Properties of Gases: Chemistry: The Molecular Nature of Matter, 6E

Chapter 11:
Properties of Gases
Chemistry: The Molecular Nature

of Matter, 6E
Jespersen/Brady/Hyslop
Properties of Common Gases
 Despite wide differences in chemical
properties, ALL gases more or less obey
the same set of physical properties.
Four Physical Properties of Gases
 Inter-related
1. Pressure (P)
2. Volume (V)
3. Temperature (T)
4. Amount = moles (n)
Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 2

Pressure, Its Measurement and Units
force
Pressure 
area
 Pressure is force per unit area
 Earth exerts gravitational force on everything
with mass near it
 Weight
 Measure of gravitational force that earth exerts
on objects with mass
 What we call weight is gravitational force
acting on object
Force vs. Pressure
 Consider a woman wearing flat shoes vs.
high "spike" heels
 Weight of woman is same = 120 lbs.
 Pressure on floor differs greatly
Shoe Area Pressure

Flat 10" x 3" 120 lbs
= 30 in2 P   4 Psi
30 in 2
Spike 0.4" x 0.4" 120 lbs

= 0.16 in2 P   750 Psi
0.16 in 2
Why airline stewardesses cannot wear spike heels!

Ways to Measure Pressure
 Atmospheric Pressure
 Resulting force per unit area
 When earth's gravity acts on molecules in air
 Pressure due to air molecules colliding with object
 Barometer
 Instrument used to measure atmospheric pressure
 Toricelli Barometer

Toricelli Barometer
 Simplest barometer
 Tube = 80 cm in
length
 Sealed at one end
 Filled w/ Hg
 In dish filled w/ Hg

Toricelli Barometer
 Air Pressure
 Pushes down on Hg
 Forces Hg up tube
 Weight of Hg in tube
 Pushes down on Hg in
dish
 When 2 forces balance
 Hg level stabilizes
 Read atmospheric
pressure

Toricelli Barometer
 A.P. high
 Pushes down on Hg in
dish
  level in tube
 A.P. low
 P on Hg in dish < P from
column
  level in tube
Result:
 Measure height of Hg in
tube
 Atmospheric pressure
Standard Atmospheric Pressure
 Typical range of P for most places where
people live
730 – 760 mm Hg
 Top of Mt. Everest A.P. = 250 mm Hg
Standard atmosphere (atm)
 Average pressure at sea level
 Pressure needed to support column of
mercury 760 mm high measures at 0oC

Units of Pressure
Pascal = Pa
 SI unit for Pressure
 Very small
 1atm  101,325 Pa = 101 kPa
 1atm  1.013 Bar = 1013 mBar
 1 atm too big for most lab work
1
1torr  atm 1 atm  760 mm Hg
760
At sea level 1 torr = 1 mm Hg
Manometers
 Used to measure P's inside closed reaction
vessels
 Pressure changes caused by gases produced
or used up during chemical reaction
 Open-end Manometer
 U tube partly filled with liquid (usually Hg)
 One arm open to atm
 One arm exposed to trapped gas in vessel

Open Ended Manometer
Pgas = Patm Pgas > Patm Pgas < Patm
 Gas pushes  Atm pushes
Hg up tube Hg down tube

Ex. 1 Using Open Ended Manometers
a. A student collected a gas in an
apparatus connected to an open-
end manometer. The mercury in
the column open to the air was
120 mm higher and the
atmospheric pressure was
measured to be 752 torr. What
was the pressure of the gas in
the apparatus?
 This is a case of Pgas > Patm

Pgas = 752 torr + 120 torr
= 872 torr
Ex. 1 Using Open Ended Manometers
b. In another experiment, it was
found that the mercury level in
the arm of the manometer
attached to the container of gas
was 200 mm higher than in the
arm open to the air. What was
the pressure of the gas?
 This is a case of Pgas < Patm

Pgas = 752 torr – 200 torr
= 552 torr

Closed-end Manometer
 Very convenient for measuring Pgas < 1 atm
 Arm farthest from vessel (gas) sealed
 Tube can be shorter
 Tube emptied of air under vacuum and Hg allowed in
 Then open system to atm and some Hg drains out
 No atm. P exists above Hg in sealed arm

Closed-end Manometer
 When gas sample
has P < 1 atm
 Hg in arm , as not
enough P to hold up
Hg.
 Patm = 0
  Pgas = PHg
 So directly read off P

