Chemistry 8ed, Whitten etal, TB/C 2007

CHAPTER GOALS
1. Comparison of Solids, Liquids, and Gases
Gases and the Kinetic 2. Composition of the Atmosphere and Some Common
Properties of Gases
Molecular Theory 3. Pressure
4. Boyle’s Law: The Volume-Pressure Relationship
5. Charles’ Law: The Volume-Temperature Relationship;
The Absolute Temperature Scale
6. Standard Temperature and Pressure
7. The Combined Gas Law Equation
8. Avogadro’s Law and the Standard Molar Volume

Chemistry 8ed, Whitten 2

etal, TB/C 2007

CHAPTER GOALS Comparison of Solids, Liquids,

and Gases
9. Summary of Gas Laws: The Ideal Gas Equation
10. Determination of Molecular Weights and Molecular • The density of gases is much less than that
Formulas of Gaseous Substances
of solids or liquids.
11. Dalton’s Law of Partial Pressures
12. Mass-Volume Relationships in Reactions Involving Densities Solid Liquid Gas
Gases (g/mL)
13. The Kinetic-Molecular Theory H2O 0.917 0.998 0.000588
14. Diffusion and Effusion of Gases
15. Real Gases: Deviations from Ideality CCl4 1.70 1.59 0.00503

Chemistry 8ed, Whitten 3 4

etal, TB/C 2007

Comparison of Solids, Liquids,

Composition of the Atmosphere
and Gases
Dry Air

Gas molecules must be very far apart Gas % by Volume
compared to liquids and solids.
N2 78.09
O2 20.94
Ar 0.93
CO2 0.03
He, Ne, Kr, Xe 0.002
CH4 0.00015
H2 0.00005
5 6
Some Common Properties of
Gases
Pressure
• Atmospheric pressure is measured using a
• Pressure barometer.
• Definitions of standard pressure
- force per unit area – 76 cm Hg
– lb/in2 – 760 mm Hg
– 760 torr
– N/m2
– 1 atmosphere
– 101.3 kPa

Hg density = 13.6 g/mL

7 8

Gas Laws
Boyle’s Law
- show the relationship between pressure,
temperature & volume of a sample of gas
• volume – pressure relationship
• Boyle’s Law
• states that the pressure of a gas is
• Charle’s Law inversely proportional to its volume at
• Combined Gas Law constant temperature
• Avogadro’s Law • or the product of a gas’s pressure and
• Ideal Gas Law volume is always constant
• Dalton’s Law of Partial Pressures
9 10

Boyle’s Law Boyle’s Law

• V ∝ 1/P or
• V= k (1/P) or PV = k
• P1V1 = k1 for one sample of a gas.
• P2V2 = k2 for a second sample of a gas.
• k1 = k2 for the same sample of a gas at
the same T.
• Thus we can write it mathematically as
P1V1 = P2V2

11 12
Boyle’s Law Charles’ Law
• Example: At 25oC a sample of He has a volume of • states that the volume of a gas is
4.00 x 102 mL under a pressure of 7.60 x 102 torr.
What volume would it occupy under a pressure of directly proportional to the absolute
2.00 atm at the same T? temperature at constant pressure.
P1 V1 = P2 V2
P1 V1 • note: gas laws must use the Kelvin
V2 =
P2 scale to be correct.
=
(760 torr )(400 mL )
1520 torr K = o C + 273
= 2.00 × 10 2 mL
13 14

Charles’ Law Charles’ Law

15 16

Charles’ Law: Charles’ Law:

• Example: A sample of hydrogen, H2, occupies 1.00 x
V
V ∝ T or V = kT or =k 102 mL at 25.0oC and 1.00 atm. What volume would it
T occupy at 50.0oC under the same pressure?
V1 V
= k and 2 = k T1 = 25 + 273 = 298
T1 T2 T2 = 50 + 273 = 323
however the k' s are equal so
V1 V2 VT
= ∴ V2 = 1 2
V1 V T1 T2 T1
= 2 in the most useful form
T1 T2 1.00 × 10 2 mL × 323 K
V2 =
298 K
= 108 mL
17 18
Standard Temperature and
The Combined Gas Law
Pressure
• combined Boyle’s and Charles’ Laws
• Standard temperature and pressure is
• useful when the V, T, and P of a gas are
given the symbol STP. changing.
– It is a reference point for some gas
calculations. Boyle' s Law Charles' Law
V1 V2
• Standard P ≡ 1.00000 atm or 101.3 kPa P1V1 = P2 V2 =
T1 T2
• Standard T ≡ 273.15 K or 0.00oC For a given sample of gas : The combined gas law is :
PV P1 V1 P2 V2
=k =
T T1 T2

