AP* Chemistry

GASES
The gaseous state of matter is the simplest and best-understood state of matter. You inhale approximately
8,500 L of air each day. This amounts to about 25 lbs of air. Breathing is a three-step process: inhaling, gas
exchange with the circulatory system, and exhaling. Approximately 80% pressure differences created by your
body allow you to breathe. Nearly the Earths entire atmosphere is made up of only five gases: nitrogen,
oxygen, water vapor, argon, and carbon dioxide.
PROPERTIES OF GASES
Only FOUR quantities are needed to define the state of a gas:
1. the quantity of the gas, n (in moles)
2. the temperature of the gas, T (in KELVINS)
3. the volume of the gas, V (in liters)
4. the pressure of the gas, P (in atmospheres)
A gas uniformly fills any container, is easily compressed & mixes
completely with any other gas.

GAS PRESSURE is a measure of the force that a gas

exerts on its container. Force is the physical quantity
that interferes with inertia. Gravity is the force
responsible for weight.
Force = mass acceleration; (Newtons 2nd Law)
The SI units follow:
N = kg m/s2
Pressure-- Force/ unit area; N/m2; which is the
definition of 1.0 Pascal

Barometer--invented by Evangelista Torricelli in 1643; uses the height of a column of mercury to measure gas
pressure (especially atmospheric P)
1 mm of Hg = 1 torr
1.00 atm = 760.00 mm Hg = 760.00 torr = 29.92 in Hg = 14.7 psi = 101.325 kPa 105 Pa
At sea level all of the above define STANDARD PRESSURE.
The SI unit of pressure is the Pascal (named after Blaise Pascal);
1 Pa = 1 N / m2
The manometera device for measuring the pressure of a gas in a
container. The pressure of the gas is given by h [the difference in
mercury levels] in units of torr (equivalent to mm Hg).
a) Gas pressure = atmospheric pressure h
b) Gas pressure = atmospheric pressure + h
*AP is a registered trademark of the College Board, which was not involved in the production of, and does not endorse, this product.
2014 by Ren McCormick. All rights reserved. Some art copyright Pearson Education Inc. 2014

Exercise 1
Pressure Conversions
The pressure of a gas is measured as 49 torr. Represent this pressure in both atmospheres and Pascals.

Exercise 2
Pressure Comparisons
Rank the following pressures in decreasing order of magnitude (largest first, smallest last): 75 kPa, 300. torr,
0.60 atm and 350. mm Hg.

GAS LAWS: THE EXPERIMENTAL BASIS

BOYLES LAW: Father of Chemistry--the volume of a confined
gas is inversely proportional to the pressure exerted on the gas.
ALL GASES BEHAVE IN THIS MANNER!

Robert Boyle was an Irish chemist. He studied PV relationships

using a J-tube set up in the multi-story entryway of his home.
(Thus his was MUCH larger than the one shown right.)
o P 1/V
o pressure and volume are inversely proportional
o Volume Pressure at constant temperature, the
converse is also true
o for a given quantity of a gas at constant temperature, the product of pressure
and volume is a constant

PV = k

Therefore, V =

k
1
=k
P
P
which is the equation for a straight line of the type y = mx + b,
where m = slope, and b is the y-intercept

In this case, y = V, x = 1/P and b = 0. Check out the plot on the right (b).
The data Boyle originally collected is graphed on (a) above on the right.

P1V1 = P2V2 is the easiest form of Boyles law to memorize

Boyles Law has been tested for over three centuries.

It holds true only at low pressures.

Gases

Exercise 3
Boyles Law I
Sulfur dioxide (SO2), a gas that plays a central role in the formation of acid rain, is found in the exhaust of
automobiles and power plants. Consider a 1.53- L sample of gaseous SO2 at a pressure of 5.6 103 Pa.
If the pressure is changed to 1.5 104 Pa at a constant temperature, what will be the new volume of the gas?