Your Turn!
Gas pressure is measured using a close-ended
mercury manometer. The height of fluid in the
manometer is 23.7 in Hg. What is this
pressure in atm?
A. 23.7 atm
B. 0.792 atm
C. 602 atm
D. 1.61 atm
2.54cm 10mm 1atm
23.7inHg     0.792 atm
in cm 760mm
Using Liquids Other Than Mercury
in Manometers and Barometers
Problem:
 Hg has d = 13.6 g/mL
 So dense that little difference in P close to
1 atm
  Not very accurate when P ~1 atm
Solution:
 Go to less dense liquid
 Then differences in liquid levels 
  get more precision in P measurement
Comparison of Hg and H2O
 1 mm column of Hg
and 13.6 mm column
of water exert same
pressure
 Mercury is 13.6 times
more dense than
water
 Both columns have
same weight and
diameter, so they
exert same pressure d = 13.6 g/mL d = 1.00 g/mL
Using Liquids Other Than Mercury
in Manometers and Barometers
 For example: use H2O (d = 1.00 g/mL)
 P = 1 mm Hg
 Now 13.6 mm change with H2O
 Simple relationship exists between two
systems.
hA  d A
hB  d B  h A  d A
or hB 
db
 Use this relationship to convert pressure
change in mm H2O to pressure change in
mm Hg
Ex 2. Converting mm Acetone to
mm Hg
 Acetone has a density of 0.791 g/mL.
Acetone is used in an open-ended
manometer to measure a gas pressure
slightly greater than atmospheric
pressure, which is 756 mm Hg at the time
of the measurement. The liquid level is
20.4 mm higher in the open arm than in
the arm nearest the gas sample. What is
the gas pressure in torr?
Ex. 2 Solution
First convert mm acetone to mm Hg
20.4 mm  0.791 g / mL
hHg   1.19 mm Hg
13.6 g / mL
Then add PHg to Patm to get Ptotal
 Pgas = Patm + PHg

 = 756.0 torr + 1.19 torr
 Pgas = 757.2 torr
22
Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E
Boyle’s Law
 Studied relationship
between P and V
 Work done at
constant T as well as
constant number of
moles (n)
 T1 = T2
 As V , P 

Charles’s Law
 Charles worked on
relationship of how
V changes with T
 Kept P and n
constant
 Showed V  as T 

Gay-Lussac’s Law
 Worked on relationship between pressure and
temperature
 Volume (V) and number of moles (n) are constant
 P  as T 
 This is why we don’t heat canned foods on a
campfire without opening them!
 Showed that gas pressure
is directly proportional Low T, Low P
to absolute temperature
P
High T, High P
P T
T (K)
Combined Gas Law
PV
 Ratio
T
 Constant for fixed amount of gas (n)
PV
 C for fixed amount (moles)
T
 OR can equate 2 sets of conditions to
give combined gas law
P1V 1 P2V 2

T1 T2
Combined Gas Law
P1V1 P2V 2

T1 T2
 All T's must be in K
 Value of P and V can be any units as long
as they are the same on both sides
 Only equation you really need to remember
 Gives all relationships needed for fixed
amount of gas under two sets of conditions

How Other Laws Fit into Combined
Gas Law
P1V 1 P2V 2

T1 T2
Boyle’s Law T1 = T2 P1V1 = P2V2
Charles’ Law P1 = P2 V1 V 2

T1 T 2
Gay-Lussac’s V1 = V2 P1 P2

Law T1 T 2

Combined Gas Law P1 V1

P2 V2
T1 T2
Used for calculating effects of changing
conditions
 T in Kelvin
 P and V any units, as long as units cancel
 Ex. If a sample of air occupies 500. mL at
STP*, what is the volume at 85 °C and 560
torr? 760 torr  500. mL 560 torr  V2

273.15 K 358.15 K
890 mL
*Standard Temperature (273.15K) and Pressure
(1 atm) Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 29
Ex.3. Using Combined Gas Law
 What will be the final pressure of a sample
of nitrogen gas with a volume of 950 m3 at
745 torr and 25.0 °C if it is heated to 60.0
°C and given a final volume of 1150 m3?
 First, number of moles is constant even
though actual number is not given
 You are given V, P and T for initial state of
system as well as T and V for final state of
system and must find Pfinal
 This is a clear case for combined gas law
Ex. 3
 List what you know and what you don’t know
 Convert all Temperatures to Kelvin
 Then solve for unknown—here P2
P1 = 745 torr P2 = ?
V1 = 950 m3 V2 = 1150 m3
T1 = 25.0 °C + 273.15 T2 = 60.0 °C + 273.15
= 298.15 K
= 333.15 K
P1V1T 2 745torr  950m  333.15K 3
P2  
T 1V 2 298.15K  1150m 3
P2 = 688 torr
Ex. 4. Combined Gas Law
 Anesthetic gas is normally given to a patient
when the room temperature is 20.0 °C and
the patient's body temperature is 37.0°C.
What would this temperature change do to
1.60 L of gas if the pressure and mass stay
the same?
 What do we know?
 P and n are constant
V1 V 2
 So Combined Gas Law simplifies to 
T1 T2
Ex. 4
V1 = 1.60 L V2 = ?
T1 = 20.0 °C + 273.15 T2 = 37.0 °C + 273.15
= 293.15 K
= 310.15 K
 List what you know and what you don’t know
 Convert all Temperatures to Kelvin
 Then solve for unknown—here V2
V 1T 2 1.60L  310.15K
V2  
T1 293.15K
V2 = 1.69 L
Your Turn!
Which units must be used in all gas law
calculations?
A. K
B. Atm
C. L
D. no specific units as long as they cancel

