TABLE OF C ONTENTS

G AS P RESSURE AND ITS M EASUREMENT

C HEM 16 G ENERAL C HEMISTRY 1 T HE G AS L AWS

10 G ASES
T HE I DEAL G AS L AW
Dr. Gil C. Claudio
S OLVING G AS L AW P ROBLEMS
University of the Philippines, Diliman
D ALTON S L AW OF PARTIAL P RESSURES
First Semester 2014-2015
T HE K INETIC M OLECULAR T HEORY OF G ASES

R EAL G ASES : D EVIATIONS FROM I DEAL B EHAVIOR

R EFERENCES C HARACTERISTICS OF G ASES

Some characteristics of gases

References of these notes
expands spontaneously to fill its container
General Chemistry, 10th ed, by Ralph H. Petrucci, F. Geoffrey
Vgas = Vcontainer
Herring, Jeffy D. Madura, and Carey Bisonnette.
highly compressible
Chemistry: The Central Science, 13th ed., by Theodore
L. Brown, H. Eugene LeMay Jr., Bruce E. Bursten, Catherine
two or more gases form a homogeneous mixture regardless of
J. Murphy, Patrick M. Woodward, and Matthew W. Stoltzfus. the identities or relative proportions of the gases
due to large distances between gas molecules
P RESSURE S TANDARD ATMOSPHERE

The height of mercury in a barometer provides a measure of

barometric pressure.
density of mercury = 13.5951 g/cm3 (0 C), g = 9.80655
Pressure is a force per unit area. m/s2
Applied to gases, pressure is most easily understood in terms
of the height of a liquid column that can be maintained by the P = g hd
gas. = (9.80655 m/s2 )(0.7600 m)(1.35951 104 kg/m3 )
SI unit: N/m2 = Pa, kPa is more commonly used = 1.01325 105 kg/m-s2 1 atm
1 bar = 105 Pa = 105 N/m2

One standard atmosphere (atm) is defined to be exactly 101,325

Pa (or 101.325 kPa).

1 atm = 760 torr 760 mmHg

S OME C OMMON P RESSURE U NITS B OYLE S L AW

Boyles law states that tor a fixed amount of gas at a constant

temperature, the gas volume is inversely proportional to the gas
Atmosphere atm 1 atm
pressure.
Millimeter of mercury mmHg 760 mmHg 1
Torr Torr = 760 Torr P
V
Pascal Pa = 101,325 Pa
1
Kilopascal kPa = 101.325 kPa V = constant or PV = constant
P
Bar bar = 1.01325 bar
Millibar mbar = 1013.25 mbar Because PV products of two states are equal to the same value,

P1 V1 = P2 V2
B OYLE S L AW G RAPH C HARLES L AW

Charles Law state that the volume of a fixed amount of gas at

constant pressure is directly proportional to the Kelvin (absolute)
temperature.
V T
V
V = constant T or = constant
T
For a transformation of a gas from state 1 to 2 at constant P
V1 V2
=
T1 T2

commons.wikimedia.org/wiki/File:Boyles Law.svg

S TANDARD C ONDITIONS OF T AND P AVOGADRO S L AW

Avogadros law states that At a fixed temperature and pressure,

the volume of a gas is directly proportional to the amount of gas.
Standard conditions of temperature and pressure (or STP).
0 C = 273.15 K V n and V = c n
1 bar = 105 Pa (not 1 atm)
where is c is the molar volume.

1 mol gas = 22.414 L (at 0 C, 1 atm) = 22.711 L (at STP)

C OMBINED G AS L AW S UMMARIZING THE T HREE L AWS

Changes in one variable have on the gas volume when the other
The combined gas law states that for a fixed quantity of gas two variables are held constant.
P1 V1 P2 V2 1. Boyles law describes the effect of pressure, V 1/P
= n constant 2. Charless law describes the effect of temperature, V T .
T1 T2
3. Avogadros law describes the effect of the amount of gas,
V n.