Ideal Gases
At normal conditions such as standard temperature and pressure,
most real gases behave qualitatively like an ideal gas. Many gases
such as nitrogen, oxygen, hydrogen, noble gases, and some heavier
gases like carbon dioxide can be treated like ideal gases within
reasonable tolerances. Generally, a gas behaves more like an ideal gas
at higher temperature and lower pressure, as the work which is against
intermolecular forces becomes less significant compared with the
particles' kinetic energy, and the size of the molecules becomes less
significant compared to the empty space between them.
An ideal gas is expected to have a constant value of PV, as shown by
the dotted line on the graph pictured above. CO2 shows the largest
change in PV, and this change is actually quite small: PV changes from about 22.39 Latm at 0.25 atm to
22.26 Latm at 1.00 atm. Thus Boyles Law is a good approximation at these relatively low pressures.
So, why does CO2 deviate from ideal behavior the most? It has more electrons, thus is more polarizable, thus
has higher dispersion forces (a type of intermolecular force a.k.a. London dispersion forces or LDFs), therefore
the molecules are more attracted to each other, so carbon dioxide gas deviates from ideal behavior more than
oxygen or carbon dioxide do.
Gases

Exercise 4
Boyles Law II
In a study to see how closely gaseous ammonia obeys Boyles law, several volume measurements were made at
various pressures, using 1.0 mol NH3 gas at a temperature of 0C. Using the results listed below; calculate the
Boyles law constant for NH3 at the various pressures. Calculate the deviation from ideal behavior in each case.
Account for the trend apparent in the data.
Experiment
1
2
3
4
5
6

Pressure (atm)
0.1300
0.2500
0.3000
0.5000
0.7500
1.000

Volume (L)
172.1
89.28
74.35
44.49
29.55
22.08

Exercise 5
Boyles Law III
Next, PLOT the values of PV vs. P for the six experiments in Exercise 4. Extrapolate to determine what
PV equals at a hypothetical 0.00 atm pressure. Compare it to the PV vs. P graph on page 3 of these lecture
notes. What is the value of the y-intercept?

Gases

CHARLESS LAW: If a given quantity of gas is held at a constant pressure, then its volume is directly
proportional to the absolute temperature. Must use KELVINS Why?

Jacques Charles was a French physicist and the first

person to fill a hot air balloon with hydrogen gas
and made the first solo hot air balloon flight!
o V T plot = straight line
o V1T2 = V2T1
o Temperature Volume at constant pressure
o This figure shows the plots of V vs. T (Celsius) for
several gases. The solid lines represent
experimental measurements on gases.
The dashed lines represent extrapolation of the
data into regions where these gases would become
liquids or solids. Note that the samples of the
various gases contain different numbers of moles.
o What is the temperature when the volume
extrapolates to zero? Sound familiar?

Exercise 6
Charless Law
A sample of gas at 15C and 1 atm has a volume of 2.58 L. What volume will this gas occupy at 38C and
1 atm?

Each of the balloons below contains the same number of particles in the gas phase. This is yet another example
of heat em up and speed em up!. As the molecules warm, they gain kinetic energy, move faster, and thus
collide with the walls of their container with more energy. (Umph! If you prefer) In this case, the walls of the
container are made of rubber which can expand and contract.

Gases

GAY-LUSSACS LAW of combining volumes: volumes of gases always combine with one another in the
ratio of small whole numbers, as long as volumes are measured at the same T and P.
-

P1T2 = P2T1

Avogadros hypothesis: equal volumes of gases under the same conditions of temperature and pressure
contain equal numbers of molecules.

These balloons each hold 1.0 L of gas at 25C

and 1 atm. Each balloon contains 0.041 mol
of gas, or 2.5 1022 gas molecules.

AVOGADROS LAW: The volume of a gas, at a given temperature and pressure, is directly proportional to
the quantity of gas.
Vn
n Volume at constant T & P
HERES AN EASY WAY TO MEMORIZE ALL OF THIS!
Start with the combined gas law:

P1V1T2 = P2V2T1
Memorize just this use a simple pattern to figure the rest out:

Place the scientist names in alphabetical order.

Boyles Law uses the first 2 variables, Charles Law the second 2 variables & Gay-Lussacs Law the
remaining combination of variables.
Whichever variable doesnt appear in the formula is being held CONSTANT!

Exercise 7
Avogadros Law
Suppose we have a 12.2-L sample containing 0.50 mol oxygen gas (O2) at a pressure of 1 atm and a temperature
of 25C. If all this O2 were converted to ozone (O3) at the same temperature and pressure, what would be the
volume of the ozone?

Gases

THE IDEAL GAS LAW

Four quantities describe the state of a gas: pressure, volume, temperature, and # of moles (quantity).
Combine all 3 laws:
V nT
P
Replace the with a constant, R, and you get:
PV = nRT

The ideal gas law is an equation of state.

R = 0.8206 L atm/mol K also expressed as
0.8206 L atm mol1 K1
Useful only at low Pressures and high temperatures!
Guaranteed points on the AP Exam!
These next exercises can all be solved with the ideal gas law, BUT, you can use another if you like!
Exercise 8
Ideal Gas Law I
A sample of hydrogen gas (H2) has a volume of 8.56 L at a temperature of 0C and a pressure of
1.5 atm. Calculate the moles of H2 molecules present in this gas sample.

