
:
m
31.014
=
= 1.108 mol
Mw
2 14
m
68.986
=
=
= 4.312 mol
Mw 12 + 4
= n N2
n CH 4
)(593
)(594
/

:
n N2 = 1.108 mol
PN2 V = n N2 R T
n N2 R T
V
(1.108 mol ) ( 0.0821 L.atm mol-1K -1 ) (150 + 273) K
0.99456 L
= PN2
= PN2
PN2 = 38.69 atm
:
n CH 4 = 4.312 mol
PCH 4 V = n CH 4 R T
n CH 4 R T
V
( 4.312 mol ) ( 0.0821 L.atm mol-1K -1 ) (150 + 273) K
0.99456 L
= PCH 4
= PCH 4
PCH 4 = 150.570 atm
:
:

PN2 = 38.69 atm
PCH4 = 150.570 atm
Pt = PN2 + PCH4
Pt = 38.69 + 150.570
Pt = 189.260 atm
)(594
)(595
/
:
): (nt
n N2 = 1.108 mol
n CH4 = 4.312 mol
n t = n N2 + n CH 4
n t = 1.108 + 4.312
n t = 5.42 mol
:
n t = 5.42 mol
Pt V = n t R T
nt R T
V
( 5.42 mol ) ( 0.0821 L. atm mol-1 K-1 ) (150 + 273) K
0.99456
= Pt
= Pt
Pt = 189.260 atm
)(
) (25 C
) (190 cm3 ) (740 mmHg

) (25 C ) (24 mmHg ) (dry gas
) (760 mmHg .
) (V = 190 cm3
:
)(595
)(596
/
Pt = Pdry gas + PH2 O
Pdry gas = Pt PH2O
Pdry gas = 740 24
Pdry gas = 716 mmHg
) (P1 = 716 mmHg ).(V1 = 190 cm3
) (P2 = 760 mmHg

)(V2
) (V2 :
P1 = 736 mmHg, V1 = 190 cm3
? = V2
P2 = 760 mmHg,
P1V1 = P2 V2
736 mmHg 190 cm3 = 760 mmHg V2

736 mmHg 190 cm3
760 mmHg
= V2
V2 = 184 cm 3
)(
) (0.495 g ) (A ) (66 g/mol

) (0.182 g ) (B ) .(45.5 g/mol
) .(76.2 cmHg .
)(596
)(597
/
mA
0.495
=
= 0.0075 mol
Mw A
66
= nA
mB
0.182
=
= 0.004 mol
Mw B
45.5
= nB
nt = 0.0075 + 0.004 = 0.0115 mol

n A 0.0075
=
= 0.6520
n t 0.0115
= XA
nB
0.004
=
= 0.3480
nt
0.0115
= XB
A :
PA = X A Pt
PA = 0.6520 76.2 cmHg
PA = 49.680
: B
PB = X B Pt
PB = 0.3480 76.2 cmHg
PB = 26.520
:
PA = 49.680
PB = 26.520
Pt = PA + PB
Pt = 49.680 + 26.520
Pt = 76.2 cmHg
.
)(

) Chloropicrin (CCl3NO2 :

35 C

731 mmHg

2.151 L

0.92 g
.
)(597
(598)
/
(C = 12, Cl = 35.5, N = 14, O = 16)
.(R = 0.0821 L. atm mol-1 K-1)
:
PCCl3 NO2 = X CCl3 NO2 Pt
(X
:
X CCl3NO 2 =
n CCl NO
3
CCl3 NO 2
n CCl NO + n air
3
m CCl3NO 2
Mw
CCl3 NO 2
X CCl3NO 2 =
m CCl3NO 2 PV
Mw
RT
CCl3 NO 2
0.92
164.5
X CCl3NO 2 =
731
0.92
760 2.151V
+
164.5 0.0821 (35 + 273)

