1

30231

3 .

(Gas)

()

3 .

3 .

1.

(volume)
Unit
L or l
mL or ml
cm3
dm3
m3

3 .

Pressure
Unit

SI Unit
1 atm

= 1.013 x 105 pascal

= 1.013 x 106 dyne cm -2
= 14.7 lb inch-2
= 760 torr
1 pascal = 1 N m-2

Evangelista Torricelli 1608-1647(Italian Physicist)

Barometer

1643
Torricellian vacuum

3 .

Pressure

Barometer

3 .

Pressure = force/area
P = F/A (1)

F = mg
g =

m = = V
= V=

F = V g
... (2)
1
F = (r2h) g . (3)
3 .

r =
h =

P = [(r2h) g ]/ r2
r2

P = hg
(4)

g
4
P h
3 .

P
h

h P

2 . .
3 .

10

2
Pgas = Patm + Ph

.(5)

2
Pgas = Patm - Ph
3 .

.(6)

11

2
..(7)
Pgas = P h
(
)
P
=
760 torr
mmHg
0o C

3 .

00C 273.15 K
1 atm
1.013 x 105 Pa
STP (standard
temperature and
pressure)
NTP(normal
temperature and
pressure)

3 .

12

13

2. (Boyles law)
Robert Boyle 1662

T
V
V

1/P
= k1 .(1/P)

(V P k )

VP = k1
(8)

P1V1 = P2V2 = k1
3 .

14

P V (hyperbola)

(isotherm) [iso ]

B
P

P1V1

P2V2

T4=800 K
T3=600 K
T2 =400 K
T1 =200 K

P3V3
A
V
3 P-V
T

3 .

V
3 P-V T

15

8

P = k. (1/V)

V = k. (1/P)
(origin)
4. 4.

B
P

A
V

B
1/V

4
P 1/V
3 .

1/P
4
V 1/P

16

A
PV

P
4 PV P
P
PV P
4

3 .

1.

2.

3.

4.

3 .

17

18

1 350 cm3 0.92 atm

21 oC 1.4 atm
P1V1 = P2V2
21 oC P1 = 0.92 atm, V1= 350 cm3
P2 = 1.4 atm, V2= ? Cm3

0.92 atm x 350 cm3

V2 = (0.92 x 350)/1.4
= 230 cm3

3 .

= 1.4 atm x V2

1.

3 .

19

20

3. (Charless Law)

(Jacques Charles)
V T

P T
. T 1 oC
V 1/273 V 0oC
... 273 cm3 0oC
1 ( 1 0oC)
1/273 273 cm3
1 cm3
274 cm3 1 oC
3 .

21

V t o C
V0 0 o C

V = V0 + (1/273) t V0
= V0[1+ (t/273)]
= V0[(273 + t)/273]
= 273 + t

(9)

= V0 (T/273)

(10)

= (V0 /273)T
= k 2T
(V/T) = k2
(11)

T1 T2
V1/T1 = V2/T2 = k2
3 .

(12)

 P (K)

P4
P
3

-273.15 K

P
1

-300 -200 -150 -100

-50

50

100

t(oC)

5 V t
(P1 > P2 > P3 > P4)
3 .

22

23

273 0C 0 K

.......
2 79.5 cm3 45 0C
0 0C

V1/T1 = V2/T2
V1 = 79.5 cm3
T1 = 273 + 45 K = 318 K
V2 = ?

T2 = 273 + 0 K = 273 K
(79.5 cm3)/318 K = (V2/273 K)

V2 = (79.5 cm3)(273 K) /318 K

= 68.3 cm3
3 .

1.

3 .

24

 - ( Joseph Gay-Lussac)

P
P

T
kT ( V

P/V
=
k
k
P1/T1

= P2/T2 = k . (13)

2 10 (L)
2.00 atm 2.50 atm
P1/T1 = P2/T2

2.00 atm/ 273 K

P1 = 2.00 atm
P2 = 2.50 atm
=

T1 = 273 K
T2 = ? K

2.50 atm/ T2

3 .

25

26

3 .

27

T2

= (2.50 atm)(273 K)/ 2.00 atm

= 341 K
= 341-273 oC = 68 oC ()

4 10 L 50 atm 25 oC
70 atm 38 oC

P1/T1 = P2/T2
P1 = 50 atm T1 = 273+25
P2 = ?