Exercise 9
Ideal Gas Law II
Suppose we have a sample of ammonia gas with a volume of 3.5 L at a pressure of 1.68 atm. The gas is
compressed to a volume of 1.35 L at a constant temperature. Use the ideal gas law to calculate the final
pressure.

Exercise 10
Ideal Gas Law III
A sample of methane gas that has a volume of 3.8 L at 5C is heated to 86C at constant pressure. Calculate its
new volume.

Gases

Exercise 11
Ideal Gas Law IV
A sample of diborane gas (B2H6), a substance that bursts into flame when exposed to air, has a pressure of
345 torr at a temperature of -15C and a volume of 3.48 L. If conditions are changed so that the temperature
is 36C and the pressure is 468 torr, what will be the volume of the sample?

Exercise 12
Ideal Gas Law V
A sample containing 0.35 mol argon gas at a temperature of 13C and a pressure of 568 torr is heated to 56C
and a pressure of 897 torr. Calculate the change in volume that occurs.

GAS STOICHIOMETRY
Use PV = nRT to solve for the volume of one mole of gas at STP:

Look familiar? This is the molar volume of a gas at STP. Work stoichiometry problems using your favorite
method, dimensional analysis, mole map, the table wayjust work FAST! Use the ideal gas law to convert
quantities that are NOT at STP.
Exercise 13
Gas Stoichiometry I
A sample of nitrogen gas has a volume of 1.75 L at STP. How many moles of N2 are present?

Gases

Exercise 14
Gas Stoichiometry II
Quicklime (CaO) is produced by the thermal decomposition of calcium carbonate (CaCO3). Calculate the
volume of CO2 at STP produced from the decomposition of 152 g CaCO3 by the reaction
CaCO3(s) CaO(s) + CO2(g)

Exercise 15
Gas Stoichiometry III
A sample of methane gas having a volume of 2.80 L at 25C and 1.65 atm was mixed with a sample of oxygen
gas having a volume of 35.0 L at 31C and 1.25 atm. The mixture was then ignited to form carbon dioxide and
water. Calculate the volume of CO2 formed at a pressure of 2.50 atm and a temperature of 125C.

Gases

THE DENSITY OF GASES

d = m = P(MM) {for ONE mole of gas}= MM

V
RT
22.4 L

AND

Molar Mass = MM = dRT

P

Molecular Mass kitty catall good cats put dirt [dRT] over their pee [P]. Corny? Yep! Crude and socially
unacceptable? You bet! But youll thank me later when youre flying through such gas law problems.
Just remember that densities of gases are reported in g/L NOT g/mL.
What is the approximate molar mass of air expressed in g/L?
List 3 gases that float in air:
List 3 gases that sink in air:
Exercise 16
Gas Density/Molar Mass
The density of a gas was measured at 1.50 atm and 27C and found to be 1.95 g/L. Calculate the molar mass of
the gas.

GAS MIXTURES AND PARTIAL PRESSURES

The pressure of a mixture of gases is the sum of the pressures of the different components of the
mixture:
Ptotal = P1 + P2 + . . . Pn
John Daltons Law of Partial Pressures also uses the concept of mole fraction,

A =
so now,

moles of A
.
moles A + moles B + moles C + . . .
PA = A Ptotal

The partial pressure of each gas in a mixture of gases in a container depends on the number of
moles of that gas. The total pressure is the SUM of the partial pressures and depends on the
total moles of gas particles present, no matter what they are!
Gases

10

Exercise 17
Daltons Law I
Mixtures of helium and oxygen are used in scuba diving tanks to help prevent the bends. For a particular dive,
46 L He at 25C and 1.0 atm and 12 L O2 at 25C and 1.0 atm were pumped into a tank with a volume of 5.0 L.
Calculate the partial pressure of each gas and the total pressure in the tank at 25C.

Exercise 18
Daltons Law II
The partial pressure of oxygen was observed to be 156 torr in air with a total atmospheric pressure of 743 torr.
Calculate the mole fraction of O2 present.

Exercise 19
Daltons Law III
The mole fraction of nitrogen in the air is 0.7808. Calculate the partial pressure of N2 in air when the
atmospheric pressure is 760. torr.