T HE I DEAL G AS E QUATION C ALCULATIONS U SING THE I DEAL G AS E QUATION

PHMB 10 E , E XAMPLES 6.4 AND 6.5, PP 205-206

Ideal Gas Equation

PV = nRT

1. What is the volume occupied by 13.7 g Cl2 (g) at 45 C and

P pressure in atm
745 mmHg?
V volume in L
2. What is the pressure, in kilopascals, exerted by 1.00 1020
n quantity in moles molecules of N2 in a 305 mL flask at 175 C?
T temperature in K
ANSWERS:
R universal gas constant. Some values of R
0.082057 L-atm/mol-K
1. 5.14 L
0.083145 bar-L/mol-K 2. 2.03 kPa
8.3145 J/mol-K
8.3145 Pa-m3 /mol-K
8.3145 kPa-L/mol-K
T HE G ENERAL G AS E QUATION E FFECT OF T EMPERATURE C HANGES ON P RESSURE
BLBMWS 13 E , E XERCISE 10.5, P 411

Applying the ideal gas law to a change of a gas from an initial to a

final state, we get the general gas equation
Pi Vi P V The gas pressure in an aerosol can is 1.5 atm at 25 C. Assuming
= f f that the gas obeys the ideal-gas equation, what is the pressure
ni Ti nf T f
when the can is heated to 450 C?
At constant n, we get the combined gas law
Pi Vi P V ANSWER: 3.6 atm.
= f f constant n
Ti Tf

C OMBINED G AS L AW D ETERMINING A M OLAR M ASS

BLBMWS 13 E , E XERCISE 10.6, P 412 PHMB 10 E , E XAMPLE 6-7, P 208

Propylene is an important commercial chemical (about ninth in the

An inflated balloon has a volume of 6.0 L at sea level (1.0 atm)
and is allowed to ascend until the pressure is 0.45 atm. During
ascent, the temperature of the gas falls from 22 C to 21 .
Calculate the volume of the balloon at its final altitude.
ANSWER: 11 L
amount produced among manufactured chemicals) used in the
synthesis of other organic chemicals and in production of plastics
(polypropylene). A glass vessel weighs 40.1305 g when clean, dry,
and evacuated; it weighs 138.2410 g when filled with water at
25.0 C (density of water = 0.9970 g/mL) and 40.2959 g when
filled with propylene gas at 740.3 mmHg and 24.0 C. What is the
molar mass of propylene?

ANSWER: 42.08 g/mol

C ALCULATING A G AS D ENSITY L AW OF C OMBINING V OLUMES
PHMB 10 E , E XAMPLE 6-8, P 209

Gay-Lussacs law of combining volumes states that, when

What is the density of oxygen gas O2 at 298 K and 0.987 atm?
compared at the same temperature and pressure, the volumes of
gases involved in a reaction are in the ratio of small whole numbers.
ANSWER: 1.29 g/L

R EACTION S TOICHIOMETRY C ALCULATIONS L AW OF C OMBINING V OLUMES

PHMB 10 E , E XAMPLE 6-9, P 211 PHMB 10 E , E XAMPLE 6-10, P 212

Zinc blende ZnS is the most important zinc ore. Roasting (strong
heating) of ZnS in oxygen is the first step in the commercial
What volume of N2 , measured at 735 mmHg and 26 C, is production of zinc.
produced when 75.0 g NaN 3 is decomposed?

2 ZnS(s) + 3 O2 (g) 2 ZnO(s) + 2 SO2 (g)
2 NaN3 (s) 2 Na(l) + 3 N2 (g)
What volume of SO2 (g) can be obtained from 1.00 L O2 (g) and
ANSWER: 43.9 L excess ZnS(s)? Both gases are measured at 25 C and 745 mmHg.