Relationships between Gas Volumes
 In reactions in which products and reactants
are gases:
 If T and P are constant
 Simple relationship among volumes
 hydrogen + chlorine  hydrogen chloride
1 vol 1 vol 2 vol
 hydrogen + oxygen  water (gas)
2 vol 1 vol 2 vol
 ratios of simple, whole numbers

Avogadro’s Principle
 When measured at same T and P, equal V's
of gas contain equal number of moles
 Volume of a gas is directly proportional to its
number of moles, n
 V  n (at constant P and T)
H2 (g) + Cl2 (g)  2 HCl (g)
Coefficients 1 1 2
Volumes 1 1 2
Molecules 1 1 2 (Avogadro's Principle)
Moles 1 1 2
Standard Molar Volume
 Volume of 1 mole gas must be identical for
all gases under same P and T
 Standard Conditions of Temperature and
Pressure — STP
 STP = 1 atm and 273.15 K (0.0°C)
 Under these conditions
 1 mole gas occupies V = 22.4 L
 22.4 L  standard molar volume

Learning Check:
Calculate the volume of ammonia formed

by the reaction of 25L of hydrogen with
excess nitrogen.
N2 (g) + 3H2 (g)  2NH3 (g)
25 L H2 2 L NH3
  17 L NH3
1 3 L H2

Learning Check:
N2 (g) + 3H2 (g)  2NH3 (g)
If 125 L H2 react with 50L N2, what volume of

NH3 can be expected?
125 L H2 2 L NH3
  83.3 L NH3
1 3 L H2
50 L N2 2 L NH3
  100 L NH3
1 1 L N2
H2 is limiting reagent 83.3 L
Learning Check:
How many liters of N2 (g) at 1.00 atm and 25.0 °C
are produced by the decomposition of 150. g of
NaN3? 2NaN3 (s)  2Na (s) + 3N2 (g)
150.g NaN3 1 mol NaN3 3 mol N2
   3.461 mol N2
1 65.0099 g 2 mol NaN3
3.461 mol N2 22.4 L
  77.53 L
1 1 mol at STP
V1 V2 V1 T2
 ; V2 
T1 T2 T1
177.53 L  298.15 K
V2   84.62 L
273.15K
Your Turn!
How many liters of SO3 will be produced when
25 L of sulfur dioxide reacts with 75 L of
oxygen ? All gases are at STP.
2 L SO3
A. 25 L 25 L SO2 x  25 L SO3
2 L SO2
B. 50 L
2 L SO3
C. 100 L 75 L O2 x  150 L SO3
1 L O2
D. 150 L
E. 75 L

Ideal Gas Law
 With Combined Gas Law we saw that
PV
C
T
 With Avogadro’s results we see that this is
modified to PV
 n R
T
 Where R = a new constant = Universal
Gas constant
PV  nRT
Ideal Gas Law
PV = nRT
 Equation of state of a gas:
 If we know 3 of these variables, then we can
calculate 4th
 Can define state of the gas by defining 3 of
these values
Ideal Gas
 Hypothetical gas that obeys Ideal Gas Law
relationship over all ranges of T, V, n and P
 As T and P, real gases  ideal gases

What is the value of R?
 Plug in values of T, V, n and P for 1 mole
of gas at STP (1 atm and 0.0°C)
 T = 0.0°C = 273.15 K
 P = 1 atm
 V = 22.4 L
 n = 1 mol
PV 1atm  22.4L
R  
nT 1mol  273.15K
R = 0.082057 L·atm·mol1·K1
Learning Check: PV = nRT
How many liters of N2(g) at 1.00 atm and 25.0 °C
are produced by the decomposition of 150. g of
NaN3? 2NaN3(s)  2Na(s) + 3N2(g)
V=? P = 1 atm
T = 25C + 273.15 = 298.15 K
V = nRT/P
150.g NaN3 1 mol NaN3 3 mol N2
n  mol N2   
1 65.0099 g 2 mol NaN3
n = 3.461 mol N2
3.461mol N2  0.082057 Lmol
 atm  298.15K 
K
V 
1atm
V=84.62L
Ex. 5. Ideal Gas Law Problem
 What volume in milliliters does a sample of

nitrogen with a mass of 0.245 g occupy at
21°C and 750 torr?
 What do I know?
 Mass and identity (so molecular mass MM) of
substance – can find moles
 Temperature
 Pressure
 What do I need to find?
 Volume in mL
Ex. 5 Solution
V = ? (mL)
mass = 0.245 g MM = 214.0 = 28.0 g/mol
 Convert T from °C to K
T = 21°C + 273.15 K = 294 K
 Convert P from torr to atm
1atm
P  750torr   0.987atm
760torr
 Convert mass to moles
m 0.245g
n   8.75  10 3 mol
MM 28.0g / mol
Ex. 5 Solution
nRT
V
P
8.75  10 3 moles  0.082057L  atm  mol 1  K 1
 294K
V 
0.987atm
1000mL
V  0.214L  = 214 mL
1L