19 20

The Combined Gas Law Avogadro’s Law and the

• Example: A sample of nitrogen gas, N2, occupies
7.50 x 102 mL at 75.00C under a pressure of 8.10 x
Standard Molar Volume
102 torr. What volume would it occupy at STP?
V1 = 750 mL V2 = ?
• at the same temperature and pressure,
equal volumes of two gases contain the
T1 = 348 K T2 = 273 K
same number of molecules (or moles) of
P1 = 810 torr P2 = 760 torr gas.
P1 V1 T2
Solve for V2 = • At STP, then one mole of that gas has a
P2 T1
volume called the standard molar
=
(810 torr )(750 mL )(273 K ) volume.
volume
(760 torr )(348 K )
= 627 mL
21 22

Avogadro’s Law and the Avogadro’s Law

Standard Molar Volume
• Example. One mole of a gas occupies 36.5 L
and its density is 1.36 g/L at a given temperature
• The standard molar volume is and pressure. (a) What is its molar mass? (b)
22.4 L at STP. What is its density at STP?
– For gases, the volume is
proportional to the number ? g 36.5 L 1.36 g
= × = 49.6 g/mol
of moles. mol mol L
?g 49.6 g 1 mol
= × = 2.21 g/L
L STP mol 22.4 L

23 24
The Ideal Gas Law The Ideal Gas Law
• relates pressure, temperature, volume and number of
moles of a gas sample • R has other values if the units are changed.
• the relationship is associated with a universal constant, R • R = 8.314 J/mol K
– since one mole of a gas at 1.00 atm, and 273 K (STP), the – Use this value in thermodynamics.
volume is 22.4 L  we can use these values in the ideal gas law.
• R = 8.314 kg m2/s2 K mol
– Use this later in this chapter for gas velocities.
PV (1.00 atm )(22.4 L ) • R = 8.314 dm3 kPa/K mol
R= =
nT (1.00 mol)(273 K ) – This is R in all metric units.
• R = 1.987 cal/K mol
L atm
= 0.0821 – This the value of R in calories rather than J.
mol K
25 26

The Ideal Gas Law The Ideal Gas Law

• Example: What volume would 50.0 g of
nR T
ethane, C2H6, occupy at 1.40 x 102 oC under a V=
pressure of 1.82 x 103 torr? P
(1.67 mol ) 0.0821 L atm (413 K )
1. T = 140 + 273 = 413 K =  mol K 
2. P = 1820 torr (1 atm/760 torr) = 2.39 atm 2.39 atm
3. 50 g (1 mol/30 g) = 1.67 mol = 23.6 L

27 28

The Ideal Gas Law The Ideal Gas Law

• Example: Calculate the number of moles
in, and the mass of, an 8.96 L sample of n=
PV
=
(1.00 atm)(8.96 L ) = 0.400 mol CH
4
RT  L atm 
methane, CH4, measured at standard  0.0821 (273 K )
conditions.  mol K 
16.0 g
? g CH4 = 0.400 mol × = 6.40 g
mol

29 30
Dalton’s Law of Partial
Pressures
• states that the pressure exerted by a
mixture of gases is the sum of the
partial pressures of the individual
gases.
Ptotal = PA + PB + PC + .....
31
Dalton’s Law of Partial
Pressures
• Example: If 1.00 x 102 mL of hydrogen, measured at
25.0 oC and 3.00 atm pressure, and 1.00 x 102 mL of
oxygen, measured at 25.0 oC and 2.00 atm pressure,
were forced into one of the containers at 25.0 oC,
what would be the pressure of the mixture of gases?
PTotal = PH 2 + PO 2
= 3.00 atm + 2.00 atm
= 5.00 atm
33
Dalton’s Law of Partial
Pressures
• Example. A sample of hydrogen was collected by
displacement of water at 25.0 oC. The atmospheric
pressure was 748 torr. What pressure would the dry
hydrogen exert in the same container?
PTotal = PH2 + PH2O
∴PH2 = PTotal − PH2O
PH2 = (748− 24) torr=724torr
note: PH20 is temperature dependent. table for its
values can be found in your laboratory manual
35
Dalton’s Law of Partial
Pressures
32
Dalton’s Law of Partial
Pressures
• Vapor Pressure is the pressure exerted by a
substance’s vapor over the substance’s liquid
at equilibrium.
– accounted for in measuring pressures in of gases
above liquid samples
34
Determination of Molecular Weights
and Molecular Formulas of Gaseous
Substances
• considers the dependence of the number of
moles of a gas molecule to pressure,
temperature & volume conditions
• Example: A compound that contains only
carbon and hydrogen is 80.0% carbon and
20.0% hydrogen by mass. At STP, 546 mL of
the gas has a mass of 0.732 g . What is the
molecular (true) formula for the compound?
36
Determination of Molecular Weights Determination of Molecular Weights
and Molecular Formulas of Gaseous and Molecular Formulas of Gaseous
Substances Substances
PV 1.00 atm (0.546 L)
1 mol C n= = = 0.02232 mol
? mol C atoms = 80.0 g C × = 6.67 mol C RT
0.0821
L - atm
(298 K)
12.0 g C mol - K
1 mol H 0.732 g g
? mol H atoms = 20.0 g H × = 19.8 mol H n= = 32.8
1.01 g H 0.02232 mol mol
actual mass 32.8
19.8 = ≈2
= 3 ∴ EF : CH 3 with mass = 15 empirical mass 15.0
6.67
(CH3 )2 = C2H6

