Gas Laws

1
Properties of Gases
 Variable volume and shape
 Expand to occupy volume available
 Volume, Pressure, Temperature,
and the number of moles present
are interrelated
 Can be easily compressed
 Exert pressure on whatever
surrounds them
 Easily diffuse into one another

2
Mercury Barometer
 Used to define and
measure atmospheric
pressure
 On the average at sea
level the column of
mercury rises to a height of
about 760 mm.
 This quantity is equal to 1
atmosphere
 It is also known as
standard atmospheric
pressure

3
Barometer
 The mercury barometer was
the basis for defining
pressure, but it is difficult to
use or to transport
 Furthermore Mercury is very
toxic and seldom used
anymore
 Most barometers are now
aneroid barometers or
electronic pressure sensors,

4
Pressure Units & Conversions

 The above represent some of the more common units for

measuring pressure. The standard SI unit is the Pascal or
kilopascal. (kPa)
 The US Weather Bureaus commonly report atmospheric
pressures in inches of mercury.
 Pounds per square inch or PSI is widely used in the United
States.
 Most other countries use only the metric system.
5
Standard Temperature and
Pressure
 Standard Temperature and Pressure or
STP = 0oC or 273.15 Kelvin and a pressure
of 1 atmosphere.
 This is used as a reference point when
comparing quantities of gases
 Gases are seldom measured at exactly these
conditions.
 We need to be able to compute the volume
at various temperature and pressures
Sample Problem 1:
If the pressure of helium gas in a balloon
has a volume of 4.00 dm3 at 210 kPa, what
will the pressure be at 2.50 dm3?
P1 V1 = P2 V2

(210 kPa) (4.00 dm3) = P2(2.50 dm3)

P2 = (210 kPa) (4.00 dm3)

(2.50 dm3)
= 340 kPa

7
Boyle’s Law
 According to Boyle’s Law
the pressure and volume
of a gas are inversely
proportional at constant
pressure.
 PV = constant.
 P1V1 = P2V2

8
Boyle’s Law

 A graph of pressure and volume gives an inverse

function
 A graph of pressure and the reciprocal of volume
gives a straight line
9
Standard Temperature and Pressure
(STP)
The volume of a gas varies with temperature
and pressure. Therefore it is helpful to have
a convenient reference point at which to
compare gases.
For this purpose standard temperature and
pressure are defined as:
Temperature = 0oC 273 K
Pressure = 1 atmosphere
= 760 torr
= 101.3 kPa
This point is often called STP 10
Charles’ Law
According to Charles’ Law the volume of a
gas is proportional to the Kelvin temperature
as long as the pressure is constant
V = kT Note: The temperature
for gas laws must
always be expressed
V1 V2 in Kelvin where Kelvin
= = oC +273.15 (or 273
T1 T2 to 3 significant digits)

11
 Charles’ Law

 A graph of temperature and volume yields a straight line.

 Where this line crosses the x axis (x intercept) is defined
as absolute zero
12
Sample Problem 2
A gas sample at 40 oC occupies a volume of
2.32 dm3. If the temperature is increased to 75
o
C, what will be the final volume?
V1 = V2
T1 T2
Convert temperatures to Kelvin. 40oC = 313K
75oC = 348K
2.32 dm3 = V2
313 K 348K

(313K)( V2) = (2.32 dm3) (348K)

2.58 dm3
V2 = 13
Gay-Lussac’s Law
Gay-Lussac’s Law defines the
relationship between pressure
and temperature of a gas.

The pressure and temperature

of a gas are directly
proportional

P1 = P2
T1 T2

14
Sample Problem 3:
The pressure of a gas in a tank is 3.20 atm at 22
o
C. If the temperature rises to 60oC, what will be
the pressure in the tank?
P1 = P2
T1 T2
Convert temperatures to Kelvin. 22oC = 295K
60oC = 333K
3.20 atm = P2
295 K 333K

(295K)( P2) = (3.20 atm)(333K)

3.6 atm
P2 = 15
The Combined Gas Law
1. If the amount of the gas is constant, then
Boyle’s Charles’ and Gay-Lussac’s Laws
can be combined into one relationship
2. P1 V1 = P2 V2

