Chapter 5

The Gas Laws

 Pressure
 Force per unit area.
 Gas molecules fill container.
 Molecules move around and hit
sides.
 Collisions are the force.
 Container has the area.
 Measured with a barometer.
Vacuum
Barometer
 The pressure of the
atmosphere at sea
760 level will hold a
mm column of mercury
1 atm
Hg 760 mm Hg.
Pressure
 1 atm = 760 mm Hg
 Manometer
 Column of
mercury to
measure
pressure.
h
 h is how much

Gas lower the

pressure is
than outside.
 Manometer
 h is how much
higher the gas
pressure is than
the atmosphere.
h

Gas
 Units of pressure
 1 atmosphere = 760 mm Hg
 1 mm Hg = 1 torr
 1 atm = 101,235 Pascals = 101.325 kPa
 Can make conversion factors from
these.
 What is 724 mm Hg in kPa?
 in torr?
 in atm?
 The Gas Laws
 Boyle’s Law
 Pressure and volume are inversely
related at constant temperature.
 PV= k
 As one goes up, the other goes
down.
 P1V1 = P2 V2
 Graphically
V

P (at constant T)
V Slope = k

1/P (at constant T)

 22.41 L atm

PV O2
CO2

0 P (at constant T)
 Examples
 20.5 L of nitrogen at 25ºC and 742
torr are compressed to 9.8 atm at
constant T. What is the new volume?
 30.6 mL of carbon dioxide at 740 torr
is expanded at constant temperature
to 750 mL. What is the final pressure
in kPa?

1
 Charle’s Law
 Volume of a gas varies directly with
the absolute temperature at constant
pressure.
 V = kT (if T is in Kelvin)
 V1 = V 2
T1 = T 2
 Graphically

2
 He
CH4

H2O
V (L)

H2

-273.15ºC T (ºC)
3
 Examples
 What would the final volume be if 247
mL of gas at 22ºC is heated to 98ºC ,
if the pressure is held constant?

4
 Examples
 At what temperature would 40.5 L of
gas at 23.4ºC have a volume of 81.0
L at constant pressure?

5
 Avogadro's Law
 Avagadro’s
 At constant temperature and
pressure, the volume of gas is directly
related to the number of moles.
 V = k n (n is the number of moles)
 V1 = V2
n1 = n2

6
 Gay- Lussac Law
 At constant volume, pressure and
absolute temperature are directly
related.
 P=kT
 P1 = P 2
T1 = T 2

7
 Combined Gas Law
 If the moles of gas remains constant,
use this formula and cancel out the
other things that don’t change.
 P1 V1 = P 2 V2
. T1 T2

8
 Examples
 A deodorant can has a volume of 175
mL and a pressure of 3.8 atm at 22ºC.
What would the pressure be if the
can was heated to 100.ºC?
 What volume of gas could the can
release at 22ºC and 743 torr?

9
 Ideal Gas Law
 PV = nRT
 V = 22.41 L at 1 atm, 0ºC, n = 1 mole,
what is R?
 R is the ideal gas constant.
 R = 0.08306 L atm/ mol K
 Tells you about a gas is NOW.
 The other laws tell you about a gas
when it changes.

0
 Ideal Gas Law
 An equation of state.
 Independent of how you end up
where you are at. Does not depend
on the path.
 Given 3 you can determine the
fourth.
 An Empirical Equation - based on
experimental evidence.

1
 Ideal Gas Law
 A hypothetical substance - the ideal
gas
 Think of it as a limit.
 Gases only approach ideal behavior
at low pressure (< 1 atm) and high
temperature.
 Use the laws anyway, unless told to
do otherwise.
 They give good estimates.