37 38

Determination of Molecular Weights Determination of Molecular Weights

and Molecular Formulas of Gaseous and Molecular Formulas of Gaseous
Substances Substances
1 mol C
• Example: A 1.74 g sample of a compound ? mol C atoms = 1.44 g C × = 0 .120 mol C
12 .0 g C
that contains only carbon and hydrogen
1 mol H
contains 1.44 g of carbon and 0.300 g of ? mol H atoms = 0.300 g H × = 0 .297 mol H
1.01 g H
hydrogen. At STP 101 mL of the gas has a
mass of 0.262 gram. What is its molecular 0.297
= 2 .5
formula? 0.120
∴ C 2 H 5 with mass = 29

n=
PV
=
(1 .00 atm )(0.101 L ) = 0 .00451 mol
 L atm 
 (273 K )
RT
 0.0821
 mol K 
39 40

Determination of Molecular Weights Mass-Volume Relationships

and Molecular Formulas of Gaseous
Substances in Reactions Involving Gases

?g 0 . 262 g 2 &∆
= = 58 . 1 g/mol 2 KClO3(s) MnO
 → 2 KCl(s) + 3 O2 (g)
mol 0.00451 mol
= 2 ∴ (C 2 H 5 )2 = C 4 H 10
58.1 2 mol KClO3 yields 2 mol KCl and 3 mol O2
29 2(122.6g) yields 2 (74.6g) and 3 (32.0g)

Those 3 moles of O2 can also be thought of as:

3(22.4L) or 67.2 L at STP

41 42
Mass-Volume Relationships in Mass-Volume Relationships in
Reactions Involving Gases Reactions Involving Gases
• Example: What volume of oxygen
measured at STP, can be produced 1 molKClO3
LSTP O2 = 120.0g KClO3 ×
by the thermal decomposition of 120.0 122.6g KClO3
g of KClO3? 3 molO2 22.4 LSTP O2
× ×
2 molKClO3 1 molO2
= 32.9 LSTP O2

43 44

The Kinetic-Molecular Theory The Kinetic-Molecular Theory

• Postulate 1 • Postulate 2
– Gases consist of discrete molecules that are – Gas molecules are in constant, random,
relatively far apart.
straight line motion with varying velocities.
– Gases have few intermolecular attractions.
• Proof - Brownian motion displays molecular
– The volume of individual molecules is very
small compared to the gas’s volume. motion.
• Proof - Gases are easily compressible.

45 46

The Kinetic-Molecular Theory The Kinetic-Molecular Theory

• Postulate 4
• Postulate 3
– The kinetic energy of the molecules is
– Gas molecules have elastic collisions with
proportional to the absolute temperature.
themselves and the container.
– The average kinetic energies of molecules
– Total energy is conserved during a
of different gases are equal at a given
collision.
temperature.
• Proof - A sealed, confined gas exhibits no
• Proof - Brownian motion increases as
pressure drop over time.
temperature increases.