Your Turn!
Solid CaCO2 decomposes to solid CaO and CO2
when heated. What is the pressure, in atm, of
CO2 in a 50.0 L container at 35 oC when 75.0
g of calcium carbonate decomposes?
A. 0.043 atm
B. 0.010 atm
C. 0.38 atm
D. 0.08 atm
E. 38 atm
Your Turn! - Solution
1 mol CaCO3 1 mol CO2 L atm

75.0 g CaO2 x x x 0.0821 x 308 K
100.1 g 1 mol CaCO3 K mol
50.0 L
 0.38 atm

Determining Molecular Mass of Gas
If you know P, T, V and mass of gas
 Use Ideal Gas Law to determine moles (n)
of gas
 Then use mass and moles to get MM
If you know T, P, and Density (d) of a gas
 Use density to calculate volume and mass
of gas
 Use Ideal Gas Law to determine moles (n)
of gas
 Then use mass and moles to get MM

Ex. 6.
 The label on a cylinder of an inert gas
became illegible, so a student allowed
some of the gas to flow into a 300 mL gas
bulb until the pressure was 685 torr. The
sample now weighed 1.45 g; its
temperature was 27.0°C. What is the
molecular mass of this gas? Which of the
Group 0 gases (inert gases) was it?
 What do I know?
 V, mass, T and P
Ex. 6 Solution
1L
 V  300mL  1000mL  0.300L
 Mass = 1.45 g
 Convert T from °C to K.
 T = 27.0°C + 273.15 K = 300.2 K
1atm
P  685torr   0.901atm
760torr
 Use V, P, and T to calculate n
PV 0.901atm  0.300L
n   0.01098
RT 0.082057( atm  L / mol  K )  300.2K mole
Ex. 6 Solution (cont)
 Now use the mass of the sample and the

moles of the gas (n) to calculate the
molecular mass (MM)
mass 1.45g
MM    132 g/mol
n 0.01098mol
 Gas = Xe (At. Mass = 131.29 g/mol)

Ex. 7.
 A gaseous compound of phosphorus and
fluorine with an empirical formula of PF2
was found to have a density of 5.60 g/L at
23.0 °C and 750 torr. Calculate its
molecular mass and its molecular formula.
 Know
 Density
 Temperature
 Pressure

Ex. 7. Solution
 d = 5.60 g/L 1 L weighs 5.60 g

 So assume you have 1 L of gas
 V = 1.000 L
 Mass = 5.60 g
 Convert T from °C to K
 T = 23.0°C + 273.15 K = 296.2 K
1atm
P  750torr   0.9868atm
760torr
Ex. 7. Solution (cont)
PV 0.9868atm  1.000L
n  
RT 0.082057( atm  L / mol  K )  296.2K
0.04058 mole
 Use n and mass to calculate MM
mass 5.60g
MM    138 g/mol
n 0.04058mol

Ex. 7. Solution (cont)
 Now to find molecular formula given
empirical formula and MM
 First find mass of empirical formula unit
 1 P = 1  31g/mol = 31g/mol
 2 F = 2  19 g/mol = 38 g/mol
 Mass of PF2 = 69 g/mol
molecular mass 138g / mol
MM   2
empirical mass 69g / mol
 the correct molecular formula is P2F4
Which Gas Law to Use?
 Which Gas Law to Use in Calculations?
 If you know Ideal Gas Law, you can get all the rest
Amount of gas Amount of gas

given or asked remains constant
for in moles or g or not mentioned
Use Combined
Use Ideal Gas
Law
Gas Gas Law
Law P1V1 P2V2

PV  nRT Problems n1T1 n2T2
59
Your Turn!
7.52 g of a gas with an empirical formula of
NO2 occupies 2.0 L at a pressure of 1.0 atm
and 25 oC. Determine the molar mass and
molecular formula of the compound.
A. 45.0 g/mol, NO2

B. 90.0 g/mol, N2O4
C. 7.72 g/mol, NO
D. 0.0109 g/mol, N2O
E. Not enough data to determine molar mass
L atm
7.52 g x 0.0821 x 298 K
MW = K mol 90.0 g/mol
1.0 atm x 2.0 L
g 1 mol NO2 2 mol NO2