2
 Examples
 A 47.3 L container containing 1.62 mol of
He is heated until the pressure reaches
1.85 atm. What is the temperature?
 Kr gas in a 18.5 L cylinder exerts a
pressure of 8.61 atm at 24.8ºC What is
the mass of Kr?
 A sample of gas has a volume of 4.18 L
at 29ºC and 732 torr. What would its
volume be at 24.8ºC and 756 torr?
3
 Gas Density and Molar Mass
 D = m/V
 Let M stand for molar mass
 M = m/n
 n= PV/RT
 M= m
PV/RT
 M = mRT = m RT = DRT
PV V P P

4
 Examples
 What is the density of ammonia at
23ºC and 735 torr?
 A compound has the empirical
formula CHCl. A 256 mL flask at
100.ºC and 750 torr contains .80 g of
the gaseous compound. What is the
empirical formula?

5
 Gases and Stoichiometry
 Reactions happen in moles
 At Standard Temperature and
Pressure (STP, 0ºC and 1 atm) 1
mole of gas occuppies 22.42 L.
 If not at STP, use the ideal gas law to
calculate moles of reactant or
volume of product.

6
 Examples
 Mercury can be achieved by the
following reaction
heat
HgO  Hg(l) + O 2 (g)
What volume of oxygen gas can
be produced from 4.10 g of mercury
(II) oxide at STP?
 At 400.ºC and 740 torr?

7
 Examples
 Using the following reaction
NaHCO 3 (s) + HCl 
NaCl(aq) + CO 2 (g) +H 2 O(l)
calaculate the mass of sodium hydrogen
carbonate necessary to produce 2.87 L
of carbon dioxide at 25ºC and 2.00 atm.
 If 27 L of gas are produced at 26ºC and
745 torr when 2.6 L of hCl are added
what is the concentration of HCl?

8
 Examples
 Consider the following reaction
4NH 3 (g) + 5 O 2 ( g )  4 NO(g) + 6H 2 O(g)
What volume of NO at 1.0 atm and
1000ºC can be produced from 10.0 L
of NH3 and excess O2 at the same
temperture and pressure?
 What volume of O measured at STP
2
will be consumed when 10.0 kg NH3 is
reacted?
9
 The Same reaction
4NH 3 (g) + 5 O 2 ( g )  4 NO(g) + 6H 2 O(g)

 What mass of H2O will be produced

from 65.0 L of O2 and 75.0 L of NH3
both measured at STP?
 What volume Of NO would be
produced?
 What mass of NO is produced from
500. L of NH3 at 250.0ºC and 3.00 atm?

0
 Dalton’s Law
 The total pressure in a container is
the sum of the pressure each gas
would exert if it were alone in the
container.
 The total pressure is the sum of the
partial pressures.
 PTotal = P1 + P2 + P3 + P4 + P5 ...
 For each P = nRT/V

1
 Dalton's Law
 PTotal = n1RT + n2RT + n3RT +...
V V V
 In the same container R, T and V are the
same.
 PTotal = (n1+ n2 + n3+...)RT
V
 PTotal = (nTotal)RT
V
2
 The mole fraction
 Ratio of moles of the substance to
the total moles.

symbol is Greek letter chi 
 
  = n1 = P1
nTotal PTotal

3
 Examples
 The partial pressure of nitrogen in air
is 592 torr. Air pressure is 752 torr,
what is the mole fraction of
nitrogen?
 What is the partial pressure of
nitrogen if the container holding the
air is compressed to 5.25 atm?

4
 Examples

4.00 L 1.50 L 3.50 L

CH4 N2 O2

2.70 atm 4.58 atm 0.752 atm

 When these valves are opened, what is
each partial pressure and the total
pressure?

5
 Vapor Pressure
 Water evaporates!
 When that water evaporates, the
vapor has a pressure.
 Gases are often collected over water
so the vapor. pressure of water must
be subtracted from the total
pressure.
 It must be given.