T1 T2

16
Sample Problem 4:

A gas at 110 kPa and 30 oC fills a container

at 2.0 dm3. If the temperature rises to 80oC
and the pressure increases to 440 kPa, what
is the
P1Vnew
= volume?
P V2 Convert temperatures to Kelvin. 30oC = 303K
1 2
80oC = 353K
T1 T2
V2 = V1 P1 T2 = (2.0 dm3) (110 kPa ) (353K)
P2 T1 (440 kPa ) (303 K)

V2 = 0.58 dm3

17
Advogadro’s Law
 Equal volumes of a gas under the same temperature
and pressure contain the same number of particles.
 If the temperature and pressure are constant the
volume of a gas is proportional to the number of
moles of gas present
V = constant * n
where n is the number of moles of gas
V/n = constant
V1/n1 = constant = V2 /n2
V1/n1 = V2 /n2

18
Universal Gas Equation
 Based on the previous laws there are four factors
that define the quantity of gas: Volume, Pressure,
Kelvin Temperature, and the number of moles of
gas present (n).
 Putting these all together:
PV = Constant = R
nT
The proportionality constant R is known as the
universal gas constant

19
Universal Gas Equation
The Universal gas equation is usually written as
PV = nRT
Where P = pressure
V = volume
T = Kelvin Temperature
n = number of moles
The numerical value of R depends on the pressure unit
(and perhaps the energy unit) Some common values of
R include:
R = 62.36 dm3 torr mol-1 K-1
= 0.0821 dm3 atm mol-1 K-1
= 8.314 dm3kPa mol-1 K-1
20
 Sample Problem 5
Example: What volume will 25.0 g O2 occupy
at 20oC and a pressure of 0.880 atmospheres? :

Data (25.0 g)
n = ----------------- = 0.781 mol
(32.0 g mol-1)

V =? P = 0.880 atm; T = (20 + 273)K = 293K

R = 0.08205 dm-3 atm mol-1 K-1
Formula PV = nRT so V = nRT/P
Calculation V = (0.781 mol)(0.08205 dm-3 atm mol-1 K-1)(293K)
0.880 atm
Answer V = 21.3 dm3
21
Universal Gas Equation –
Alternate Forms
Density (d) Calculations
m PM m is the mass of the gas in g
d= =
V RT M is the molar mass of the gas

Molar Mass (M ) of a Gaseous Substance

dRT d is the density of the gas in g/L
M=
P

22
Sample Problem 6
A 2.10 dm3 vessel contains 4.65 g of a gas at 1.00
atmospheres and 27.0oC. What is the molar mass of
the gas?

dRT m 4.65 g g
M= d=
P V =2.10 dm3= 2.21dm3

g dm3•atm
2.21 dm3 x 0.0821
mol•K
x 300.15 K
M=
1 atm

M = 54.6 g/mol
23
Dalton’s Law of Partial Pressures
The total pressure of a mixture of gases is
equal to the sum of the pressures of the
individual gases (partial pressures).

PT = P 1 + P 2 + P 3 + P 4 + . . . .

where PT = total pressure

P1 = partial pressure of gas 1
P2 = partial pressure of gas 2
P3 = partial pressure of gas 3
P4 = partial pressure of gas 4
24
Dalton’s Law of Partial Pressures
 Applies to a
mixture of
gases
 Very useful
correction when
collecting gases
over water
since they
inevitably
contain some
water vapor.

25
 Sample Problem 7
Henrietta Minkelspurg
generates Hydrogen
gas and collected it
over water.
If the volume of the gas
is 250 cm3 and the
barometric pressure is
765.0 torr at 25oC, what
is the pressure of the
“dry” hydrogen gas at
STP?
(PH2O = 23.8 torr at 25oC)

26
 Sample Problem 8
 Henrietta Minkelspurg generated Hydrogen gas and collects it
over water. If the volume of the gas is 250 cm3 and the
barometric pressure is 765 torr at 25oC, what is the volume of
the “dry” oxygen gas at STP?
 From the previous calculation the adjusted pressure is 742.2
torr
P1= PH2 = 742.2 torr; P2= Std Pressure = 760 torr
T1= 298K; T2= 273K; V1= 250 cm3; V2= ?
(V1P1/T1) = (V2P2/T2) therefore V2= (V1P1T2)/(T1P2)
V2 = (250 cm3)(742.2 torr)(273K)
(298K)(760.torr)
V2 = 223.7 cm3
27
Kinetic Molecular Theory
 Matter consists of particles (atoms or molecules)
that are in continuous, random, rapid motion
 The Volume occupied by the particles has a
negligibly small effect on their behavior
 Collisions between particles are elastic
 Attractive forces between particles have a
negligible effect on their behavior
 Gases have no fixed volume or shape, but take
the volume and shape of the container
 The average kinetic energy of the particles is
proportional to their Kelvin temperature
28
Maxwell-Boltzman Distribution
 Molecules are in
constant motion
 Not all particles
have the same
energy
 The average kinetic
energy is related to
the temperature
 An increase in
temperature
spreads out the
distribution and the
mean speed is
shifted upward