90 x =
mol 45.0 g mol
Molecular formula is N2O 4

Stoichiometry of Reactions
Between Gases
 Can use stoichiometric coefficients in
equations to relate volumes of gases
 Provided T and P are constant
 Volume  moles Vn
Ex. 8. Methane burns according to the
following equation.
CH4 (g) + 2 O2 (g)  CO2 (g) + 2 H2O
(g )
1 vol 2 vol 1 vol 2 vol

Ex. 8
 The combustion of 4.50 L of CH4 consumes
how many liters of O2? (Both volumes
measured at STP.)
 P and T are all constant so just look at
ratio of stoichiometric coefficients
2L O 2
Volume of O2  4.50L 
1L CH4
= 9.00 L O2

Ex. 9.
 In one lab, the gas collecting apparatus used
a gas bulb with a volume of 250 mL. How
many grams of Na2CO3 (s) would be needed
to prepare enough CO2 (g) to fill this bulb
when the pressure is at 738 torr and the
temperature is 23 °C? The equation is:
Na2CO3(s) + 2 HCl(aq)  2 NaCl(aq) + CO2(g) + H2O(l)

Ex. 9. Solution
 What do I know?
 T, P, V and MM of Na2CO3
 What do I need to find?
 grams Na2CO3
 How do I find this?
 Use Ideal Gas Law to calculate moles CO2
 Convert moles CO2 to moles Na2CO3
 Convert moles Na2CO3 to grams Na2CO3

1. Use Ideal Gas Law to calculate moles CO2
a. First convert mL to L
1L
V  250mL   0.250L
1000mL
b. Convert torr to atm
1atm
P  738torr   0.971atm
760torr
c. Convert °C to K
T = 23.0°C + 273.15 K = 296.2 K

1. Use Ideal Gas Law to calculate moles CO2
PV 0.971atm  0.250L
n 
RT 0.082057( atm  L / mol  K )  296.2K
= 9.989 x 103 mole CO2

2. Convert moles CO2 to moles Na2CO3
1mol Na 2CO 3
9.989  10 mol CO 2 
3
1mol CO 2
= 9.989 x 103 mol Na2CO3
3. Convert moles Na2CO3 to grams Na2CO3
3 106g Na 2CO 3
9.989  10 mol Na 2CO 3 
1mol Na 2CO 3
= 1.06 g Na2CO3

Your Turn!
2Na(s) + 2H2O(l ) → 2NaOH(aq) + H2(g )
How many grams of sodium are required to

produce 20.0 L of hydrogen gas at 25.0 C,
and 750 torr ?
A. 18.6 g
B. 57.0 g
C. 61.3 g
D. 9.62 g
E. 37.1 g
 Moles of H2 produced:
1 atm
750 torr x x 20.0 L
n= 760 torr = 0.807 mol H2
L atm
0.0821 x 298 K
K mol
 Grams of sodium required:
2 mol Na 23.0 g
g Na = 0.807 mol H2 x x = 37.1 g
mol H2 mol Na

Dalton's Law of Partial Pressure
 For mixture of non-reacting gases in
container
 Total pressure exerted is sum of the
individual partial pressures that each gas
would exert alone
 Ptotal = Pa + Pb + Pc + ···
 Where Pa, Pb, and Pc = partial pressures
 Partial pressure
 Pressure that particular gas would exert if it were
alone in container

Dalton’s Law of Partial Pressures
 Assuming each gas behaves ideally
 Partial pressure of each gas can be
calculated from Ideal Gas Law
n a RT n b RT nc RT
Pa  Pb  Pc 
V V V
 So Total Pressure is
Ptotal  Pa  Pb  Pc    
n a RT n b RT nc RT
    
V V V
 Rearranging
 RT 
Ptotal  ( n a  n b  n c    )  
V 
 Or
 RT 
Ptotal  ntotal  
V 
 Where ntotal = na + nb + nc + ···
ntotal = sum of # moles of various gases in
mixture

Means for Mixture of Ideal Gases
 Total number of moles of particles is important
 Not composition or identity of involved particles
 Pressure exerted by ideal gas not affected by
identity of gas particles
 Reveals 2 important facts about ideal gases
1. Volume of individual gas particles must be
important
2. Forces among particles must not be important
 If they were important, P would be dependent on identity
of gas

Ex. 10
 Mixtures of helium and oxygen are used in
scuba diving tanks to help prevent “the
bends.” For a particular dive, 46 L He at
25 °C and 1.0 atm and 12 L O2 at 25 °C
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 25 °C.