6
 Example
 N2O can be produced by the
following reaction
heat
NH 4 NO 3 ( s)    NO 2 (g) + 2H 2 O ( l )
what volume of N2O collected
over water at a total pressure of 94
kPa and 22ºC can be produced from
2.6 g of NH4NO3? ( the vapor
pressure of water at 22ºC is 21 torr)

7
 Kinetic Molecular Theory
 Theory tells why the things happen.
 explains why ideal gases behave the
way they do.
 Assumptions that simplify the
theory, but don’t work in real gases.
 The particles are so small we can
ignore their volume.
 The particles are in constant motion
and their collisions cause pressure.

8
 Kinetic Molecular Theory
 The particles do not affect each other,
neither attracting or repelling.
 The average kinetic energy is
proportional to the Kelvin
temperature.
 Appendix 2 shows the derivation of
the ideal gas law and the definition of
temperature.
 We need the formula KE = 1/2 mv2
9
 What it tells us
 (KE)avg = 3/2 RT
 This the meaning of temperature.
 u is the particle velocity.
 u is the average particle velocity.
 u 2 is the average particle velocity
squared.
 the root mean square velocity is
 u2 =
u
urms
0
 Combine these two equations
 (KE)avg = NA(1/2 mu 2 )
 (KE)avg = 3/2 RT

1
 Combine these two equations
 (KE)avg = NA(1/2 mu 2 )
 (KE)avg = 3/2 RT
3RT
u rms =
M

Where M is the molar mass in

kg/mole, and R has the units 8.3145
J/Kmol.
 The velocity will be in m/s
2
 Example
 Calculate the root mean square
velocity of carbon dioxide at 25ºC.
 Calculate the root mean square
velocity of hydrogen at 25ºC.
 Calculate the root mean square
velocity of chlorine at 25ºC.

3
 Range of velocities
 The average distance a molecule
travels before colliding with another
is called the mean free path and is
small (near 10-7)
 Temperature is an average. There are
molecules of many speeds in the
average.
 Shown on a graph called a velocity
distribution
4
 number of particles 273 K

Molecular Velocity
5
 number of particles 273 K

1273 K

Molecular Velocity
6
 number of particles 273 K

1273 K

1273 K

Molecular Velocity
7
 Velocity
 Average increases as temperature
increases.
 Spread increases as temperature
increases.

8
 Effusion
 Passage of gas through a small hole,
into a vacuum.
 The effusion rate measures how fast
this happens.
 Graham’s Law the rate of effusion is
inversely proportional to the square
root of the mass of its particles.

9
 Effusion
 Passage of gas through a small hole,
into a vacuum.
 The effusion rate measures how fast
this happens.
 Graham’s Law the rate of effusion is
inversely proportional to the square
root of the mass of its particles.
Rate of effusion for gas 1 M2

Rate of effusion for gas 2 M1
0
 Deriving
 The rate of effusion should be
proportional to urms
 Effusion Rate 1 = urms 1
Effusion Rate 2 = urms 2

1
 Deriving
 The rate of effusion should be
proportional to urms
 Effusion Rate 1 = urms 1
Effusion Rate 2 = urms 2
3RT
effusion rate 1 u rms 1 M1 M2
  
effusion rate 2 u rms 2 3RT M1
M2
2
 Diffusion
 The spreading of a gas through a
room.
 Slow considering molecules move at
100’s of meters per second.
 Collisions with other molecules slow
down diffusions.
 Best estimate is Graham’s Law.

3
 
Examples
A compound effuses through a porous
cylinder 3.20 time faster than helium. What is
it’s molar mass?
 If 0.00251 mol of NH3 effuse through a hole
in 2.47 min, how much HCl would effuse in
the same time?
 A sample of N2 effuses through a hole in 38
seconds. what must be the molecular weight
of gas that effuses in 55 seconds under
identical conditions?

4
 Diffusion
 The spreading of a gas through a
room.
 Slow considering molecules move at
100’s of meters per second.
 Collisions with other molecules slow
down diffusions.
 Best estimate is Graham’s Law.

5
 Real Gases
 Real molecules do take up space and
they do interact with each other
(especially polar molecules).
 Need to add correction factors to the
ideal gas law to account for these.