0.005593
0.087410
= 0.0640
X CCl3NO 2 =
X CCl3NO 2
:
X CCl3 NO2 = 0.0640
PCCl3 NO2 = X CCl3 NO2 Pt
PCCl3 NO2 = 0.0640 731 mmHg
PCCl3 NO2 = 46.784 mmHg
(598)
)(599
/
* )(
) (30.2341 g )(30.6771 g
) (N2O ) (270 g
) (15 C ) .(740 mmHg .
N2O .
) .(1 g/cm3 )(R = 0.0821 L. atm mol-1 K-1
).(N = 14, O = 16
*
N2O
: N2O
m N2O = 30.6771 - 30.2341
m N2O = 0.443 g
:
m H2O = 270 - 30.2341
m H2O = 239.7659 cm3

:
m
V
= d H2O
m
d
239.7659
=V
1 g cm3
=V
V = 239.7659 cm3
)(599
)(600
/
PV = n R T
m
RT
Mw
mRT
= Mw
PV
( 0.443 g ) ( 0.0821 L. atm mol-1 K -1 ) (15 + 273) K
= Mw
239.7659 cm3
740
3
-1
760
1000 cm L
Mw = 44.87 g/mol
= PV
:
Mw N 2O = 14 + ( 2 16 ) = 46 g/mol
)( .
)(
) (0.152 g
(C4H5)n ) (36.0 cm3
) (16 C ) (764.0 mmHg
).(13.6 mmHg
.
:
Pt = Pg + PH 2O
Pg = Pt - PH2 O
Pg = 764.0 - 13.6
Pg = 750.4 mm Hg
)(600
)(601
/
PV=nRT
PV
= n (C4 H5 )n
RT
750.4
36.0
760
1000
=
( 0.0821 L . atm mol-1 K -1 ) (16 + 273) K
n (C4 H5 )n
n (C4 H5 )n = 1.49810 10-3 mol

:
m
Mw (C4 H5 )n
m
n
= n (C4 H5 )n
= Mw (C4 H5 )n
0.152
1.49810 10-3
= 101.462 g/mol
= Mw (C4 H5 )n
Mw (C4 H5 )n
) (n (C4H5)n
): (101.462 g/mol
Mw (C 4 H 5 ) n = n ( 4 12 + 5 1) = 101.462
n ( 53) = 101.462
101.462
53
n = 1.9 2
=n
:
= C8 H10
( C4 H 5 )2
)(
) (Ar ) (1.40 g/cm3

) .(- 186 C
) (1 mol
) (1 atm .
)(601
)(602

:
m Ar
V
= d Ar
m Ar
d Ar
= )V (Ar
39.95 g
1.40 g cm - 3
= )V (Ar
V (Ar) = 28.5360 cm 3
V (Ar) = 0.0285360 L
.
:
PV = nRT
nRT
= )Vg (Ar
P
(1 mol ) ( 0.0821 L . atm mol-1K -1 ) ( -186 + 273) K
= )Vg (Ar
1 atm
Vg (Ar) = 7.1427 L
)(1 mol Ar
:
V (Ar) = 0.0285360 L
Vg(Ar) = 7.1427 L
V = Vg - V
V = 7.1427 - 0.0285360
V = 7.114164 L
.
)(602
)(603
/
)(
) (0.1525 g
) (35.05 cm3 )(20 C
) (730 mmHg :
C
22.10 %

H
4.58 %
Br
73.32 %
.
)(R = 0.0821 L. atm mol-1 K-1
).(C = 12, H = 1, Br = 79.9
:
PV=nRT
PV
=n
RT
730
35.05
atm
L
760
1000
=n
( 0.0821 L . atm mol-1K -1 ) ( 20 + 273) K
n = 0.00140 mol
:
n = 0.00140 mol
m
=n
Mw
m
= Mw
n
0.1525
= Mw
0.00140
Mw = 108.930 g/mol
:
)(603
)(604
/
22.10
108.930 = 24.07
100
4.58
= wt. of H
108.930 = 4.990
100
73.32
= wt. of Br
108.930 = 79.867
100
= wt. of C
:
wt. of C = 24.07 , wt. of H = 4.990 , wt. of Br = 79.867
C : H : Br
24.07 4.990 79.867
:
:
12
1
79.9
2.006 : 4.990 : 0.9996
2:5:1
C2H5Br :
).(108.9 g/mol
)(
) (0.050 cm3 ) (54 C