Ex. 10 Solution
 Have 2 sets of conditions

 Before and after being put into the tank
He O2
Pi = 1.0 atm Pf = PHe Pi = 1.0 atm Pf = PO2
Vi = 46 L Vf = 5.0 L Vi = 12 L Vf = 5.0 L

 First calculate pressure of each gas in 5 L
tank (Pf) using combined gas law
PiV i 1atm  46L
PHe    9.2atm
Vf 5L
PiV i 1atm  12L
PO 2    2.4atm
Vf 5L
 Then use these partial pressures to
calculate total pressure
Ptotal  PHe  PO 2  9.2atm  2.4atm  11.6atm

Your Turn!
250 mL of methane, CH4, at 35 oC and 0.55 atm
and 750 mL of propane, C3H8, at 35 oC and
1.5 atm, were introduced into a 10.0 L
container. What is the final pressure, in torr,
of the mixture?
A. 95.6 torr
B. 6.20 x 104 torr
C. 3.4 x 103 torr
D. 760 torr
E. 59.8 torr
0.55 atm x 0.250 L

P(CH4 )  = 0.0138 atm
10.0 L
1.5 atm x 0.750 L
P(C3H8 )  = 0.112 atm
10.0 L
760 torr
PT =  0.0138 + 0.112  atm x = 95.6 torr
atm

Mole Fractions and Mole Percents
Mole Fraction
 Ratio of number moles of given component
in mixture to total number moles in mixture
nA nA
XA  
n A  n B  nC      n Z ntotal
Mole Percent (mol%)
Mole %  X A  100

Mole Fractions of Gases from
Partial Pressures
V 
n A  PA  
 RT  V
 If V and T are constant then, RT =
constant
 For mixture of gases in one container
V 
PA  
 RT 
XA 
V  V  V  V 
PA    PB    PC        PZ  
 RT   RT   RT   RT 
Mole Fractions of Gases from
Partial Pressures
V
cancels, leaving
RT
PA
XA 
PA  PB  PC      PZ
or
PA nA
XA  
Ptotal ntotal

Ex. 11
 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
PA
 Use XA 
Ptotal
156torr
XO2   0.210
743torr
Partial Pressures and Mole
Fractions
 Partial pressure of particular component of
gaseous mixture
 Equals mole fraction of that component
times total pressure
PA  X A  Ptotal

Ex. 12
 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.
PN 2  X N 2  Ptotal
PN 2  0.7808  760torr  593torr

Your Turn!
250 mL of methane, CH4, at 35 oC and 0.55 atm
and 750 mL of propane, C3H8, at 35 oC and 1.5
atm were introduced into a 10.0 L container.
What is the mole fraction of methane in the
mixture?
A. 0.50
B. 0.11
C. 0.89
D. 0.25
E. 0.33
0.55 atm x 0.250 L

P(CH4 )  = 0.0138 atm
10.0 L
1.5 atm x 0.750 L
P(C 3H8 )  = 0.112 atm
10.0 L
0.0138 atm
X CH4 = = 0.110
(0.0138 + 0.112) atm

Collecting Gases over Water
 Application of Dalton’s Law of Partial Pressures
 Gases that don’t react with water can be trapped
over water
 Whenever gas is collected by displacement of water,
mixture of gases results
 Gas in bottle is mixture of water vapor and gas being
collected

Collecting Gases over Water
 Water vapor is present because molecules of water
escape from surface of liquid and collect in space
above liquid
 Molecules of water return to liquid
 When rate of escape = rate of return
 Number of water molecules in vapor state remains constant
 Gas saturated with water vapor = “Wet” gas

Vapor Pressure
 Pressure exerted by vapor present in
space above any liquid
 Constant at constant T
 When wet gas collected over water, we
usually want to know how much “dry” gas
this corresponds to
 Ptotal = Pgas + Pwater
 Rearranging
 Pgas = Ptotal – Pwater

Ex. 13
A sample of oxygen is collected over water
at 20.0 °C and a pressure of 738 torr. Its
volume is 310 mL. The vapor pressure of
water at 20°C is 17.54 torr.
a. What is the partial pressure of O2?
b. What would the volume be when dry at
STP?
a. PO2 = Ptotal – Pwater
= 738 torr – 17.5 torr = 720 torr

Ex. 13 Solution
b. Use the combined gas law to calculate PO2
at STP
P1 = 720 torr P2 = 760 torr
V1 = 310 mL V2 = ?
T1 = 20.0 + 273.12 = 293 K
T2 = 0.0 + 273 K = 273 K
P1V1 P2V 2 P1V1T 2
 V2 
T1 T2 T 1P2
720torr  310mL  273K
V2  V2 = 274 mL
293K  760torr
Your Turn!
An unknown gas was collected by water
displacement. The following data was
recorded: T = 27.0 oC; P = 750 torr; V = 37.5
mL; Gas mass = 0.0873 g; Pvap(H2O) = 26.98
torr
Determine the molecular weight of the gas.
A. 5.42 g/mol
B. 30.2 g/mol
C. 60.3 g/mol
D. 58.1 g/mol
E. 5.81 g/mol
L atm
0.0873 g x 0.0821 x 300 K
gRT K mol
MW  
PV (750 - 26.98)torr x 0.0375 L
MW  60.3 g/mol