WATER DISPLACEMENT
It is common to collect a gas in the laboratory by water
displacement. The confounding factor is that some of the
pressure in the collection vessel is due to water vapor
collected as the gas was passing through!
You must correct for this in order to report the P of dry
gas.
How? You simply look up the partial pressure due to water
vapor at a given temperature and subtract that value from
the total pressure.
The experiment pictured is a classic! You may have done it
with Mg rather than zinc and used a eudiometer or inverted
and sealed buret to measure the volume of the gas collected
over water.
Gases

11

Exercise 20

Gas Collection over Water

A sample of solid potassium chlorate (KClO3) was heated

in a test tube (see the figure above) and decomposed by the
following reaction:
2 KClO3(s) 2 KCl(s) + 3 O2(g)
The oxygen produced was collected by displacement of
water at 22C at a total pressure of 754 torr. The volume
of the gas collected was 0.650 L, and the vapor pressure
of water at 22C is 21 torr. Calculate the partial pressure
of O2 in the gas collected and the mass of KClO3 in the
sample that was decomposed.

KINETIC MOLECULAR THEORY OF GASES

Assumptions of the MODEL:
1.
2.
3.
4.

All particles are in constant, random, motion.

All collisions between particles are perfectly elastic.
The volume of the particles in a gas is negligible
The average kinetic energy of the molecules is its Kelvin temperature.

This theory neglects any intermolecular forces as well. And it is important to note that gases expand to fill their
container, solids/liquids do not. And that gases are compressible; solids/liquids are not appreciably
compressible.

Gases

12

This helps explain Boyles Law:

If the volume is decreased that means that the gas particles will hit the
wall more often, thus increasing pressure
1
P = (nRT )
V
Constant
And also helps explain Charles Law
When a gas is heated, the speeds of its particles increase and thus hit
the walls more often and with more force. The only way to keep the P
constant is to increase the volume of the container.
nR
V = T
P

Constant
Yep, you guessed it! It also helps explain Gay-Lussacs Law
When the temperature of a gas increases, the speeds of its particles
increase, the particles are hitting the wall with greater force and greater
frequency. Since the volume remains the same this would result in
increased gas pressure.

nR
P = T
V
Constant
And it even helps explain Avogadros Law
An increase in the number of particles at the same temperature
would cause the pressure to increase if the volume were held
constant. The only way to keep constant P is to vary the V.

RT
V =
n
P
Constant
What about Daltons Law? The P exerted by a mixture of gases is the SUM of the partial pressures since gas
particles are acting independent of each other and the volumes of the individual particles DO NOT matter.

Gases

13

DISTRIBUTION OF MOLECULAR SPEEDS

Plot # of gas molecules having various speeds vs. the speed and you get a curve. Changing the temperature
affects the shape of the curve NOT the area beneath it. Change the # of molecules and all bets are off!
Maxwells equation:

3RT
MM
Use the energy R or 8.314510 J/K mol for this equation since kinetic energy is involved.
=
u 2 u=
rms

Exercise 21
Root Mean Square Velocity
Calculate the root mean square velocity for the atoms in a sample of helium gas at 25C.

If we could monitor the path of a single molecule it would be very erratic.

Mean free paththe average distance a particle travels between collisions.
Its on the order of a tenth of a micrometer. WAAAAY SMALL!
Examine the effect of temperature on the numbers of molecules with a given
velocity as it relates to temperature.
HEAT EM UP, SPEED EM UP!!
Drop a vertical line from the peak of each of the
three bell shaped curvesthat point on the x-axis
represents the AVERAGE velocity of the sample
at that temperature. Note how the bells are
squashed as the temperature increases. You
may see graphs like this on the AP exam where
you have to identify the highest temperature based
on the shape of the graph!

GRAHAMS LAW OF DIFFUSION AND EFFUSION

Effusion is closely related to diffusion. Diffusion is the term used to describe the
mixing of gases. The rate of diffusion is the rate of the mixing.
Effusion is the term used to describe the passage of a gas through a tiny orifice
into an evacuated chamber as shown on the right.
The rate of effusion measures the speed at which the gas is transferred into the
chamber.

Gases

14

The rates of effusion of two gases are inversely proportional to the square roots of their molar masses at the
same temperature and pressure.
Rate of effusion of gas 1
=
Rate of effusion of gas 2

MM 2
MM 1

REMEMBER rate is a change in a quantity over time, NOT just the time!
Exercise 22
Effusion Rates
Calculate the ratio of the effusion rates of hydrogen gas (H2) and uranium hexafluoride (UF6), a gas used in the
enrichment process to produce fuel for nuclear reactors.

Exercise 23
A pure sample of methane is found to effuse through a porous barrier in 1.50 minutes. Under the same
conditions, an equal number of molecules of an unknown gas effuses through the barrier in 4.73 minutes.
What is the molar mass of the unknown gas?