ANSWER: 0.667 L SO2 (g)

PARTIAL P RESSURE G AS M IXTURES
PHMB 10 E , E XAMPLE 6-11, P 213

A partial pressure is the pressure exerted by an individual gas in a

mixture, independently of other gases.
Each gas in the mixture expands to fill the container and What is the pressure, in bar, exerted by a mixture of 1.0 g H2 and
exerts its own partial pressure. 5.00 g He when the mixture is confined to a volume of 5.0 L at
ntot RT 25 C?
Ptot = constant T and V
V
ntot RT ANSWER: 8.5 bar
Vtot = constant T and P
P

D ALTON S L AW OF PARTIAL P RESSURES M OLE F RACTIONS AND PARTIAL P RESSURES

BLBMWS 13 E , E XERCISE 10.11, PP 417-418
Daltons law of partial pressures states that in a mixture of
gases, the total pressure is the sum of the partial pressures of the
gases present. A study of the effects of certain gases on plant growth requires a
synthetic atmosphere composed of 1.5 mol % CO2 , 18.0 mol %
Ptot = PA + PB + . . . O2 , and 80.5 mol % Ar.
   
RT RT
= nA + nB +... 1. Calculate the partial pressure of O2 in the mixture if the total
V V pressure of the atmosphere is to be 745 torr.
RT RT
= ( nA + nB + . . . ) = ntot 2. If this atmosphere is to be held in a 121-L space at 295 K,
V V
how many moles of O2 are needed?
ANSWERS:
The mole fraction xA of a gas in the mixture is 1. 134 torr
nA P V 2. 0.880 mol
xA = = A = A
ntot Ptot Vtot
K INETIC M OLECULAR T HEORY OF G ASES D ISTRIBUTION OF M OLECULAR S PEEDS
The kinetic-molecular theory of gases is a model for describing
gas behavior. The assumptions are
1. Gases consist of large numbers of molecules that are in
continuous, rapid, random, straight-line motion. The Maxwell distribution of speeds F (v )
2. The combined volume of all the molecules of the gas is 3/2
Mv 2
  
negligible relative to the total volume in which the gas is M
F (v ) = 4v 2 exp
contained. 2RT 2RT
3. Attractive and repulsive forces between gas molecules are
negligible. F (0) = 0
4. Energy can be transferred between molecules during collisions the probability density increases with the speed up to a
but, as long as temperature remains constant, the average maximum and then declines.
kinetic energy of the molecules does not change with time.
Perfectly elastic collisions.
5. The average kinetic energy of the molecules is proportional to
the absolute temperature. At any given temperature, the
molecules of all gases have the same average kinetic energy.

M AXWELL B OLTZMANN D ISTRIBUTION AVERAGE S PEEDS

N OBLE G ASES The most probable speed vmp is the speed at the maximum of
F (v )
2kB T 1/2 2RT 1/2
   
Maxwell-Boltzmann Molecular Speed Distribution for Noble Gases
vmp = =
m M
0.004 The mean speed hv i is calculated as the average of v using the
Probability density (s/m)

probability distribution F (v )
0.003 4
He  1/2  1/2
20
Ne 8kB T 8RT
0.002
40 Ar hv i = =
132
Xe m M
0.001 The root-mean-squared speed is

3kB T 1/2 3RT 1/2

   

1/2
0 500 1000 1500 2000 2500 vrms = v 2 = =
m M
Speed (m/s)
From these three calculations
en.wikipedia.org/wiki/File:MaxwellBoltzmann-en.svg

vrms > hv i > vmp

AVERAGE S PEEDS S PEEDS OF G AS M OLECULES

Various types of average speeds of gas molecules at 298 K

vrms hv i vmp
gas (m/s) (m/s) (m/s)
H2 1920 1769 1568
O2 482 444 394
CO2 411 379 336
CH4 681 672 556

M EAN F REE PATH M EAN F REE PATH OF O XYGEN

SAB 4 E , E XAMPLE 17.8, P 630

The mean free path is the average distance traveled between

collisions For oxygen at 25 C the collision diameter is 0.361 nm.