47 48
The Kinetic-Molecular Theory The Kinetic-Molecular Theory
• The gas laws that we have looked at earlier in this chapter
• The kinetic energy of the molecules is are proofs that kinetic-molecular theory is the basis of
gaseous behavior.
proportional to the absolute temperature.
• Boyle’s Law
• Displayed in a Maxwellian distribution.
– P ∝ 1/V
– As the V increases the molecular collisions with
container walls decrease and the P decreases.
• Dalton’s Law
– Ptotal = PA + PB + PC + .....
– Because gases have few intermolecular attractions,
their pressures are independent of other gases in the
container.
• Charles’ Law
– V∝T
– An increase in temperature raises the molecular
49 velocities, thus the V increases to keep the P constant.
50

The Kinetic-Molecular Theory The Kinetic-Molecular Theory

• The root-mean square velocity of gases is • Example: What is the root mean square velocity
a very close approximation to the average of N2 molecules at room T, 25.0oC?
gas velocity.
• Calculating the root-mean square velocity
 kg m 2 
is simple:
3 8.314  (298 K )
u rm s =
3R T
 sec K mol 
2

Mm u rms =
0 .028 kg/mol
• To calculate this correctly:
= 515 m/s
– The value of R = 8.314 kg m2/s2 K mol
– And M must be in kg/mol.
51 52

Diffusion and Effusion of

The Kinetic-Molecular Theory
Gases
• Example. What is the root mean square velocity of • Diffusion is the intermingling of gases.
He atoms at room T, 25.0oC?
• Effusion is the escape of gases through
 tiny holes.
kg m 2 
3 8.314 (298 K )
 sec 2 K mol 
urms =
0.004 kg/mol
= 1363 m/s

53 54
 Diffusion and Effusion of Diffusion and Effusion of
Gases Gases
• The rate of effusion is inversely
proportional to the square roots of the
molecular weights or densities.
R1 M2
=
R2 M1
or
R1 d2
=
R2 d1

55 56

Diffusion and Effusion of Diffusion and Effusion of

Gases
• Example: Calculate the ratio of the rate of effusion of
He to that of sulfur dioxide, SO2, at the same
temperature and pressure.
Gases
• Example: A sample of hydrogen, H2, was found to effuse through
a pinhole 5.2 times as rapidly as the same volume of unknown
gas (at the same temperature and pressure). What is the
molecular weight of the unknown gas?

M SO 2 R H2 M unk
R He =
= R unk M H2
R SO 2 M He
M unk
5.2 =
. g / mol
641 2.0 g/mol
=
4.0 g / mol M unk
27 =
2.0 g/mol
= 16 = 4 ∴ R He = 4 R SO 2 M unk = 27( 2.0 g/mol) = 54 g/mol

57 58

Real Gases: Real Gases:

Deviations from Ideality Deviations from Ideality
• At low temperatures and high pressures real • van der Waals’ equation accounts for the
gases do not behave ideally. behavior of real gases at low temperatures and
high pressures.
• The reasons for the deviations from ideality
are:
 n 2a
 ( V − nb ) = nRT
1. The molecules are very close to one
another, thus their volume is important. P +
2. The molecular interactions also become  V2 
important.

59 60
 Real Gases: Real Gases:
Deviations from Ideality Deviations from Ideality
• The van der Waals constants a and b take into • What are the intermolecular forces in
account two things: gases that cause them to deviate from
1. a accounts for intermolecular attraction ideality?
2. b accounts for volume of gas molecules
1. For nonpolar gases the attractive forces
• At large volumes a and b are relatively small are London Forces.
and van der Waal’s equation reduces to ideal 2. For polar gases the attractive forces are
gas law at high temperatures and low
pressures.
dipole-dipole attractions or hydrogen
bonds.

61 62

Real Gases: Real Gases:

Deviations from Ideality Deviations from Ideality
• Example: Calculate the pressure exerted by • Example: Solve the previous example using
84.0 g of ammonia, NH3, in a 5.00 L the van der Waal’s equation.
container at 200. oC using the ideal gas law.
L2 atm
n = 4.94 mol a = 4.17 b = 0.0371 L
1 mol mol 2 mol
n = 84.0 g NH3 × = 4.94 mol
17.0 g
 2 
 P + n a  (V - nb ) = nRT ∴
(4.94 mol) 0.0821 L atm (473 K ) 
 V 2 
P=
nRT
=  mol K 
nRT n2a
V 5.00 L P= − 2
P = 38.4 atm V - nb V
63 64

Real Gases:
Deviations from Ideality
“So, if you think you are standing firm, be
careful that you don't fall!”
473K ) (4.94 mol )  4.17 mol 2 
2 L2 atm 
(4.94 mol ) (0.0821 mol
L atm )( - 1 Corinthians 10:12 -
P= K
−
5.00 L − ( 4.94 mol )( 0.0371 mol
L )
(5.00 L )2
191 .8 L atm
P= − 4.07 atm = (39 .8 atm − 4.1 atm )
4.817 L
P = 35 .7 atm which is a 7.6% difference from ideal questions?

65