Diffusion
This is a classic! https://www.youtube.com/watch?v=GRcZNCA9DxE (animation) Effusion of a Gas:
http://www.youtube.com/watch?v=0uBK7VxT00E

https://www.youtube.com/watch?v=o7C4lo5n0zU (actual, but not great)

Distance traveled by NH3 = urmsfor NH3 =

Distance traveled by HCl
urms for HCl
Gases

MM HCl
=
MM NH3

36.5
= 1.5
17

15

The observed ratio is LESS than a 1.5 distance ratiowhy?

This diffusion is slow despite considering the molecular velocities are 450 and 660 meters per secondwhich
one is which?
This tube contains air and all those collisions slow the process down in the real world. Speaking of real
world.
REAL, thus NONIDEAL GASES
Most gases behave ideally until you reach high pressure and low temperature. (By the way, either of these can
cause a gas to liquefy, go figure!)
van der Waals Equation--corrects for negligible volume of molecules and accounts for inelastic collisions
leading to intermolecular forces (his real claim to fame).

[ P + a(

n 2
) ][V bn] = nRT
V

The coefficients a and b are van der Waals constants; no need to work problems, its the concepts that are
important! Notice pressure is increased (intermolecular forces lower real pressure, youre correcting for this)
and volume is decreased (corrects the container to a smaller free volume).
These graphs are classics and make great multiple choice questions on the AP exam.

When PV/nRT = 1.0, the gas is ideal

All of these are at 200K.
Note the Ps where the curves
cross the dashed line [ideality].

This graph is just for nitrogen gas.

Note that although nonideal behavior
is evident at each temperature, the
deviations are smaller at the higher Ts.

Dont underestimate the power of understanding these graphs. We love to ask question comparing the behavior
of ideal and real gases. Its not likely youll be asked an entire free-response gas problem on the real exam in
May. Gas Laws are tested extensively in the multiple choice since its easy to write questions involving them!
You will most likely see PV = nRT as one part of a problem in the free-response, just not a whole problem!
GO FORTH AND RACK UP THOSE MULTIPLE CHOICE POINTS!!

Gases

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And, just for fun:

Collapsing Can: http://www.graspr.com/videos/The-Collapsing-Can-1
Shall we try a bigger can? http://www.youtube.com/watch?v=Uy-SN5j1ogk&NR=1
How about the biggest can we can find? http://www.youtube.com/watch?v=E_hci9vrvfw
Boiling water with ice: http://www.youtube.com/watch?v=zzVtbvVS2lQ
Cooling gases with liquid nitrogen MIT: http://www.youtube.com/watch?v=ZvrJgGhnmJo
Getting a boiled egg into a bottle: http://www.youtube.com/watch?v=xZdfcRiDs8I&NR=1&feature=fvwp
Gravity has nothing to do with it! http://www.youtube.com/watch?v=BofIBaYk5e0&feature=related
Getting egg OUT of bottle! http://www.youtube.com/watch?v=x--4l-SL77Y&feature=related
Peeps in a vacuum: http://www.youtube.com/watch?v=lfNJJEdKgLU&NR=1
and another: http://www.youtube.com/watch?v=ciPr4Tg9k78&feature=related
Ideal Gas Law: http://www.youtube.com/watch?v=Mytvt0wlZK8&feature=related
Diffusion of ammonia and HCl (animation): http://www.youtube.com/watch?v=L41KhBPBymA&feature=related
Diffusion of ammonia and HCl (real deal): http://www.youtube.com/watch?v=WAJAslkwolk&feature=related
Putting it all together:
http://www.mhhe.com/physsci/chemistry/animations/chang_7e_esp/gam2s2_6.swf

Why R as in PV = nRT?
This is the kind of stuff that drives me crazy as well! I went in search of the answer some time
ago, so I'll share what I found:
As usual, the answer relates to a history lesson. It was Clausius in the mid 1800s that refined
the conversion factor for converting degrees Celsius to Kelvins (from adding 267 to adding 273
to the Celsius temperature. He did so using the careful experimental data of another French
scientist, Regnault.
Clausius also noted that Regnaults data indicated that the farther the temperature and pressure
conditions were from the condensation point of the gas, the more correctly the Ideal Gas Law
applies. So, there is speculation that the constant was assigned the letter R to honor
Regnaults work.
In the spirit of giving credit where credit is due, my source was a Journal of Chem. Ed article
written by William B. Jensen Department of Chemistry, University of Cincinnati, Cincinnati,
OH 45221-0172

Gases

17