1 kB T P PNA
The mean free path at 1 bar pressure is 7.11 108 m, or
= = where = = 197 molecular diameters.
2d 2 2d 2 P kB T RT
The mean free path at 0.1 Pa pressure is 0.071 m (or 7.1 cm),
where d is the collision diameter of an ideal gas molecule. or 1.97 108 molecular diameters
D ISTRIBUTION OF K INETIC E NERGY D IFFUSION AND E FFUSION

The kinetic energy distribution F () can be solved as

2
F () = 1/2 e /kB T Diffusion refers to the spreading of a substance (usually a gas or
(kB T )3/2
liquid) into a region where it is not originally present as a result of
and the average kinetic energy of an ideal gas molecule is random molecular motion.

3 Effusion is the escape of a gas through a tiny hole in its container.

h i = kB T
2
The Kelvin temperature of a gas is directly proportional to the
average translational kinetic energy of its molecules.

G RAHAM S L AW G ASES E FFUSING T HROUGH AN O RIFICE

PHMB 10 E , E XAMPLE 6-15, P 225

Grahams law states that the rates of effusion or diffusion of two

different gases are inversely proportional to the square roots of
their molar masses. For example
If 2.2 104 mol N2 (g) effuses through a tiny hole in 105 s, then
rate of effusion of A v M how much H2 (g) would effuse through the same orifice in 105 s?
= rms,A = B
rate of effusion of A vrms,B MA
ANSWER: 8.2 104 mol H2
Can be applied to
molecular speeds, effusion rates, effusion times, distances
traveled by molecules, or amounts of gas effused
R ELATING E FFUSION T IMES AND M OLAR M ASSES T HE VAN DER WAAL S E QUATION
PHMB 10 E , E XAMPLE 6-16, P 225

The van der Waals equation is an equation of state for nonideal

gases. It includes correction terms to account for intermolecular
forces of attraction and for the volume occupied by the gas
molecules themselves.
A sample of Kr(g) escapes through a tiny hole in 87.3 s. The same
an2
 
amount of an unknown gas escapes in 42.9 s under identical P + 2 (V nb ) = nRT
conditions. What is the molar mass of the unknown gas? V

ANSWER: 20.0 g/mol b is the excluded volume per mole. It is (approximately)

the volume that one mole of gas occupies when it condenses
to a liquid.
The proportionality constant a provides a measure of how
strongly the molecules attract each other.

C OMPRESSIBILITY FACTOR C OMPRESSIBILITY FACTOR OF A IR

Real gases behave like ideal gases in the limits of low pressures and
high temperatures, but they deviate significantly at high pressures
and low temperatures. A convenient measure of the deviation from
ideal gas behavior is the compressibility factor
PV
Z =
nRT

At P 0, Z 1, ideal gas
At very high P, V > Videal because the molecules of the gas
are pushed closer together and a significant fraction of the
volume is occupied by the molecules themselves.
In some cases at low P, Z < 1 is possible due to IFA.
en.wikipedia.org/wiki/File:Compressibility Factor of Air 250 - 1000 K.png
VDW C ONSTANTS AND C OMPRESSIBILITY FACTORS T HE VAN DER WAALS E QUATION
AT 10 BAR AND 300 K, PHMB 10 E , TABLE 6.5, P 226 PHMB 10 E , E XAMPLE 6-17, PP 228-228

a bar-L2 /mol2 b L/mol Z

H2 0.2452 0.0265 1.006
He 0.0346 0.0238 1.005
N2 1.37 0.0387 0.998
CO 1.472 0.0395 0.997 Use the van der Waals equation to calculate the pressure exerted
O2 1.382 0.0319 0.994 by 1.00 mol Cl2 (g) confined to a volume of 2.00 L at 273 K. The
CH4 2.303 0.0431 0.983 value of a = 6.49 L2 atm mol2 , and that of b = 0.0562 L mol1 .
NF3 3.58 0.0545 0.965
CO2 3.658 0.0429 0.95 ANSWER: 9.9 atm
N2 O 3.852 0.0444 0.945
C2 H6 5.58 0.0651 0.922
NH3 4.225 0.0371 0.887
SF6 5.58 0.0651 0.88
C3 H8 9.39 0.0905 a
SO2 7.857 0.0879 a