Diffusion
 Complete
spreading out
and
intermingling of
molecules of one
gas into and
among those of
another gas
 Ex. Perfume in
room

Effusion
 Movement of gas
molecules
 Through extremely
small opening into
vacuum
Vacuum
 No other gases
present in other half

Thomas Graham
 Studied relationship between effusion rates
and molecular masses for series of gases
 Wanted to minimize collisions
 Slow molecules down
 Make molecules bump aside or move to rear

Graham's Law of Effusion
 Rates of effusion of gases are inversely
proportional to square roots of their
densities, d, when compared at identical
pressures and temperatures
1
Effusion Rate  (constant P and T)
d
Effusion Rate  d  k (constant P and T)
k is virtually identical for all gases

Effusion Rate (A)  d A  Effusion Rate (B)  d B  k
 Rearranging
Effusion Rate ( A ) dB dB
 
Effusion Rate (B ) dA dA
 Finally, dA  MM (constant V and n)
Effusion Rate ( A ) dB MB
 
Effusion Rate (B ) dA MA
 Result: Rate of effusion is inversely
proportional to molecular mass of gas
Effusion Rate  MM  k (constant P and T)

Effusion Rate  MM  k
 Heavier gases effuse more slowly
 Lighter gases effuse more rapidly
Ex.14. 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.

Ex.14. Solution
 First must compute MM's

 MM (H2) = 2.016 g/mol
 MM (UF6) = 352.02 g/mol
Effusion Rate (H2 ) M UF6 352.02

   13.2
Effusion Rate (UF6 ) MH2 2.016
 Thus the very light H2 molecules effuse
~13 times as fast as the massive UF6
molecules.
Your Turn!
If it takes methane 3.0 minutes to diffuse 10.0
m, how long will it take sulfur dioxide to travel
the same distance ?
A. 1.5 min
B. 12.0 min
C. 1.3 min
D. 0.75 min
E. 6.0 min

Remember, velocity and time are inversely related.

t1 MW1

t2 MW 2
3.0 min 16.04 g/mol

t2 64.06 g/mol
t 2  6.0 min

Ex.15.
 For the series of gases He, Ne, Ar, H2, and
O2 what is the order of increasing rate of
effusion?
substance He Ne Ar H2 O2
MM 4 20 40 2 32
 Lightest are fastest

 So H2 > He > Ne > O2 >Ar

Kinetic Theory and Gas Laws
 So far, considered gases from experimental
point of view
 At P < 1 atm, most gases approach ideal
 Ideal gas law predicts behavior
 Does NOT explain it
 Recall scientific method
 Law is generalization of many observations
 Laws allow us to predict behavior
 Don't explain WHY

Kinetic Theory and the Gas Law
 To answer WHY it happens—must construct
Theory or Model
 Models consist of speculations about what
individual atoms or molecules might be doing to
cause observed behavior of macroscopic system
(large number of atoms/molecules)
 For model to be successful:
 Must explain observed behavior in question
 Predict correctly results of future experiments

Kinetic Theory and the Gas Law
 Model can never be proved absolutely true
 Approximation by its very nature
 Bound to fail at some point
 One example of model is kinetic theory of
gases
 Attempts to explain properties of ideal gases.
 Speculates on behavior of individual gas
particles

Postulates of Kinetic Theory of Gases
1. Particles are so small compared with
distances between them, so volume of
individual particles can be assumed to be
negligible.
 Vgas ~ 0
2. Particles are in constant motion

 Collisions of particles with walls of container
are cause of pressure exerted by gas
 number collisions  Pgas

3. Particles are assumed to exert no force on
each other
 Assumed neither to attract nor to repel
each other
4. Average kinetic energy of collection of gas
particles is assumed to be directly
proportional to Kelvin Temperature
 KEavg  TK

Kinetic Theory of Gases
 Kinetic theory of matter and heat transfer (ch
7)
 Heat  PV  KEave
 But for constant # moles of ideal gas
 PV = nRT
 where nR is proportionality constant
 This means T  KEave
 Specifically 3
KEave  RT
2
 As increase T,  KEave,
  number collisions with walls, thereby increasing P
Real Gases
 Don’t conform to these assumptions
 Have finite volumes
 Do exert forces on each other
 However, KTG does explain Ideal Gas
behavior
 True test of model is how well its predictions
fit experimental observations

 Picture ideal gas consisting of particles

having no volume and no attractions for
each other
 Assumes that gas produces pressure on its
container by collisions with walls

Kinetic Theory Explains Gas Laws
P and V (Boyle's Law)
 For given sample of ideal gas at given T (n and T constant)
 If V , P 
By KT Gases
1
  V, means gas particles
P  (nRT )
hit wall more often
 P V

P and T (Gay-Lussac's Law)
 For given sample of
ideal gas at constant
V (n and V
constant)
 P is directly
proportional to T
 nR 
P T
 V 