29
 Velocity of a Gas

The distribution of speeds

of three different gases
at the same temperature

The distribution of speeds

for nitrogen gas molecules
at three different temperatures

urms =  3RT
M 30
Diffusion
Gas diffusion is the gradual mixing of molecules of
one gas with molecules of another by virtue of their
kinetic properties.

NH4Cl

NH3 HCl
17.0 g/mol 36.5 g/mol 31
DIFFUSION AND EFFUSION
 Diffusion is the  Effusion is the
gradual mixing of movement of
molecules through
molecules of a small hole into an
different gases. empty container.

32
Graham’s Law
Graham’s law governs
effusion and diffusion of
gas molecules.
KE=1/2 mv2

The rate of effusion is

inversely proportional Thomas Graham, 1805-1869.
Professor in Glasgow and London.
to its molar mass.
33
Sample Problem 9
1 mole of oxygen gas and 2 moles of ammonia are placed in a
container and allowed to react at 850 oC according to the equation:

4 NH3(g) + 5 O2(g)  4 NO(g) + 6 H2O(g)

Using Graham's Law, what is the ratio of the effusion rates of

NH3(g) to O2(g)?

34
Scheffler
Sample Problem 10
What is the rate of effusion for H2 if 15.00 cm3 of CO2
takes 4.55 sec to effuse out of a container?
Rate for CO2 = 15.00 cm3/4.55 s = 3.30 cm3/s

35
Sample Problem 11
What is the molar mass of gas X if it effuses
0.876 times as rapidly as N2(g)?

36
Scheffler
Ideal Gases v Real Gases
 Ideal gases are gases that obey the Kinetic
Molecular Theory perfectly.
 The gas laws apply to ideal gases, but in
reality there is no perfectly ideal gas.
 Under normal conditions of temperature and
pressure many real gases approximate ideal
gases.
 Under more extreme conditions more polar
gases show deviations from ideal behavior.

37
In an Ideal Gas ---
 The particles (atoms or molecules) in continuous,
random, rapid motion.
 The particles collide with no loss of momentum
 The volume occupied by the particles is essentially zero
when compared to the volume of the container
 The particles are neither attracted to each other nor
repelled
 The average kinetic energy of the particles is proportional
to their Kelvin temperature
At normal temperatures and pressures gases closely
approximate idea behavior

38
Real Gases
 For ideal gases the product of pressure and
volume is constant. Real gases deviate somewhat
as shown by the graph pressure vs. the ratio of
observed volume to ideal volume below.

These deviations occur because

 Real gases do not actually have zero volume
 Polar gas particles do attract if compressed
39
van der Waals Equation
The van der Waals equation shown below includes
corrections added to the universal gas law to account
for these deviations from ideal behavior

(P + n2a/V2)(V - nb) = nRT

where a => attractive forces between molecules
b => residual volume or molecules
The van der Waals constants for some elements are shown below
Substance a (dm6atm mol-2) b (dm3 mol-1)
He 0.0341 0.02370
CH4 2.25 0.0428
H 2O 5.46 0.0305
CO2 3.59 0.0437 40
 Sample Problem 12

What is the volume of CO2 produced at 370 C and

1.00 atm when 5.60 g of glucose are used up in the
reaction:
C6H12O6 (s) + 6O2 (g) 6CO2 (g) + 6H2O (l)

g C6H12O6 mol C6H12O6 mol CO2 V CO2

1 mol C6H12O6 6 mol CO2
5.60 g C6H12O6 x x = 0.187 mol CO2
180 g C6H12O6 1 mol C6H12O6

dm3•atm
0.187 mol x 0.0821 x 310.15 K
nRT mol•K
V= = = 4.76 dm3
P 1.00 atm 41