50 atm /298 K

T2

= 298 K
= 273 +38 = 311 K

= P2/311 K
P2
= 52 atm
70 atm
3 .


Joseph Gay-Lussac

V

2

T P
V / V =

(Amadeo Avogadro)

V
n

V
=
kn
(14)

3 .

28






1.

2.

3 .

29

4.

V P, T n
V = V(P,T,n)
. (15)
(total differential)
dV = (V/ P)T,ndP + (V/ T)P,ndT + (V/ n)p,Tdn
(16)

(V/ P)T,n

V = k1/P T n
= -k1/P2 = -V/P

(V/ T)P,ndT = k2

= V/n

(V/ n)p,T = k3 = V/n
3 .

V = k2T

. (17)

P n
..(18)
(19)

30

31

(17), (18), (19) (16)

dV = -(V/P) dP + (V/T)dT + (V/n) dn
dV/V = -dP/P + dT/T + dn/n
(dP/P) + (dV/V) = (dT/T) + (dn/n)

p2

dP
p1 P

ln

V2

dV
V1 V

P2
P1

+
ln

ln V2

P2 V2
P1 V1
P2 V2
P1 V1

V1

T2

dT
T1 T

=
=

ln T2

ln

T1

ln

.(20)

n2

+
n1

dn
n

n2
n1

n2 T2
n1 T1

3 .

n2 T2
n1 T1

R (21)

32

R
(gas constant)
(21)
PV
nT

pV

nRT.

(the ideal gas law)

T
P
6

3 .

(22)

33

B
P

A
1/V

6 P -V

6 P (1/V)

B
A
log V

A
B
1/P

6 V (1/P)
3 .

log P

6 log V - log P

34

22
m
M
PV

m
M

RT

(23)

m
V

RT
M

(24)

RT
M

(25)

= m/V =
1 mol

STP

P = 1 atm, V = 22.4 L, n = 1 mol , T = 273 K (25)

3 .

35

PV
nT

(1 atm)(22.4 L)

=
R

(1 mol)(273 K)
0.08206 L atm K-1 mol-1

R
R
=
=

= 0.08206 x 103 cm3 )(1.0133 x 106 dyne cm-2 K-1 mol-1)

8.314 x 107 erg K-1 mol-1)
8.314 J K-1 mol-1)
1.987 cal K-1 mol-1)

=
3 .

36

= 0.08206 L atm K-1 mol-1

= 1.987 cal K-1 mol-1

= 8.314 J K-1 mol-1)

3 .

37

5
0.950 atm 6.35 cm3
(21)
P1 V 1
n1T1

P1 = 1 atm, V1 = ? cm3, T1 = 273 K, n1 = n2

P2 = 0.950 atm, V2 = ? cm3, T2 = 300 K
(1 atm)V1
273 K

(0.950 atm) (6.35 cm3)

300 K

3 .

P2 V 2
n2T2

38

V1 =
V1 =

(0.950 atm) (6.35 cm3)(273 K)

(1 atm) (300 K)
549 cm3

3 .

39

6 0.452 L
87 oC 0.620 atm
(21)
n =

PV
RT

P = 0.620 atm, V1 = 0.452 L,

R = 0.08205 L atm K-1 mol-1 , T1 = 273 K,
n=?
(0.620 atm)(0.452 L)
n =
(0.08205 L atm K-1 mol-1)(360 K)
n =

9.49 x 10-3 mol

3 .

40

7
500 cm3 0.326 g 100 oC 380 torr
m RT
(23) PV
=
M

P = (380 torr /760 torr atm 1) = 0.5 atm

V1 = 500 cm3 = 0. 5 L,
R = 0.08205 L atm K-1 mol-1 , T1 = 373 K,
m = 0.326 g
M=?

(0.326 g)(0.08205 L atm K-1 mol-1)(373 K)

(0.5 atm)(0.5 L)

39.9 g mol -1

3 .

(Molecular kinetic theory of gas)

(Daniel Bernoulli, 1738)

James Clerk Maxwell,
Ludwig Boltzmann, 1880
The Kinetic molecular theory of gases

[
]

3 .

41

42

3
1.



2 .

3 .
(elastic collision)


P, V

3 .

43

N l
A 7
m x v
mv
x

z
y
x
l

7 l
3 .

44

elastic

=
mvx

= -mvx
= mvx ( -mvx)
= 2mvx

( )

= 2l
()
= 2 l/vx
2

=

3 .