P and T (Gay-Lussac's Law)
KT Gases accounts for this
 As T 
 KEave 
 Speeds of molecules 
 Gas particles hit wall
more often as V same
 So  P

T and V (Charles' Law)
 For given sample of
ideal gas at constant
P (n and P constant)
 V is directly
proportional to T
 nR 
V  T
 P 

T and V (Charles' Law)
KT Gases account for
this
 As T 
 KEave 
 Speeds of
molecules 
 Gas particles hit wall
more often as P
same
 So  V
V and n (Avogadro's Principle)
 For ideal gas at constant T and P
 V is directly proportional to n
 RT 
V  n
 P 
 KT Gases account for this
 As  n (number gas particles), at same T
 Since P constant
 Must  V

Dalton's Theory of Partial Pressures
Ptotal   Pindividual gases
 Expected from Kinetic Theory of Gases
 All gas particles are independent of each other
 Volume of individual particles is unimportant
  Identities of gases do not matter
 Conversely, can think of Dalton's Law of Partial
Pressures as evidence for KTG
 Gas particles move in straight lines, neither
attracting nor repelling each other
 Particles act independently
 Only way for Dalton's Law to be valid
Law of Effusion (Graham's Law)
Effusion Rate (A) MB

Effusion Rate (B) MA
 Key conditions:
 Comparing 2 gases at same P and T
 Conditions where gases don't hinder each other
 Hence, particles of 2 gases have same KEave
KE 1  KE 2
 Let v 2 = average of velocity squared of
molecules of gases
 Then 1 1
2
m v
1 1
2
 2
m v
2 2
2

Law of Effusion (Graham's Law)
v 12 m1
 Rearranging 
v 22 m2
v1 m1
 Taking square root of both sides 
v2 m2
 Since m1  M 1 v m1 M1
1
 
v2 m2 M2
 Now Rate of Effusion  v
 So Effusion Rate = k v
Effusion Rate of Gas 1 M2

Effusion Rate of Gas 2 M1
Absolute Zero
1
T  KE ave  m( v )
2
 If KEave = 0, then T must = 0.

 Only way for KEave = 0, is if v = 0 since m
 0.
 When gas molecules stop moving, then
gas as cold as it can get = Absolute Zero

Real Gases: Deviations from Ideal
Gas Law
PV
 Combined Gas Law  constant
T
 Ideal Gas Law PV
R
nT
 Real Gases deviate Why?

Real Gases Deviate from Ideal Gas
Law
1. Gas molecules
have finite V's
  Take up space
 Less space of
kinetic motions
 Vmotions < Vcontainer
  particles hit walls
of container more
often
  P over ideal
Real Gases
2. Particles DO attract each other
 Even weak attractions means they hit walls of
container less often
   P over ideal gas

Effect of Attractive Forces on Real
Gas

van der Waal's equation for Real
Gases
 n a
2
 P  2   V  nb   nRT
 V 
corrected P corrected V
 a and b are van der Waal's constants

 Obtained by measuring P, V, and T for
real gases over wide range of conditions

Gases
 n a
2
 P  2   V  nb   nRT
 V 
corrected P
 a — Pressure correction
 Indicates some attractions between molecules
 Large a
 Means strong attractive forces between
molecules
 Small a
 Means weak attractive forces between molecules
Gases
 n a
2
 P  2   V  nb   nRT
 V 
corrected V
 b — Volume correction
 Deals with sizes of molecules
 Large b
 Means large molecules
 Small b
 Means small molecules
 Gases that are most easily liquefied have largest van
der Waal's constants

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Chapter 11:

Chemistry: The Molecular Nature

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 2

Shoe Area Pressure

Spike 0.4" x 0.4" 120 lbs

Why airline stewardesses cannot wear spike heels!

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 5

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 6

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 7

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Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 11

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 12

 This is a case of Pgas > Patm

 This is a case of Pgas < Patm

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 14

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 15

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 16

 Pgas = Patm + PHg

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 23

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 24

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 27

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 28

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 34

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 35

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 37

Calculate the volume of ammonia formed

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 38

If 125 L H2 react with 50L N2, what volume of

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 41

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 43

 What volume in milliliters does a sample of

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 48

1 mol CaCO3 1 mol CO2 L atm

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 50

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 51

 Now use the mass of the sample and the

 Gas = Xe (At. Mass = 131.29 g/mol)

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 54

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 55

 d = 5.60 g/L 1 L weighs 5.60 g

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 57

Amount of gas Amount of gas

A. 45.0 g/mol, NO2

g 1 mol NO2 2 mol NO2

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 61

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 62

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 63

Na2CO3(s) + 2 HCl(aq)  2 NaCl(aq) + CO2(g) + H2O(l)

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 64

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 65

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 66

= 9.989 x 103 mole CO2

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 68

How many grams of sodium are required to

 Grams of sodium required:

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 70

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 71

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 73

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 74