) (1 L
)(0.9862 g/cm3
) .(112.5 mmHg
.
)(604

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(135)

) (NO2 ) ) (reddish brown

Have definite shape (resist Have

shape Have no definite shape (fill

(assume shapes of container)

Are nearly incompressible Have definite volume (are only

very slightly compressible).

Have high density

Have low density

Are not fluids

Diffuse only very slowly

Diffuse through other liquids

density than liquids

ordered Consist of disordered clusters Consist

together, particles usually random

have empty space between them;

motion in three dimensions

(solids and liquids are almost

Fig. 3 : Diffusion of bromine vapor in air. Some liquid (dark reddish

) circumstances ) (99.9% ) .(empty space

) 10300 103g (9.80665 m/s 2

) torr ) Evangelista Torricelli (1608 1647

) (0 C = 273 K ).(1 atm

Fig. 7 : Temperature scales. Zero on the absolute scale is the lowest

) (SI unit ) (m/s )(cm/s

Properties that describe a Gas

= 1 .013252 10 6 g. cm /cm 2 s 2 = 1.013 10 6 dyne/cm 2

) (torr ) (Torricelli) (Pa

F = ( 50 kg ) ( 9.81 m/s2 ) = 490 kg.m/s2 = 490 N

Fig. 10 : A mercury barometer is used to measure atmospheric pressure by

Fig. 11 : A Torricellian barometer

Fig. 13 : Torricelli's mercury barometer

) (1 atm ) (760 mm Hg ) (101325Pa :

P = ( 0.760 m ) (1.35951 104 kg/m3 ) ( 9.80665 m/s2 ) = 101325 Pa

Fig. 14 : Some commercial pressure-measuring devices.

1 atm 760 mmHg

Length of H 2O clumn = Length of Hg column

Length of H 2O clumn = 10.3 m

Pgas > Patm ) (Pgas

Fig. 15 : Open-end manometers for measuring pressure in a gas-filled

Fig. 19 : A apparatus for studying the relationship between pressure

Fig. 21 : Boyle's law. Boyle's experiment showing the compressibility of

Fig. 22 : A representation of Boyle's experiment. A sample of air is

Fig. 23 : Boyle's law: As volume decreases, gas molecules become more

Fig. 24 : Boyle's law.

Fig. 25 : A demonstration of Boyle's Law. Temperature is constant.

Fig. 27 : Compression of gases

Fig. 29 : Graphs showing variation of the volume of a gas with the

Fig. 30 : Boyle's law summarizes the effect of pressure on the volume of

Fig. 31 : When the pressure is plotted against 1/volume, a straight line is

Fig. 33 : Graphical illustration of Boyle's law.

Fig. 34 : Boyle's law.

) (0.5 ) (1.0 atm

2 L ) (O2 760 mmHg ) 1.42 g

Fig. 39 : A molecular interpretation of Charles Law the change in volume of a gas

Fig. 42 : Variation of the volume of a gas sample with temperature, at constant

Fig. 43 : A demonstration of Charle's Law. Pressure is constant.

) (V0 = 273 cm3

Fig. 51 : Variation of the volume of a gas sample with temperature, at constant

)(Absolute Kelvin Temperature Scale

)V2 = V1 (ratio of temperature that increase in volume

) (V2 ) (V1 650 cm3

) (T2 ) (V2 (0.6

) (Cl2 ) (H2 HCl