45

2 mvx

F =

mvx2

2 l/vx

1
(P)

P =

mvx2
2
F

mvx

P =

lA

3 .

 vxi i x
N
m
V

P =

vix2

. (26)

i=1

x
vx2

vx12 + vx22 + vx32 + vxi2 +.. + vxN2

N
N

i=1
N

P
PV

=
=

vix2

. (27)

Nm vx2
V
Nm vx2

3 .

. (28)

46


x , y z
= v
vx , vv , vz
=

V2

V x2 + V y2 + V z2

V x2 + V y2 + V z2
=

V2

Vx

= V

2
y

= V

2
z

1
3

Nmv2
PV

3 .

. (29)

V2
. (30)

47

48

PV

PV

(30)

2
N [(1/2) mv2]
3
2
N
3
1
mv2
2

. (31)

N = NA ( L) (31)

PV

2 E
3

3 .

. (32)

49

E=

NA

(23) (32)
E

2
RT
3

. (33)

(33) 0 K = 0


(thermal energy)

3 .

50

1 NA
E

1
NA 2 mv2

3RT

M

root mean-square velocity(speed) vrms
NA

v2

2 Mv2
2

vrms

v2

3 .

3RT
M

. (34)

51

3 .

6.

(The distribution of molecular velocity)

(kinetic theory of gas)

J.C.Maxwell
(Boltzmann distribution)
Maxwell-Boltzmann distribution
P(v) = 4 (m/2kT)3/2 . v2exp(-mv2/2kT) ..(31)

3 .

52

53

P(v) (probability)
v v+dv
k (Boltzmann constant)
k = R/NA = 8.314 J K-1 mol-1/ 6.023 x 1023 mol-1 = 1.38 x 10-23 J K-1
e = 2.71

3 .

54

T1

vmp

v
vrms

P(v)

P(v)

T2

12 16
v(m s-1)

20

8
O2 T1 T2

3 .

8
12
v(m s-1)

vmp, v

vrms

55

= v
(Boltzmann constant)

P(v)

k
k = R/NA
R (gas constant)

NA (Avocadros constant ,
Avocadros number

k = 1.38 x 10-23 J K-1

R = 8.314 J K-1 mol-1

NA = 6.023 x 1023 mol-1

e (natural log) = 2.71..

3 .

56

v (mean velocity)
vmp
(most probable velocity)

v = 8kT/m
v = 8RT/m

vm

()
()

2RT
M

(36a)
(36b)
(37)

(34) , (36) (37)

T molecular weight (M)
3 .

 8 , 9

vmp : v : vrms = 1: 1.13:1.2
( 9)

A B
vA/vB

MB/MA

3 .

(38)

57

 8 vrms (v)
1 25o C
vrms =

(3RT/M)
[(3 x 8.314 J K-1 mol-1) x (273

=
= 1927 m s-1

+25) K]/0.002 kg mol-1

(36)
v = 8RT/M

= 8 ( 8.314 J K-1 mol-1)(298 K)/ (3.14 )(0.002 kg mol-1)

= 1775 m s-1

-


3 .

58

7.

59

(effusion)
(diffusion)

( 10)
1831 (Thomas Graham)

()
()

( r )
r

1
d

3 .

60

rA
rB

dB
dA

(M)

rA
rB

MB
MA

(39)

rA
rB

vA
vB

(38)
rA
rB

MB
MA

(40)

10

3 .

61

10 (effusion)

3 .

62

9 NH3 CO2
(M NH3 CO2 17 44

(40)
rNH3
rCO2

MCO2
MNH3

(44/17

= 1.6

( ) 1.6 CO2

3 .


(U) 235U 0.7%
238U 99.3% F2 235UF6
238UF

r (235UF6)
r (238UF6)

M (238UF6)
M (235UF6)

(352/349)

= 1.004

235UF6

3 .

63

64

8.

PV = nRT
n = 1 PV/RT = 1
(real gas)
PV/RT = 1 ( 11 12)

3 .

2.0

65

N2

200 K

CH4
H2

500 K

NH3

1.0

PV/RT

1000 K

200 400 600 800 1000 1200

P(atm)

11
273 K

3 .

300

600

P(atm)

900

12 Z
CH4

66

( )

1873 Johanes van der Waals

(P + a 2 )(v2 b) = RT
v

.. (41)

a b
V

3 .

67

a b
PV = nRT n = 1

V (molar volume)

V
= RT/P T = 0 K, V = 0
T = 0 K, V = 0 ( )
= V b
b
(excluded volume)
= r
2r ( )

3 .

68

2 = (4/3)(2r)3
1 = (1/2) (4/3)(2r)3
= 4(4/3) r3 4 1

2r
r

(excluded volume)
3 .


( )

3 .

69


1.
2.

70

C = n/V

(n/V)2

an2/V2

a (n/V)2

a V2

a CO
a Ne]

3 .

71

P+ a/V2 (41)

2
an
(P + 2 )(v nb) = nRT
v

.. (42)

b
1.
a

3 .

(atm L2 mol-2)

H2
N2
Ne
Ar
O2
CO
CO2
H2O
NH3
CH4
CCl4
HCl

0.244
1.39
0.211
1.35
1.36
1.46
3.59
5.47
4.18
2.25
19.6
3.67

3 .

B (L mol-1)
0.0266
0.0391
0.0171
0.0322
0.0318
0.0392
0.0427
0.0305
0.0373
0.0427
0.1270
0.0408

72

73

10 CO2 18.617 mol 10 L

100oC . .
.

PV = nRT
P = nRT/V
(18.617 mol)(0.08205 L atm mol-1)(373K)
=
10 L
= 57 atm

2
an
(P + 2 )(v nb) = nRT
v

P =

nRT
(v nb)

an2
v2

3 .

.. (42)

74

(18.617 mol)(0.08205 L atm mol-1)(373K)

P =
(10 L) - (18.617 mol )(0.0427 L mol-1)

(3.59 atm L2 mol-2 )(18.617 mol)2

(10 L)2

49.5 atm

= 57 49.5 = 7.5 atm

3 .

75

9.

1L

1L
H2 0.50 atm

N2 0.75 atm

1L
O2 0.10 atm

1L
1.35 atm

3 .

76

Dalton 1802 :
2


(partial pressure)

3 .

 77

Pi i
Ptot
V
ni i
ntot

PtotV = ntotRT
= (n1 + n2 +. ni +) RT

Ptot

= n1 RT + n2 RT
V
V

. (43)

+. ni RT +
V

= P1 + P2 + + Pi+
3 .

(44)

78

(44)
Pi
Ptot
=

.. (45)

Pi = niRT/V

Pi
Pi
Ptot

niRT / V
ntotRT / V

xi = ni/ntot

Ptot

ni
ntot

xi

.. (46)

(mole fraction) i

Pi = xiPtot

3 .

.. (47)

79

A P1 V1
V PA

PAV = P1V1
PA

= (P1V1)/V

3 .

.. (48)

80

11 N2 200 cm3 25 oC 250 torr

O2 350 cm3 25 oC 300 torr
300 cm3
N2: V1 = 200 cm3

P1 = 250 torr

V = 300 cm3 PN2 = ?

PN2 =
=
PO2 =

Ptot =

P1V1
V
(250 torr)(200 cm3)
(300 cm3)
(300 torr)(350 cm3)

(300

cm3)

167 torr

=
=

350 torr

PN2 + PO2 = 167 + 350 = 517 torr

3 .

81

12 2.3 L H2 0.174
0 oC
N2 1.365 g

H2 N2
0.174 g

2 28 g mol-1
=

0.087 mol

1.365 g
28 g/mol

0.049 mol

ntot =

nH2 + nN2

xH2 =

nH2 / ntot

= .087 mol/0.136mol = 0.64

xN2 =

nN2 / ntot

= .049mol/0.136mol = 0.36

nH2 =
nN2 =

2 g/mol

3 .

0.136 mol

82

PH2 = nH2 (RT/V)

(0.087 mol)(0.082 L atm mol-1)(273 K)
=
2.83 L
=
0.69 atm
PN2 = nN2 (RT/V)
(0.049 mol)(0.082 L atm mol-1)(273 K)
=
2.83 L
=

0.39 atm

Ptot

PH2 + PN2 = 0.69 + 0.39 = 1.08 atm

3 .


Martin S. Silberberg, Chemistry: The Molecular Nature
of Matter and Change, McGraw-Hill Higher Education,
2004
Raymond Chang, Chemistry, Williams College,
McGraw-Hill Higher Education, 2002

3 .

83